CN114315496A - Preparation method of alkane compound, catalyst and application thereof - Google Patents
Preparation method of alkane compound, catalyst and application thereof Download PDFInfo
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- CN114315496A CN114315496A CN202110617424.2A CN202110617424A CN114315496A CN 114315496 A CN114315496 A CN 114315496A CN 202110617424 A CN202110617424 A CN 202110617424A CN 114315496 A CN114315496 A CN 114315496A
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- -1 alkane compound Chemical class 0.000 title claims abstract description 105
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 44
- 238000010438 heat treatment Methods 0.000 claims description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 25
- 229910006069 SO3H Inorganic materials 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 229940117975 chromium trioxide Drugs 0.000 claims description 11
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 11
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims description 11
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- WEEGYLXZBRQIMU-UHFFFAOYSA-N Eucalyptol Chemical compound C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- JARIJYUQOKFVAJ-UHFFFAOYSA-M sodium;4-carboxy-2-sulfobenzoate Chemical compound [Na+].OC(=O)C1=CC=C(C([O-])=O)C(S(O)(=O)=O)=C1 JARIJYUQOKFVAJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 3
- RPNNPZHFJPXFQS-UHFFFAOYSA-N methane;rhodium Chemical compound C.[Rh] RPNNPZHFJPXFQS-UHFFFAOYSA-N 0.000 claims description 3
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 125000002950 monocyclic group Chemical group 0.000 claims description 2
- 125000003003 spiro group Chemical group 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 2
- 150000004292 cyclic ethers Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 5
- 239000011949 solid catalyst Substances 0.000 description 5
- HSYCPONOCCYPEY-UHFFFAOYSA-N 6-pentylundecane Chemical compound CCCCCC(CCCCC)CCCCC HSYCPONOCCYPEY-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001144 powder X-ray diffraction data Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- RFFOTVCVTJUTAD-AOOOYVTPSA-N 1,4-cineole Chemical compound CC(C)[C@]12CC[C@](C)(CC1)O2 RFFOTVCVTJUTAD-AOOOYVTPSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- KJERPKPRIWFPGO-UHFFFAOYSA-N sodium;2-sulfoterephthalic acid Chemical compound [Na].OC(=O)C1=CC=C(C(O)=O)C(S(O)(=O)=O)=C1 KJERPKPRIWFPGO-UHFFFAOYSA-N 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 2
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ICMAFTSLXCXHRK-UHFFFAOYSA-N Ethyl pentanoate Chemical compound CCCCC(=O)OCC ICMAFTSLXCXHRK-UHFFFAOYSA-N 0.000 description 1
- 239000013177 MIL-101 Substances 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- JXASPPWQHFOWPL-UHFFFAOYSA-N Tamarixin Natural products C1=C(O)C(OC)=CC=C1C1=C(OC2C(C(O)C(O)C(CO)O2)O)C(=O)C2=C(O)C=C(O)C=C2O1 JXASPPWQHFOWPL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 1
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000013087 chromium-based metal-organic framework Substances 0.000 description 1
- RFFOTVCVTJUTAD-UHFFFAOYSA-N cineole Natural products C1CC2(C)CCC1(C(C)C)O2 RFFOTVCVTJUTAD-UHFFFAOYSA-N 0.000 description 1
- 229960005233 cineole Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000000686 lactone group Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- DJYPJBAHKUBLSS-UHFFFAOYSA-M sodium;hydron;terephthalate Chemical compound [Na+].OC(=O)C1=CC=C(C([O-])=O)C=C1 DJYPJBAHKUBLSS-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of an alkane compound, a catalyst and application thereof. Wherein the preparation method of the alkane compound comprises the steps of mixing the compound containing cyclic ether and MIL-101-SO3Mixture of H and a carbon-containing noble metal catalyst in H2And (4) carrying out the next reaction. The hydrodeoxygenation reaction yield and selectivity of the cyclic ether compound are high, the catalyst can be directly recovered, and the catalyst has good recycling performance.
Description
Technical Field
The invention relates to a preparation method of an alkane compound, a catalyst and application thereof.
Background
Hydrodeoxygenation (HDO) is a series reaction of C — O bond breaking and C ═ C bond hydrogenation, and is generally obtained by the concerted catalysis of acids and transition metals.
The method reported in the literature generally comprises the steps of loading transition metals (Pd, Pt, Ni and the like) on a solid acid catalyst, and synthesizing a bifunctional catalyst simultaneously provided with an acid site and a catalytic hydrogenation site. However, the structure-activity relationship between two catalytic sites of the bifunctional catalyst is complex, the quantity and proportion of the load are not easy to control, the synthesis and characterization difficulty is high, and the intermediates and products are easy to isomerize in the reaction process.
In order to solve this problem, the prior art has conducted specific studies on catalysts. Heterogeneous bifunctional catalysts MIL-101-SO are disclosed, for example, in Zhang, D, Ye, F, Guan, Y, Wang, Y, Hensen, E.J.M., Hydrogenation of gamma-valectone in ethanol over Pd nanoparticles supported on sulfonic acid functionalized MIL-101, RSC adv.2014,4(74),39558-3H can be used together with monofunctional Pd/C to catalyze the HDO reaction of esters, and gamma-valerolactone can be converted into ethyl valerate, but the defects of low yield, more side reactions, poor selectivity, obvious reduction of cyclic reaction yield and the like exist. As another example, Liu, D. -H, Marks, T.J, Li, Z., Catalytic One-Point Conversion of Renewable Platform Chemicals to Hydrocarbon and Ether Biofuels via Tandem Hf (OTf)4The combination of a "homogeneous catalyst and a heterogeneous catalyst" is disclosed in + Pd/C catalysis, chemsuschem,2019,12(24),5217-5223 for hydrodeoxygenation reaction, but it has the disadvantages of difficult recovery of the homogeneous catalyst and insufficient selectivity.
Disclosure of Invention
The invention provides a preparation method of an alkane compound, a catalyst and application thereof, aiming at overcoming the defects that an intermediate and a product can generate isomerization, more side reactions, low yield, poor selectivity and the like in the reaction process of a hydrodeoxygenation reaction in the prior art. The hydrodeoxygenation reaction yield and selectivity of the cyclic ether compound are high, the catalyst can be directly recovered, and the catalyst has good recycling performance.
The invention solves the technical problems through the following technical scheme.
The invention provides a method for combining alkaneThe preparation method of the compound comprises the steps of mixing the compound containing cyclic ether compounds and MIL-101-SO3Mixture of H and a carbon-containing noble metal catalyst in H2And (4) carrying out the next reaction.
In the invention, the alkane compound is prepared by carrying out hydrodeoxygenation reaction on the cyclic ether compound.
In the present invention, the cyclic ether compound may be a cyclic ether compound that is conventional in the art, and is generally classified into one or more of a saturated cyclic ether compound, an unsaturated cyclic ether compound, and an oxa-aromatic compound. The saturated cyclic ether compound and the unsaturated cyclic ether compound can be monocyclic, spiro, bridged or parallel (the cyclic ether compound refers to an oxygen heterocyclic hydrocarbon compound without a lactone group).
Preferably, the cyclic ether compound is
1, 8-cineole,
Wherein R is independently H or alkyl with 1-6 carbon atoms; r1Is an alkyl group having 1 to 6 carbon atoms or
R3Is H, an alkyl group having 1 to 6 carbon atoms, or
R4Is a bond or an alkylene group having 1 to 6 carbon atoms.
More preferably, the cyclic ether compound is
Wherein, preferably, the alkane compound is
Wherein R is H or alkyl with 1-6 carbon atoms, R2Is an alkyl group having 1 to 16 carbon atoms.
In one embodiment of the present invention, the cyclic ether compound is
Or 1, 8-cineole, the alkane compound is
In one embodiment of the present invention, the cyclic ether compound is
The alkane compound is
In one embodiment of the present invention, the cyclic ether compound is
The alkane compound is
In one embodiment of the present invention, the cyclic ether compound is
The alkane compoundThe object is
In the invention, the MIL-101-SO3H may be MIL-101-SO conventional in the art3H, namely MIL-101-SO3H (100), which is commercially available. The MIL-101-SO3H is derived by ligand replacement of a chromium-based metal organic framework material MIL-101-Cr which is thermally stable, acid stable, high in porosity and strong in water absorption, and has good thermal stability and strong acidity.
Wherein, preferably, the MIL-101-SO3The preparation method of H comprises the following steps: sequentially heating and reacting 2-sulfoterephthalic acid monosodium salt, chromium trioxide, water and hydrochloric acid solution, acidifying, drying and activating.
Preferably, the molar ratio of the 2-sulfonic acid terephthalic acid monosodium salt to the chromium trioxide is 1: 1.
Preferably, the monosodium 2-sulfonate terephthalate salt and the chromium trioxide are dissolved in water, for example, ultrasonically, prior to the heating reaction. More preferably, the monosodium 2-sulfonate terephthalate salt and the chromium trioxide are dissolved in water separately, filtered and mixed. MIL-101-SO prepared by the preparation method3The H crystal form is good, and the crystal size is uniform.
Preferably, the temperature of the heating reaction is 180 ℃.
Preferably, the heating reaction time is 6 days.
Preferably, the acidification is carried out by subjecting the product obtained by the heating reaction to a mixed solution of methanol, water and hydrochloric acid.
Preferably, the drying is vacuum drying.
Preferably, the activation is performed at 120 ℃ under vacuum.
In the present invention, the carbon-containing noble metal catalyst may be a carbon-containing noble metal catalyst that is conventional in the art.
Wherein, the carbon-containing noble metal catalyst is preferably one or more of rhodium carbon, palladium carbon, platinum carbon and ruthenium carbon.
Among them, the mass percentage of the noble metal in the carbon-containing noble metal catalyst is preferably 0.1% to 30%, for example, 5% or 10%.
In the invention, preferably, the MIL-101-SO3H accounts for 0.2-2.5% of the mole percentage of ether bonds in the cyclic ether compound, for example, 0.5% or 1%.
In the present invention, the metal in the carbon-containing noble metal catalyst preferably accounts for 0.2 to 4 mol%, for example, 0.4% or 0.8 mol%, of the ether bond in the cyclic ether compound.
In the present invention, the reaction temperature is preferably 70 to 240 ℃.
Wherein, preferably, when the cyclic ether compound is an unsaturated cyclic ether compound, the reaction is heating in stages, the first stage heating temperature is 70-80 ℃, and the second stage heating temperature is 120-240 ℃, for example, 200 ℃.
Preferably, the first heating period is 3-10 hours.
Preferably, the time for the second stage heating is 3 to 20 hours, for example, 10 hours.
Wherein, preferably, when the cyclic ether compound is a saturated cyclic ether compound, the reaction temperature is 200-240 ℃.
Said H2The pressure of (a) may be a pressure conventional in such reactions in the art; in the present invention, the pressure is preferably 30 to 40 bar.
In one aspect of the present invention, when the cyclic ether compound is an oxaaromatic compound, or when the number of ether bonds is 3 or more, or when the boiling point of the mixture is 150 ℃ or less, the mixture further contains cyclohexane, and the ratio of the amount of the cyclic ether compound to the amount of the cyclohexane is (0.2 to 10 mmol): 10mL, for example 1 mmol: 10 mL.
In the invention, preferably, when the cyclic ether compound is a saturated cyclic ether compound, the reaction time is 3-10 hours.
In the present invention, preferably, the alkane is a compound of the alkane familyThe preparation method of the compound also comprises a post-treatment step, wherein the post-treatment step is filtration and separation to obtain the MIL-101-SO3H and carbonaceous noble metal catalyst solids, and said paraffinic compounds; the MIL-101-SO3The H and the carbon-containing noble metal catalyst solid can be repeatedly used for preparing the alkane compound.
The invention provides a hydrodeoxygenation reaction method of a cyclic ether compound, which comprises the following steps:
mixing with cyclic ether compound and MIL-101-SO3Mixture of H and a carbon-containing noble metal catalyst in H2And (4) carrying out the next reaction.
In the invention, preferably, the cyclic ether compound and MIL-101-SO3Preferred embodiments of H and the carbonaceous noble metal catalyst, reaction conditions, operating parameters may be as described previously.
The invention also provides a catalyst for hydrodeoxygenation reaction, which comprises MIL-101-SO3H and a carbon-containing noble metal catalyst, the MIL-101-SO3The molar ratio of H to the metal in the carbon-containing noble metal catalyst is 0.625-5.
Wherein, the carbon-containing noble metal catalyst is preferably one or more of rhodium carbon, palladium carbon, platinum carbon and ruthenium carbon.
The invention also provides the application of the catalyst for hydrodeoxygenation reaction.
Wherein, the hydrodeoxygenation reaction is preferably the hydrodeoxygenation reaction method of the cyclic ether compound.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
the catalyst combination has very excellent promotion effect on HDO reaction of cyclic ether compounds, can obtain saturated alkane with very high yield, high purity and high selectivity, and can be recycled for multiple times to maintain the catalytic effect. And because the catalytic sites of the two heterogeneous catalysts are separated, the isomerization of the intermediate and the product in the reaction process is avoided, the accurate serial hydrogenation-hydrodeoxygenation reaction can be repeatedly realized, and finally, the only target product is obtained, and the selectivity is high. The invention can realize high-efficiency and high-selectivity conversion under the condition of no solvent, is simple and convenient to operate and can be used for large-scale production.
Drawings
FIG. 1 shows MIL-101-SO obtained by the preparation3SEM image of H.
FIG. 2 shows MIL-101-SO obtained by the preparation3H PXRD pattern.
FIG. 3 is a graph showing the comparison of the productivity of the catalyst cycle performance test (7 times).
FIG. 4 shows MIL-101-SO after the hydrodeoxygenation reaction of example 4.2 was completed3H PXRD pattern.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples, PXRD (powder X-Ray differentiation) data were obtained from Bruker D8 ADVANCE test.
SEM images were obtained from JSM-7800F Prime test by JEOL.
In the following examples, MIL-101-SO3The preparation method comprises the following steps:
respectively weighing the monosodium 2-sulfoterephthalic acid and the chromium trioxide in equal amount in a bottle, and respectively adding deionized water for ultrasonic dissolution to obtain aqueous solutions of the monosodium 2-sulfoterephthalic acid and the chromium trioxide. Filtering the above two solutions with needle filter (0.22 μm, nylon) in the same container, adding hydrochloric acid, filtering the above solution with needle filter to autoclave liner, placing into a kettle, placing into 180 deg.C oven for reaction for 6 days, setting the oven temperature to room temperature, cooling to 120 deg.C, taking out the kettle, and cooling to room temperature. The obtained greenCleaning the toner powder product with deionized water, N-dimethylformamide and methanol, dispersing the toner powder product in a mixed solvent of methanol and deionized water, adding hydrochloric acid for overnight acidification, cleaning with deionized water, vacuum drying, and vacuum activating at 120 deg.C to obtain MIL-101-SO3H。
FIGS. 1 and 2 are the MIL-101-SO obtained, respectively3SEM and PXRD patterns for H measurements. MIL-101-SO prepared by the preparation method3The H crystal form is good, and the crystal size is uniform.
Example 1
TABLE 1 combination of HDO catalysts of examples 1-3 and yield comparison
| Examples | Solid acid | Hydrogenation catalyst | Yield/%) |
| 1 | MIL-101-SO3H | Pd/C(10wt％) | 96 |
| 2 | MIL-101-SO3H | Pt/C(5wt％) | 92 |
| 3 | MIL-101-SO3H | Ru/C(5wt％) | 93 |
The reaction conditions for example 1 were: mixing 1, 4-cineole (1a) (154mg, 1.0mmol), MIL-101-SO3H (9mg, 1 mol% calculated as ether bond in 1a) and Pd/C (10 wt% Pd/C, 2.2mg, 0.2 mol% calculated as ether bond in 1a) were charged into a 10mL reaction vessel, and H was used2After 3 gas replacements, 30bar of H were refilled2After sealing, the reaction was stirred at 120 ℃ for 3 hours to give the product (DF 1). After the reaction, the solid catalyst and the liquid product are separated by a simple filtration operation. The yield was determined by GC-FID of the reaction mixture and calibrated by n-undecane.
Wherein, after the first reaction is finished, liquid is extracted by a reduced pressure distillation mode, collected, weighed and the yield is calculated. The remaining solid catalyst was directly used in the next experiment for a total of 7 reactions, and the yield was shown in FIG. 3.
Example 2
The same process conditions as in example 1 were used except that the catalysts were different as shown in Table 1 (Pt/C for example 2, Pt in 5 wt% based on Pt/C), to obtain the product (DF 1).
Example 3
The same process conditions as in example 1 were used except that the catalysts were different as shown in Table 1 (Ru/C for example 3, 5 wt% of Ru based on the mass of Ru/C), to obtain the product (DF 1).
From comparison of examples 1 to 3, it is found that MIL-101-SO3The combination of H and common carbon-containing noble metal catalysts (Pd/C, Pt/C and Ru/C) can obtain good catalytic effect.
Example 4.1
The reaction conditions for example 4.1 are:FP2 compound (96mg, 1.0mmol) shown in Table 2, MIL-101-SO3H (4.5mg, 0.5 mol% calculated as ether bond in FP 2) and Pd/C (10 wt% Pd/C, 8.5mg, 0.8 mol% calculated as ether bond in FP 2) were charged into a 10mL autoclave, and H was used2After 3 times of gas replacement, 40bar of H was again charged2After sealing, the reaction was stirred at 80 ℃ for 3 hours, after which the temperature was raised to 200 ℃ and the reaction was stirred for 10 hours. After the reaction, the solid catalyst and the liquid product are separated by a simple filtration operation. The yields were determined by GC-FID of the reaction mixture and were normalized by n-hexadecane and 6-pentylundecane standards.
Example 4.2
The reaction conditions for example 4.2 are: FP2 compound (961mg, 10mmol) shown in Table 2, MIL-101-SO3H (181mg, 2 mol% calculated on ether bond in FP 2) and Pd/C (10 wt% Pd/C, 42.4mg, 0.4 mol% calculated on ether bond in FP 2) were added to 10mL cyclohexane, the mixture was charged into a 20mL autoclave, gas was replaced 3 times, and then 40bar of H was charged2After sealing, the reaction was stirred at 80 ℃ for 3 hours, after which the temperature was raised to 200 ℃ and the reaction was stirred for another 20 hours. After the reaction is completed, the solid catalyst and the liquid product are separated by simple filtration and elution operations. The yield was determined by NMR of the reaction mixture and was calibrated by tetrachloroethane standards.
In example 4.2, after the reaction was complete, the product was washed with deuterated chloroform and tested for PXRD after drying in air at room temperature, as shown in FIG. 4, MIL-101-SO in catalyst3The H crystalline state is intact.
TABLE 2 comparison of yield and purity of cyclic ether compound starting materials and products obtained in examples 4-15
Note: "Bu" represents a butyl group and "Pen" represents a pentyl group; "/" indicates not tested.
Example 5
The reaction conditions for example 5 were: FP3 compound (32mg, 0.2mmol) as shown in Table 2, MIL-101-SO3H (9mg, 2.5 mol% in terms of ether bond in FP 3), Pd/C (5 wt% Pd/C, 17mg, 4.0 mol% in terms of ether bond in FP 3) and 1mL of n-hexane were charged in a 10mL autoclave, and H was used2After 3 times of gas replacement, 40bar of H was again charged2After sealing, the reaction was stirred at 80 ℃ for 3 hours, after which the temperature was raised to 200 ℃ and the reaction was stirred for 10 hours. After the reaction, the solid catalyst and the liquid product are separated by a simple filtration operation. The yields were determined by GC-FID of the reaction mixture and were normalized by n-hexadecane and 6-pentylundecane standards.
Examples 6 to 9 and 11
The product was obtained under the same process conditions as in example 4.1, except that the cyclic ether compounds shown in Table 2 were different.
Wherein the reactants are all 1mmol cyclic ether compounds, MIL-101-SO3H (0.5 mol% calculated as ether bond in FP), Pd/C (10 wt% Pd/C, 0.8 mol% calculated as ether bond in FP). The yields were determined by GC-FID of the reaction mixture and were normalized by n-hexadecane and 6-pentylundecane standards.
Examples 10, 12 to 15
The product was obtained under the same process conditions as in example 4, except that the cyclic ether compounds shown in Table 2 were different.
Wherein the reactants are all 1mmol cyclic ether compounds, MIL-101-SO3H (ether bond in FP as unit)Calculated as 2.5 mol%), Pd/C (5 wt% Pd/C, calculated as one unit of ether linkage in FP as 4.0 mol%) and 1mL of n-hexane. The yields were determined by GC-FID of the reaction mixture and were normalized by n-hexadecane and 6-pentylundecane standards.
Example 16
As shown in Table 3, 7.565g of a natural extract of 82% by mass of 1, 8-cineole, 8% by mass of alpha-pinene, 1% by mass of alpha-terpineol and 7% by mass of limonene, and 450mg of MIL-101-SO3(1 mol% calculated as ether bond in FP) and 106mg of Pd/C (10 wt% Pd/C, 0.2 mol% calculated as ether bond in FP).
The same process conditions as in example 1 were used except that the reactants were different, and the product DF1 was obtained without any by-products being detected.
TABLE 3 example 16-17 Scale Up reaction yields
Example 17
As shown in Table 3, 10g of FP9, 270mg of MIL-101-SO3H (1 mol% calculated as ether bond in FP) and 509mg of Pd/C (10 wt% Pd/C, 1.6 mol% calculated as ether bond in FP).
The other process conditions were the same as in example 11 to obtain DF9, with no detectable by-products.
Claims (10)
1. The preparation method of the alkane compound is characterized by comprising the steps of mixing a cyclic ether compound and MIL-101-SO3Mixture of H and a carbon-containing noble metal catalyst in H2Reacting to obtain the alkane compound.
2. The process for producing an alkane compound according to claim 1, wherein the process for producing an alkane compound satisfies one or more of the following conditions:
(1) the cyclic ether compound is one or more of a saturated cyclic ether compound, an unsaturated cyclic ether compound and an oxa-aromatic compound;
(2) the MIL-101-SO3The preparation method of H comprises the following steps: sequentially heating and reacting 2-sulfoterephthalic acid monosodium salt, chromium trioxide, water and hydrochloric acid solution, acidifying, drying and activating to obtain the compound;
(3) the carbon-containing noble metal catalyst is one or more of rhodium carbon, palladium carbon, platinum carbon and ruthenium carbon;
(4) the mass percentage of the noble metal in the carbon-containing noble metal catalyst is 0.1-30%;
(5) the MIL-101-SO3H accounts for 0.2-2.5% of the mole percentage of ether bonds in the cyclic ether compound;
(6) the metal in the carbon-containing noble metal catalyst accounts for 0.2-4% of the mole percentage of ether bonds in the cyclic ether compound;
(7) the reaction temperature is 70-240 ℃;
(8) said H2The pressure of (a) is 30-40 bar;
(9) the preparation method of the alkane compound also comprises a post-treatment step, wherein the post-treatment step is filtering and separating to obtain the MIL-101-SO3H and carbonaceous noble metal catalyst solids, and said paraffinic compounds;
(10) the MIL-101-SO3The molar ratio of H to the metal in the carbon-containing noble metal catalyst is 0.625-5.
3. The process for producing an alkane compound according to claim 2, wherein the process for producing an alkane compound satisfies one or more of the following conditions:
(1) the cyclic ether compounds are saturated cyclic ether compounds and unsaturated cyclic ether compounds; the rings in the saturated cyclic ether compound and the unsaturated cyclic ether compound are monocyclic, spiro, bridged or fused;
(2) the mass percentage of the noble metal in the carbon-containing noble metal catalyst is 5% or 10%;
(3) the MIL-101-SO3H accounts for 0.5 percent or 1 percent of the mole percentage of ether bonds in the cyclic ether compound;
(4) the metal in the carbon-containing noble metal catalyst accounts for 0.4 percent or 0.8 percent of the mole percentage of ether bonds in the cyclic ether compounds;
(5) the MIL-101-SO3In the preparation method of H, the molar ratio of the 2-sulfoterephthalic acid monosodium salt to the chromium trioxide is 1: 1;
(6) the MIL-101-SO3In the preparation method of H, the monosodium 2-sulfonate terephthalate and the chromium trioxide are dissolved in water before the heating reaction;
(7) the MIL-101-SO3In the preparation method of H, the temperature of the heating reaction is 180 ℃;
(8) the MIL-101-SO3In the preparation method of H, the heating reaction time is 6 days;
(9) the MIL-101-SO3In the preparation method of H, the acidification is carried out on a product obtained by heating reaction in a mixed solution of methanol, water and hydrochloric acid;
(10) the MIL-101-SO3In the preparation method of H, the drying is vacuum drying;
(11) the MIL-101-SO3In the preparation method of H, the activation is carried out at 120 ℃ under vacuum;
(12) when the cyclic ether compound is an unsaturated cyclic ether compound, the reaction is heating in a sectional manner, wherein the heating temperature of the first section is 70-80 ℃, and the heating temperature of the second section is 120-240 ℃;
(13) when the cyclic ether compound is a saturated cyclic ether compound, the reaction temperature is 200-240 ℃;
(14) when the cyclic ether compound is a saturated cyclic ether compound, the reaction time is 3-10 h;
(15) when the cyclic ether compound is an oxa-aromatic compound, or the number of ether bonds in the cyclic ether compound is more than 3, or the boiling point of the mixture is below 150 ℃, the mixture also comprises cyclohexane;
(16) the preparation method of the alkane compound also comprises a post-treatment step, wherein the post-treatment step is filtering and separating to obtain the MIL-101-SO3H and carbonaceous noble metal catalyst solids; the MIL-101-SO3H and the carbon-containing noble metal catalyst solid are repeatedly used for preparing the alkane compound.
4. The process for producing an alkane compound according to claim 3, wherein the process for producing an alkane compound satisfies one or more of the following conditions:
(1) the cyclic ether compound and the corresponding alkane compound are any one of the following groups:
or 1, 8-cineole and
and
and
and
wherein R is independently H or alkyl with 1-6 carbon atoms; r1Is alkyl with 1-6 carbon atoms or
R3Is H, alkyl with 1-6 carbon atoms or
R4Is a connecting bond or an alkylene group having 1 to 6 carbon atoms; r2Is an alkyl group having 1 to 16 carbon atoms;
(2) when the cyclic ether compound is an unsaturated cyclic ether compound, the reaction is heating in a sectional manner, wherein the heating temperature of the first section is 70-80 ℃, and the heating temperature of the second section is 200 ℃;
(3) when the cyclic ether compound is an unsaturated cyclic ether compound, the reaction is heating in a sectional manner, and the first-stage heating time is 3-10 hours; and/or the second section of heating time is 3-20 h;
(4) the mixture also comprises cyclohexane, and the dosage ratio of the cyclic ether compound to the cyclohexane is (0.2-10 mmol): 10 mL;
(5) the MIL-101-SO3In the preparation method of H, before the heating reaction, the monosodium 2-sulfoterephthalate and the chromium trioxide are ultrasonically dissolved in water;
(6) the MIL-101-SO3In the preparation method of H, the monosodium 2-sulfonate terephthalate and the chromium trioxide are dissolved in water, respectively, and then filtered and mixed before the heating reaction.
5. The process for producing an alkane compound according to claim 4, wherein the process for producing an alkane compound satisfies one or more of the following conditions:
(1) when the cyclic ether compound is an unsaturated cyclic ether compound, the reaction is heating in a sectional way, and the heating time of the second section is 10 hours;
(2) the mixture also comprises cyclohexane, and the dosage ratio of the cyclic ether compound to the cyclohexane is 1 mmol: 10 mL;
(3) the cyclic ether compound and the corresponding alkane compound are any one of the following groups:
and
and
and
and
and
and
and
and
and
and
and
or
6. A hydrodeoxygenation reaction method of a cyclic ether compound is characterized by comprising the following steps: mixing with cyclic ether compound and MIL-101-SO3Mixture of H and a carbon-containing noble metal catalyst in H2And (4) carrying out the next reaction.
7. The hydrodeoxygenation reaction process of claim 6, wherein the hydrodeoxygenation reaction process satisfies one or more of the following conditions:
(1) the cyclic ether compound is the cyclic ether compound as claimed in any one of claims 2 to 6;
(2) the MIL-101-SO3H is the same as MIL-101-SO of any one of claims 2 to 43H；
(3) The carbon-containing noble metal catalyst is the same as the carbon-containing noble metal catalyst described in claim 2 or 3;
(4) the reaction conditions of the hydrodeoxygenation reaction method are the same as those of the process for producing an alkane compound according to any one of claims 2 to 5.
8. A catalyst for hydrodeoxygenation reactions, characterised in that it comprises MIL-101-SO3H and a carbon-containing noble metal catalyst, the MIL-101-SO3The molar ratio of H to the metal in the carbon-containing noble metal catalyst is 0.625-5.
9. The catalyst for hydrodeoxygenation reactions as claimed in claim 8, wherein the carbon-containing noble metal catalyst is one or more of rhodium on carbon, palladium on carbon, platinum on carbon and ruthenium on carbon.
10. Use of a catalyst according to claim 9 for hydrodeoxygenation reactions;
preferably, the hydrodeoxygenation reaction is the hydrodeoxygenation reaction method of the cyclic ether compound as described in any one of claims 6 to 7.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018064604A1 (en) * | 2016-09-30 | 2018-04-05 | Hong Je Cho | Phosphorus-containing solid catalysts and reactions catalyzed thereby, including synthesis of p-xylene |
| CN110117499A (en) * | 2019-04-10 | 2019-08-13 | 中国科学技术大学 | A method of alkane is prepared by oxygen-containing organic compound hydrogenation deoxidation |
| CN110240923A (en) * | 2019-06-27 | 2019-09-17 | 中国科学院广州能源研究所 | A kind of method that furyl oxygen-containing organic compound hydrogenation deoxidation prepares long chain alkane |
| CN110975938A (en) * | 2019-12-18 | 2020-04-10 | 华能国际电力股份有限公司 | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof |
| US20210008529A1 (en) * | 2018-03-26 | 2021-01-14 | Research Triangle Institute | Method of making confined nanocatalysts within mesoporous materials and uses thereof |
| US20210053042A1 (en) * | 2019-08-21 | 2021-02-25 | The University Of Chicago | Strongly lewis acidic metal-organic frameworks for continuous flow catalysis |
-
2021
- 2021-05-27 CN CN202110617424.2A patent/CN114315496B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018064604A1 (en) * | 2016-09-30 | 2018-04-05 | Hong Je Cho | Phosphorus-containing solid catalysts and reactions catalyzed thereby, including synthesis of p-xylene |
| US20210008529A1 (en) * | 2018-03-26 | 2021-01-14 | Research Triangle Institute | Method of making confined nanocatalysts within mesoporous materials and uses thereof |
| CN110117499A (en) * | 2019-04-10 | 2019-08-13 | 中国科学技术大学 | A method of alkane is prepared by oxygen-containing organic compound hydrogenation deoxidation |
| CN110240923A (en) * | 2019-06-27 | 2019-09-17 | 中国科学院广州能源研究所 | A kind of method that furyl oxygen-containing organic compound hydrogenation deoxidation prepares long chain alkane |
| US20210053042A1 (en) * | 2019-08-21 | 2021-02-25 | The University Of Chicago | Strongly lewis acidic metal-organic frameworks for continuous flow catalysis |
| CN110975938A (en) * | 2019-12-18 | 2020-04-10 | 华能国际电力股份有限公司 | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| DAMIN ZHANG ET AL.: ""Hydrogenation of γ-valerolactone in ethanol over Pd nanoparticles supported on sulfonic acid functionalized MIL-101"", 《RSC ADV.》, no. 4, pages 39558 - 39564 * |
| HANGXING REN ET AL.: "Pd@MIL-101 as an efficient bifunctional catalyst for hydrodeoxygenation of anisole", RSC ADV., vol. 6, no. 88, 31 August 2016 (2016-08-31), pages 85659 - 85665 * |
| 吕杨: "MOFs衍生过渡金属催化剂的制备及其催化加氢性能研究", 中国优秀硕士学位论文全文数据库工程科技Ⅰ辑, no. 2, 15 February 2021 (2021-02-15), pages 014 - 1323 * |
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