CN114315496B - 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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- CN114315496B CN114315496B CN202110617424.2A CN202110617424A CN114315496B CN 114315496 B CN114315496 B CN 114315496B CN 202110617424 A CN202110617424 A CN 202110617424A CN 114315496 B CN114315496 B CN 114315496B
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- -1 alkane compound Chemical class 0.000 title claims abstract description 107
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 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
- 238000001914 filtration Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- WEEGYLXZBRQIMU-UHFFFAOYSA-N Eucalyptol Chemical compound C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 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 7
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 5
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 5
- RPNNPZHFJPXFQS-UHFFFAOYSA-N methane;rhodium Chemical compound C.[Rh] RPNNPZHFJPXFQS-UHFFFAOYSA-N 0.000 claims description 5
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 37
- 239000000047 product Substances 0.000 description 14
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 5
- 239000011949 solid catalyst Substances 0.000 description 5
- 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 4
- HSYCPONOCCYPEY-UHFFFAOYSA-N 6-pentylundecane Chemical compound CCCCCC(CCCCC)CCCCC HSYCPONOCCYPEY-UHFFFAOYSA-N 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 229910006069 SO3H Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000000543 intermediate Substances 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
- 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
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 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
- 239000000463 material Substances 0.000 description 2
- 238000001144 powder X-ray diffraction data Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000000126 substance Substances 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
- RAADBCJYJHQQBI-UHFFFAOYSA-N 2-sulfoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(S(O)(=O)=O)=C1 RAADBCJYJHQQBI-UHFFFAOYSA-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
- 150000001335 aliphatic alkanes 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
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 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
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 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
- 125000000686 lactone group Chemical group 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
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of alkane compounds, a catalyst and application thereof. The preparation method of the alkane compound comprises the steps of reacting a mixture containing cyclic ether compound, MIL-101-SO 3 H and a noble metal catalyst containing carbon under H 2. The hydrodeoxygenation reaction of the cyclic ether compound has high yield and selectivity, the catalyst can be directly recovered, and the catalyst has good recycling performance.
Description
Technical Field
The invention relates to a preparation method of alkane compounds, a catalyst and application thereof.
Background
Hydrodeoxygenation reactions (hydrodeoxygenation, HDO) are tandem reactions of c—o bond cleavage and c=c bond hydrogenation, typically obtained by acid and transition metal co-catalysis.
The method reported in the literature is generally to load transition metals (Pd, pt, ni and the like) on a solid acid catalyst to synthesize a bifunctional catalyst with both an acid site and a catalytic hydrogenation site. However, the structure-activity relationship between two catalytic sites of the bifunctional catalyst is complex, the number and the proportion of the load are not easy to regulate and control, the synthesis and characterization difficulties are large, and the intermediate and the product are easy to isomerize in the reaction process.
To solve this problem, the prior art has conducted specific studies on catalysts. For example Zhang,D,Ye,F,Guan,Y,Wang,Y,Hensen,E.J.M.,Hydrogenation of γ-valerolactone in ethanol over Pd nanoparticles supported on sulfonic acid functionalized MIL-101.RSC Adv.2014,4(74),39558-39564 discloses that heterogeneous bifunctional catalyst MIL-101-SO 3 H can be combined with monofunctional Pd/C to catalyze HDO reaction of esters, and can convert gamma-valerolactone into ethyl valerate, but the method has the defects of low yield, more side reactions, poor selectivity, obvious reduction of the yield of cyclic reaction and the like. For another example, ,Liu,D.-H,Marks,T.J,Li,Z.,Catalytic One-Pot Conversion of Renewable Platform Chemicals to Hydrocarbon and Ether Biofuels via Tandem Hf(OTf)4+Pd/C Catalysis.ChemSusChem,2019,12(24),5217-5223 discloses a combination of "homogeneous and heterogeneous catalysts" for hydrodeoxygenation reactions, but suffers from the disadvantage that the homogeneous catalyst is difficult to recover and the selectivity is inadequate.
Disclosure of Invention
The invention provides a preparation method of alkane compounds, a catalyst and application thereof, and aims to overcome the defects of isomerization, more side reactions, low yield, poor selectivity and the like of intermediates and products in the reaction process in hydrodeoxygenation reaction in the prior art. The hydrodeoxygenation reaction of the cyclic ether compound has high yield and selectivity, the catalyst can be directly recovered, and the catalyst has good recycling performance.
The invention solves the technical problems through the following technical proposal.
The invention provides a preparation method of alkane compounds, which comprises the steps of reacting a mixture containing cyclic ether compounds, MIL-101-SO 3 H and a noble metal catalyst containing carbon under H 2.
In the invention, the alkane compound is prepared by hydrodeoxygenation reaction of the cyclic ether compound.
In the present invention, the cyclic ether compound may be a cyclic ether compound 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 ring in the saturated cyclic ether compound and the unsaturated cyclic ether compound can be a single ring, a spiro ring, a bridged ring or a parallel ring (the cyclic ether compound refers to an oxacyclic hydrocarbon compound without a lactone group).
Preferably, the cyclic ether compound is1, 8-Cineole,/> Wherein R is independently H or alkyl with 1-6 carbon atoms; r 1 is an alkyl group having 1 to 6 carbon atoms, or is/>R 3 is H, alkyl group having 1-6 carbon atoms, orR 4 is 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, and R 2 is alkyl with 1-16 carbon atoms.
In one embodiment of the invention, the cyclic ether compound isOr 1, 8-cineole, the alkane compound is/>
In one embodiment of the invention, the cyclic ether compound isThe alkane compound is
In one embodiment of the invention, the cyclic ether compound isThe alkane compound is/>
In one embodiment of the invention, the cyclic ether compound isThe alkane compound is/>
In the invention, the MIL-101-SO 3 H can be MIL-101-SO 3 H which is conventional in the art, namely MIL-101-SO 3 H (100), and is commercially available. The MIL-101-SO 3 H is obtained by ligand replacement and derivation of a chromium-based metal organic framework material MIL-101-Cr which is stable in heat, stable in acid, high in porosity and strong in water absorption, and has good heat stability and strong acidity.
Preferably, the preparation method of the MIL-101-SO 3 H comprises the following steps: and (3) heating and reacting the solution of the monosodium salt of 2-sulfoacid terephthalic acid, chromium trioxide, water and hydrochloric acid in sequence, acidifying, drying and activating.
Preferably, the molar ratio of the monosodium salt of 2-sulfoacid terephthalic acid to the chromium trioxide is 1:1.
Preferably, the monosodium salt of 2-sulfoterephthalic acid and the chromium trioxide are dissolved in water, for example ultrasonically, prior to the heating reaction. More preferably, the monosodium salt of 2-sulfoacid terephthalic acid and the chromium trioxide are dissolved in water separately, filtered and mixed. The MIL-101-SO 3 H prepared by the preparation method has good crystal form and uniform crystal size.
Preferably, the temperature of the heating reaction is 180 ℃.
Preferably, the heating reaction time is 6 days.
Preferably, the acidification is carried out by heating the reaction product in a mixed solution of methanol, water and hydrochloric acid.
Preferably, the drying is vacuum drying.
Preferably, the activation is performed at 120 ℃ and under vacuum.
In the present invention, the carbon-containing noble metal catalyst may be a carbon-containing noble metal catalyst conventional in the art.
Wherein, preferably, the carbon-containing noble metal catalyst is one or more of rhodium carbon, palladium carbon, platinum carbon and ruthenium carbon.
Wherein, the mass percent of noble metal in the noble metal catalyst containing carbon is preferably 0.1% -30%, for example 5% or 10%.
In the present invention, the MIL-101-SO 3 H preferably accounts for 0.2 to 2.5% by mole of the ether bond in the cyclic ether compound, for example, 0.5% or 1%.
In the present invention, the metal in the carbon-containing noble metal catalyst is preferably 0.2 to 4% by mole, for example, 0.4% or 0.8% by mole 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 a staged heating, the temperature of the first stage heating is 70-80 ℃, and the temperature of the second stage heating is 120-240 ℃, for example, 200 ℃.
Preferably, the heating time of the first section is 3-10 hours.
Preferably, the second stage heating is carried out for a period of 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 ℃.
The pressure of H 2 may be that conventional in this type of reaction in the art; in the present invention, it is preferably 30 to 40bar.
In one embodiment of the present invention, when the cyclic ether compound is an oxaaromatic compound, or when the number of ether linkages is 3 or more, or when the boiling point of the mixture is 150 ℃ or less, the mixture further comprises cyclohexane, and the ratio of the cyclic ether compound to the cyclohexane is (0.2 to 10 mmol): 10mL, for example 1mmol:10mL.
In the present invention, preferably, when the cyclic ether compound is a saturated cyclic ether compound, the reaction time is 3 to 10 hours.
In the present invention, preferably, the preparation method of the alkane compound further comprises a post-treatment step, wherein the post-treatment step is filtration, and the MIL-101-SO 3 H, the carbon-containing noble metal catalyst solid and the alkane compound are obtained through separation; the MIL-101-SO 3 H and the carbon-containing noble metal catalyst solid can be reused for preparing the alkane compound.
The invention provides a hydrodeoxygenation reaction method of a cyclic ether compound, which comprises the following steps:
And (3) reacting a mixture containing a cyclic ether compound, MIL-101-SO 3 H and a noble metal catalyst containing carbon under H 2.
In the present invention, preferred embodiments of the cyclic ether compound, MIL-101-SO 3 H, and the carbon-containing noble metal catalyst, reaction conditions, and operating parameters are as described above.
The invention also provides a catalyst for hydrodeoxygenation reaction, which comprises MIL-101-SO 3 H and a carbon-containing noble metal catalyst, wherein the molar ratio of metal in the MIL-101-SO 3 H to metal in the carbon-containing noble metal catalyst is 0.625-5.
Wherein, preferably, the carbon-containing noble metal catalyst is 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 a cyclic ether compound hydrodeoxygenation reaction method as described above.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that:
The catalyst combination has very excellent promoting effect on HDO reaction of cyclic ether compounds, can obtain saturated alkane with very high yield, high purity and high selectivity, and can be recovered for many 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 unique target product is obtained, and the selectivity is high. The invention can realize high-efficiency high-selectivity conversion under the condition of no solvent, has simple and convenient operation and can realize amplified production.
Drawings
FIG. 1 is an SEM image of the MIL-101-SO 3 H prepared.
FIG. 2 is a PXRD pattern of MIL-101-SO 3 H prepared.
FIG. 3 is a graph comparing the productivity of catalyst cycle performance test (7 times).
FIG. 4 is a PXRD pattern for MIL-101-SO 3 H at the end of the hydrodeoxygenation reaction of example 4.2.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
In the following examples, PXRD (powder X-Ray diffraction) data were obtained from the Bruker D8 ADVANCE test.
SEM pictures were obtained from JSM-7800F Prime test from JEOL corporation.
In the following examples, MIL-101-SO 3 H was prepared as follows:
And respectively weighing the 2-sulfoterephthalic acid monosodium salt and the chromium trioxide with equal amounts of substances in a bottle, and respectively adding deionized water for ultrasonic dissolution to obtain an aqueous solution of the 2-sulfoterephthalic acid monosodium salt and the chromium trioxide. Filtering the two solutions into the same container by using a needle head filter (0.22 mu m, nylon), adding hydrochloric acid, filtering the solution into an autoclave liner by using the needle head filter, loading the autoclave liner into a kettle, placing the autoclave liner into a 180 ℃ oven for reaction for 6 days, setting the temperature of the oven to be room temperature, taking out the kettle and cooling the kettle to the room temperature when the temperature is cooled to 120 ℃. The obtained green powder product is washed by deionized water, N-dimethylformamide and methanol, then dispersed in a mixed solvent of methanol and deionized water, added with hydrochloric acid for overnight acidification, washed by deionized water and methanol, dried in vacuum, and finally activated in vacuum at 120 ℃ to obtain MIL-101-SO 3 H.
FIGS. 1 and 2 are SEM and PXRD images, respectively, of the obtained MIL-101-SO 3 H measurements. The MIL-101-SO 3 H prepared by the preparation method has good crystal form and uniform crystal size.
Example 1
Table 1 combinations of HDO catalysts and yield comparisons for examples 1-3
| 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: 1, 4-cineole (1 a) (154 mg,1.0 mmol), MIL-101-SO 3 H (9 mg, 1mol% based on the ether bond in 1 a) and Pd/C (Pd was 10wt%,2.2mg, 0.2mol% based on the ether bond in 1 a) were charged into a 10mL reaction vessel, and after 3 times of gas substitution with H 2, 30bar of H 2 was charged, and after sealing, the reaction was stirred at 120℃for 3 hours to obtain the product (DF 1). After the reaction is completed, the solid catalyst and the liquid product are separated by a simple filtration operation. The yield was determined by GC-FID and the reaction mixture was calibrated with n-undecane.
Wherein, after the first reaction was completed, the liquid was withdrawn by distillation under reduced pressure, collected, weighed, and the yield was calculated. The remaining solid catalyst was used directly in the next experiment for 7 total reactions, the yields are shown in figure 3.
Example 2
The procedure of example 1 was repeated except that the catalyst shown in Table 1 was changed to one (the catalyst of example 2 was Pt/C, and the mass percentage of Pt to Pt/C was 5 wt%), to obtain a product (DF 1).
Example 3
The procedure of example 1 was repeated except that the catalyst shown in Table 1 was changed to one (the catalyst of example 3 was Ru/C, the mass percentage of Ru to Ru/C was 5 wt%) to obtain a product (DF 1).
By comparing examples 1 to 3, it is clear that MIL-101-SO 3 H gives very good catalytic performance in combination with the usual noble metal catalysts containing carbon (Pd/C, pt/C, ru/C).
Example 4.1
The reaction conditions for example 4.1 were: FP2 compound (96 mg,1.0 mmol) as shown in Table 2, MIL-101-SO 3 H (4.5 mg, 0.5mol% based on the ether bond in FP 2) and Pd/C (Pd: 10wt% based on the ether bond in FP2, 8.5mg, 0.8mol% based on the ether bond in FP 2) were charged into a10 mL autoclave, and after 3 times of gas displacement with H 2, 40bar of H 2 was charged again, and after sealing, the reaction was stirred at 80℃for 3 hours, and then the temperature was raised to 200℃and the reaction was stirred for another 10 hours. After the reaction is completed, the solid catalyst and the liquid product are separated by a simple filtration operation. The yields were determined by GC-FID and calibrated with n-hexadecane and 6-amyl undecane standards.
Example 4.2
The reaction conditions for example 4.2 were: FP2 compound (961 mg,10 mmol) as shown in Table 2, MIL-101-SO 3 H (181 mg, 2mol% based on the ether bond in FP 2) and Pd/C (Pd 10wt%,42.4mg, 0.4mol% based on the ether bond in FP 2) were added to 10mL of cyclohexane, and the mixture was charged into a20 mL autoclave, after 3 times of gas displacement, 40bar of H 2 was charged again, and after sealing, the mixture was stirred at 80℃for 3 hours, and the temperature was raised to 200℃and the mixture was stirred for 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 from the reaction mixture and calibrated with tetrachloroethane standard.
In example 4.2, after the reaction was completed, the product was washed with deuterated chloroform and dried in air at room temperature to test PXRD, as shown in figure 4, the MILs-101-SO 3 H crystals in the catalyst were intact.
TABLE 2 comparison of the yields and purities of the cyclic ether compound starting materials and the obtained products of examples 4 to 15
Note that: "Bu" represents a butanoyl group, and "Pen" represents a pentanoyl group; "/" represents no test.
Example 5
The reaction conditions for example 5 were: FP3 compound (32 mg,0.2 mmol) as shown in Table 2, MIL-101-SO 3 H (9 mg, 2.5mol% based on the ether bond in FP 3), pd/C (Pd: 5wt%,17mg, 4.0mol% based on the ether bond in FP 3) and 1mL of n-hexane were charged into a 10mL autoclave, after 3 times of gas displacement with H 2, 40bar of H 2 was charged again, and after sealing, the reaction was stirred at 80℃for 3 hours, and then the temperature was raised to 200℃and the reaction was stirred for another 10 hours. After the reaction is completed, the solid catalyst and the liquid product are separated by a simple filtration operation. The yields were determined by GC-FID and calibrated with n-hexadecane and 6-amyl undecane standards.
Examples 6 to 9 and 11
The procedure of example 4.1 was followed except that the cyclic ether compound shown in Table 2 was used, to obtain the product.
Wherein the reactants are 1mmol of cyclic ether compound, MIL-101-SO 3 H (0.5 mol% is calculated by taking ether bond in FP as a unit) and Pd/C (Pd accounts for 10wt% of Pd/C and 0.8mol% is calculated by taking ether bond in FP as a unit). The yields were determined by GC-FID and calibrated with n-hexadecane and 6-amyl undecane standards.
Examples 10 and 12 to 15
The procedure of example 4 was followed except that the cyclic ether compound shown in Table 2 was used, to obtain the product.
Wherein the reactants are 1mmol of cyclic ether compound, MIL-101-SO 3 H (2.5 mol% calculated by taking ether bond in FP as a unit), pd/C (Pd accounts for 5wt% of Pd/C, 4.0mol% calculated by taking ether bond in FP as a unit) and 1mL of n-hexane. The yields were determined by GC-FID and calibrated with n-hexadecane and 6-amyl undecane standards.
Example 16
As shown in Table 3, 7.565g of a natural extract of 82% by mass of 1, 8-cineole, 8% of alpha-pinene, 1% of alpha-terpineol and 7% of limonene, and 450mg of MIL-101-SO 3 (1 mol% calculated as ether linkage in FP) H and 106mg of Pd/C (10 wt% Pd/C by mass and 0.2mol% calculated as ether linkage in FP) were reacted.
The process conditions were the same as in example 1 except for the reactants, giving the product DF1, with no by-products detected.
TABLE 3 examples 16-17 scale up reaction yields
Example 17
As shown in Table 3, 10g of FP9, 270mg of MIL-101-SO 3 H (1 mol% in terms of ether bond in FP) and 509mg of Pd/C (Pd was 10wt% in terms of mass% in Pd/C, and 1.6mol% in terms of ether bond in FP) were reacted.
Other process conditions were the same as in example 11 to obtain the product DF9, no by-products were detected.
Claims (11)
1. The preparation method of the alkane compound is characterized by comprising the steps of reacting a mixture containing cyclic ether compound, MIL-101-SO 3 H and a noble metal catalyst containing carbon under H 2 to obtain the alkane compound;
the carbon-containing noble metal catalyst is one or more of rhodium carbon, palladium carbon, platinum carbon and ruthenium carbon; the metal in the carbon-containing noble metal catalyst accounts for 0.2-4% of the mole percentage of the ether bond in the cyclic ether compound;
the cyclic ether compound and the corresponding alkane compound are any one group of the following compounds: 1, 8-cineole/> And/> And/>Or/>And/>Wherein R is independently H or alkyl with 1-6 carbon atoms; r 1 is alkyl group with 1-6 carbon atoms or/>R 3 is H, alkyl group with 1-6 carbon atoms or/>R 4 is a bond or an alkylene group having 1 to 6 carbon atoms; r 2 is an alkyl group having 1 to 16 carbon atoms.
2. The method for producing an alkane compound according to claim 1, wherein the method for producing an alkane compound satisfies one or more of the following conditions:
(1) The preparation method of MIL-101-SO 3 H comprises the following steps: sequentially heating and reacting a solution of 2-sulfoterephthalic acid monosodium salt, chromium trioxide, water and hydrochloric acid, acidifying, drying and activating;
(2) The mass percentage of noble metal in the carbon-containing noble metal catalyst is 0.1% -30%;
(3) The MIL-101-SO 3 H accounts for 0.2-2.5 mol percent of ether bonds in the cyclic ether compound;
(4) The temperature of the reaction is 70-240 ℃;
(5) The pressure of the H 2 is 30-40 bar;
(6) The preparation method of the alkane compound further comprises a post-treatment step, wherein the post-treatment step is filtering, and the MIL-101-SO 3 H, the carbon-containing noble metal catalyst solid and the alkane compound are obtained through separation;
(7) The molar ratio of MIL-101-SO 3 H to metal in the carbon-containing noble metal catalyst is 0.625-5.
3. The method for producing an alkane compound according to claim 2, wherein the method for producing an alkane compound satisfies one or more of the following conditions:
(1) The mass percentage of noble metal in the carbon-containing noble metal catalyst is 5% or 10%;
(2) The MIL-101-SO 3 H accounts for 0.5% or 1% of the mole percentage of ether bonds in the cyclic ether compound;
(3) The metal in the carbon-containing noble metal catalyst accounts for 0.4% or 0.8% of the mole percentage of the ether bond in the cyclic ether compound;
(4) In the preparation method of MIL-101-SO 3 H, the molar ratio of the 2-sulfoterephthalic acid monosodium salt to the chromium trioxide is 1:1;
(5) In the preparation method of MIL-101-SO 3 H, the 2-sulfoterephthalic acid monosodium salt and the chromium trioxide are dissolved in water before the heating reaction;
(6) In the preparation method of MIL-101-SO 3 H, the temperature of the heating reaction is 180 ℃;
(7) In the preparation method of MIL-101-SO 3 H, the heating reaction time is 6 days;
(8) In the preparation method of MIL-101-SO 3 H, the acidification is carried out by heating the product obtained by the reaction in a mixed solution of methanol, water and hydrochloric acid;
(9) In the preparation method of MIL-101-SO 3 H, the drying is vacuum drying;
(10) In the preparation method of MIL-101-SO 3 H, the activation is carried out at 120 ℃ and under vacuum;
(11) When the cyclic ether compound is an unsaturated cyclic ether compound, the reaction is sectional heating, the temperature of the first section heating is 70-80 ℃, and the temperature of the second section heating is 120-240 ℃;
(12) When the cyclic ether compound is a saturated cyclic ether compound, the reaction temperature is 200-240 ℃;
(13) When the cyclic ether compound is a saturated cyclic ether compound, the reaction time is 3-10 h;
(14) When 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 contains cyclohexane;
(15) The preparation method of the alkane compound further comprises a post-treatment step, wherein the post-treatment step is filtering, and the MIL-101-SO 3 H and the carbon-containing noble metal catalyst solid are obtained through separation; the MIL-101-SO 3 H and the carbon-containing noble metal catalyst solid are reused for preparing the alkane compound.
4. The method for producing an alkane compound according to claim 3, wherein the method 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 carried out by sectional heating, the temperature of the first section heating is 70-80 ℃, and the temperature of the second section heating is 200 ℃;
(2) When the cyclic ether compound is an unsaturated cyclic ether compound, the reaction is a sectional heating, and the first heating time is 3-10 h; and/or the second heating time is 3-20 h;
(3) The mixture also comprises cyclohexane, and the dosage ratio of the cyclic ether compound to the cyclohexane is 0.2-10 mmol:10mL;
(4) In the preparation method of MIL-101-SO 3 H, before the heating reaction, the 2-sulfoterephthalic acid monosodium salt and the chromium trioxide are ultrasonically dissolved in water;
(5) In the preparation method of MIL-101-SO 3 H, before the heating reaction, the 2-sulfoterephthalic acid monosodium salt and the chromium trioxide are respectively dissolved in water, filtered and mixed.
5. The method for producing an alkane compound according to claim 4, wherein the method 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 a sectional heating, and the second heating time is 10 hours;
(2) The mixture also comprises cyclohexane, the dosage ratio of the cyclic ether compound to the cyclohexane is 1mmol:10mL;
(3) The cyclic ether compound and the corresponding alkane compound are any one group of the following compounds: And/> And/> And/> And/> And/> And/> And/> And/> And (3) with And/> And/>Or/>And/>
6. The hydrodeoxygenation reaction method of the cyclic ether compound is characterized by comprising the following steps of: reacting a mixture containing cyclic ether compounds, MIL-101-SO 3 H and a noble metal catalyst containing carbon under H 2 to obtain alkane compounds;
the carbon-containing noble metal catalyst is one or more of rhodium carbon, palladium carbon, platinum carbon and ruthenium carbon; the metal in the carbon-containing noble metal catalyst accounts for 0.2-4% of the mole percentage of the ether bond in the cyclic ether compound;
the cyclic ether compound and the corresponding alkane compound are any one group of the following compounds: Or 1, 8-cineole And/> And/>Or/>And/>Wherein R is independently H or alkyl with 1-6 carbon atoms; r 1 is alkyl group with 1-6 carbon atoms or/>R 3 is H, alkyl group with 1-6 carbon atoms or/>R 4 is a bond or an alkylene group having 1 to 6 carbon atoms; r 2 is an alkyl group having 1 to 16 carbon atoms.
7. The hydrodeoxygenation reaction process of claim 6, wherein the process comprises the steps of,
The cyclic ether compound is the same as the cyclic ether compound according to claim 5.
8. The hydrodeoxygenation reaction process of claim 6, wherein MILs-101-SO 3 H is as set forth in any one of claims 2 to 4, MILs-101-SO 3 H.
9. The method for hydrodeoxygenation of cyclic ether compounds according to claim 6, wherein the carbon-containing noble metal catalyst is as defined in any one of claims 1 to 3.
10. The hydrodeoxygenation reaction process of claim 6, wherein the reaction conditions of the hydrodeoxygenation reaction process are the same as the conditions of the process for producing an alkane compound according to any one of claims 2 to 5.
11. The application of the catalyst for hydrodeoxygenation reaction is characterized in that the catalyst comprises MIL-101-SO 3 H and a carbon-containing noble metal catalyst, wherein the carbon-containing noble metal catalyst is one or more of rhodium carbon, palladium carbon, platinum carbon and ruthenium carbon; the molar ratio of MIL-101-SO 3 H to metal in the carbon-containing noble metal catalyst is 0.625-5;
The hydrodeoxygenation reaction is a method for hydrodeoxygenation of a cyclic ether compound according to any one of claims 6 to 7.
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