CN111495419B - Metal-supported hierarchical pore ZSM-5 molecular sieve and preparation method and application thereof - Google Patents
Metal-supported hierarchical pore ZSM-5 molecular sieve and preparation method and application thereof Download PDFInfo
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- CN111495419B CN111495419B CN201910097614.9A CN201910097614A CN111495419B CN 111495419 B CN111495419 B CN 111495419B CN 201910097614 A CN201910097614 A CN 201910097614A CN 111495419 B CN111495419 B CN 111495419B
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- furandimethanol
- metal
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- dialkyl ether
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 69
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 13
- DSLRVRBSNLHVBH-UHFFFAOYSA-N 2,5-furandimethanol Chemical compound OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- 229910052751 metal Inorganic materials 0.000 claims abstract description 51
- 239000002184 metal Substances 0.000 claims abstract description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000011068 loading method Methods 0.000 claims abstract description 19
- 239000011148 porous material Substances 0.000 claims abstract description 14
- 229910052718 tin Inorganic materials 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 62
- -1 2, 5-furan dimethanol dialkyl ether Chemical class 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 31
- 239000002994 raw material Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 24
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052710 silicon Inorganic materials 0.000 claims description 20
- 239000010703 silicon Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 16
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000001308 synthesis method Methods 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 12
- 238000006266 etherification reaction Methods 0.000 abstract description 10
- NKRNKUWYXIABEN-UHFFFAOYSA-N 2,5-bis(ethoxymethyl)furan Chemical compound CCOCC1=CC=C(COCC)O1 NKRNKUWYXIABEN-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical group [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 8
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 7
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 7
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 7
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 6
- NSQYDLCQAQCMGE-UHFFFAOYSA-N 2-butyl-4-hydroxy-5-methylfuran-3-one Chemical compound CCCCC1OC(C)=C(O)C1=O NSQYDLCQAQCMGE-UHFFFAOYSA-N 0.000 description 5
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 5
- 108091006231 SLC7A2 Proteins 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- CCDRPZFMDMKZSZ-UHFFFAOYSA-N 5-(ethoxymethyl)furan-2-carbaldehyde Chemical compound CCOCC1=CC=C(C=O)O1 CCDRPZFMDMKZSZ-UHFFFAOYSA-N 0.000 description 4
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 4
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 4
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 3
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- DZEPFNDOOWFEKN-UHFFFAOYSA-N 2,5-bis(methoxymethyl)furan Chemical compound COCC1=CC=C(COC)O1 DZEPFNDOOWFEKN-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 108091006230 SLC7A3 Proteins 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- UQYIJQXDRBKHBG-UHFFFAOYSA-N [5-(acetyloxymethyl)furan-2-yl]methyl acetate Chemical compound CC(=O)OCC1=CC=C(COC(C)=O)O1 UQYIJQXDRBKHBG-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 230000009286 beneficial effect 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
- 239000012159 carrier gas Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010702 ether synthesis reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a metal-supported hierarchical pore ZSM-5 molecular sieve, which contains mesopores; the average pore diameter of the mesopores is 2-20 nm, and the volume of the mesopores is 0.2-0.6 mL/g; the metal element in the metal-loaded hierarchical pore ZSM-5 molecular sieve is at least one of Sn, mg and Zn, and the metal element loading amount is 0.1-10wt%; the metal loading is calculated as the loading of the metal element. Also relates to a preparation method and application of the catalyst in catalyzing etherification reaction of 2, 5-furandimethanol and ethanol on a fixed bed reactor.
Description
Technical Field
The application relates to a metal-supported hierarchical pore ZSM-5 molecular sieve, a preparation method thereof and application of the metal-supported hierarchical pore ZSM-5 molecular sieve serving as a catalyst in a method for preparing 2, 5-furandimethanol diethyl ether by etherification of 2, 5-furandimethanol and ethanol in a fixed bed reactor, and belongs to the field of molecular sieves.
Background
5-Ethoxymethylfurfural (EMF) is the product of etherification of 5-Hydroxymethylfurfural (HMF) with ethanol due to its high energy density (8.7 kW hL) -1 ) And good fuel mixing, are considered to be a potential bio-based fuel additive. At present, the HMF and monohydric alcohol ether such as ethanol are relatedThere have been many reports on the chemical preparation of monoethers, and there has been much in-depth knowledge of the relationship between the reaction and the acidity of the catalyst. However, there is still one aldehyde group present in the EMF molecule, reducing the stability of the molecule. The 2, 5-furan dimethanol diethyl ether (BEMF) is prepared by preparing 2, 5-furan dimethanol (BHMF) by HMF catalytic hydrogenation, and then carrying out etherification reaction on the 2, 5-furan dimethanol diethyl ether and ethanol. BEMF has not only higher stability but also a wider carbon number range and a wider application range than EMF. Solid acid catalysts, particularly molecular sieves and Amberlyst-15, are widely used to catalyze the etherification of BHMF with monohydric alcohols to produce 2, 5-furandimethanol dialkyl ethers (BAMF). Literature [ Applied Catalysis A:general 481, 49-53 (2014) ] reports that the highest yield of 2, 5-furandimethanol dimethyl ether is 70% under optimized reaction conditions, using ZSM-5 molecular sieve as catalyst to catalyze the etherification reaction of 2, 5-furandimethanol with methanol. Document [ Synlett,28,2299-2302 (2017) ] reports Amberlyst-15's ability to catalyze the etherification of 2, 5-furandimethanol with ethanol to produce 2, 5-furandimethanol diethyl ether, the yield of 2, 5-furandimethanol diethyl ether reaching 70%. Notably, all of the above references are conducted in batch reactors. Compared with a kettle type reactor, the fixed bed reactor can greatly shorten the production time, is simple to operate, and is more suitable for realizing continuous production. However, since the reaction time for contacting the reactant molecules with the catalyst in a fixed bed reaction is short, higher demands are placed on the activity, selectivity and stability of the catalyst. The ZSM-5 molecular sieve and Amberlyst-15 reported in the current literature are reacted for 3 to 24 hours at a lower temperature (< 80 ℃). Although the reaction rate can be accelerated by increasing the reaction temperature, the selectivity of the target product is also greatly reduced.
Therefore, it is very significant to develop a high-performance fixed bed catalyst which can be effectively applied to the etherification reaction of 2, 5-furandimethanol and ethanol to prepare 2, 5-furandimethanol diethyl ether, and realize high 2, 5-furandimethanol diethyl ether yield and excellent catalyst stability.
Disclosure of Invention
According to one aspect of the application, a metal-supported hierarchical pore ZSM-5 molecular sieve is provided, is hierarchical pore, has higher activity and selectivity and excellent stability, and has good application prospect in the field of catalysts.
The metal-supported hierarchical pore ZSM-5 molecular sieve is characterized in that the metal-supported hierarchical pore ZSM-5 molecular sieve contains mesopores;
the average pore diameter of the mesopores is 2-20 nm, and the volume of the mesopores is 0.2-0.6 mL/g;
the metal element in the metal-loaded hierarchical pore ZSM-5 molecular sieve is at least one of Sn, mg and Zn, and the metal element loading amount is 0.1-10wt%;
the metal loading is calculated as the loading of the metal element.
Optionally, the metal element in the metal-loaded hierarchical pore ZSM-5 molecular sieve is one of Sn, mg and Zn, and the metal element loading amount is 1-5wt%;
the metal loading is calculated as the loading of the metal element.
Optionally, the particle size of the multistage hole ZSM-5 molecular sieve is 100-400 nm, and the specific surface area is 400-700 m 2 And/g, the silicon-aluminum atomic ratio is 10-500.
Alternatively, the multistage pore ZSM-5 molecular sieve has a silicon to aluminum atomic ratio (atomic mole ratio of Si/Al) ranging from a lower limit selected from 10, 20 or 30 to an upper limit selected from 50, 300 or 500.
Optionally, the hierarchical pore ZSM-5 molecular sieve has a silicon to aluminum atomic ratio (Si/Al atomic ratio) =30 to 300.
Optionally, the multistage pore ZSM-5 molecular sieve has a silicon to aluminum ratio (Si/Al atomic ratio) =30 to 150.
According to another aspect of the application, a preparation method of the metal-supported hierarchical pore ZSM-5 molecular sieve is provided, and the method is simple, low in energy consumption and suitable for industrial production.
The method for preparing the metal-supported hierarchical pore ZSM-5 molecular sieve is characterized by comprising the following steps of:
1) Preparing a raw material containing a silicon source, an aluminum source, a template agent and an alcohol compound into xerogel;
2) Crystallizing the xerogel in an atmosphere containing water vapor under a closed condition to obtain a hierarchical pore ZSM-5 molecular sieve;
3) Immersing the hierarchical pore ZSM-5 molecular sieve in a solution containing a metal element precursor, and then drying and roasting to obtain the metal-loaded hierarchical pore ZSM-5 molecular sieve.
Optionally, the silicon source is selected from at least one of ethyl orthosilicate, methyl orthosilicate, hexadecyltrimethoxysilane, octadecyltrimethoxysilane.
Optionally, the aluminum source is selected from at least one of organoaluminum compounds.
Optionally, the aluminum source is aluminum isopropoxide.
Optionally, the template agent is selected from at least one of compounds having a chemical structural formula shown in formula II:
in formula II, R 5 ,R 6 ,R 7 ,R 8 Independently selected from methyl, ethyl, propyl or butyl;
X — selected from OH — 、F — 、Cl — 、Br — 、I — At least one of them.
Optionally, the template is tetrapropylammonium hydroxide (abbreviated as TPAOH).
Optionally, the alcohol compound is at least one selected from ethanol and isopropanol.
Optionally, the alcohol compound is ethanol.
Optionally, in the step 1), the molar ratio of the silicon source, the aluminum source, the template agent and the alcohol compound in the raw materials is:
silicon source: aluminum source: template agent: alcohol compound=1.01 to 1.1: 0.002-0.1: 0.1 to 0.3:10 to 1000.
Optionally, the raw materials comprise silicon source, aluminum source, template agent and alcohol compound in the molar ratio of:
silicon source: aluminum source: template agent: alcohol compound = 1.05: 0.002-0.1: 0.2:20.
optionally, the raw materials comprise silicon source, aluminum source, template agent and alcohol compound in the molar ratio of:
silicon source: aluminum source: template agent: alcohol compound = 1.05:0.0035:0.2:20.
wherein the mole number of the silicon source is SiO 2 Calculated in terms of mole number of aluminum source and Al 2 O 3 The mole number of the template agent is calculated by the mole number of the template agent per se, and the mole number of the alcohol compound is calculated by the mole number of the alcohol compound per se.
Alternatively, the xerogel in step 1) is prepared by a process comprising the steps of:
mixing a silicon source, an aluminum source, a template agent and an alcohol compound to obtain raw material gel;
and (3) drying the obtained raw material gel at 20-40 ℃ for at least 24 hours to obtain the xerogel.
Alternatively, the gel drying time is 72 hours to form a xerogel.
Optionally, step 1) includes: the raw materials containing the silicon source, the aluminum source, the template agent and the alcohol compound are stirred at 25 ℃ to form gel, and then dried to form xerogel.
Optionally, the crystallization time of the xerogel in the step 2) in the atmosphere containing water vapor is 48-120 h, and the crystallization temperature is 150-200 ℃.
Optionally, the atmosphere containing water vapor is a water vapor atmosphere.
Optionally, the crystallization time in the step 2) is 60-96 h.
Optionally, the crystallization temperature in the step 2) is 160 ℃ to 190 ℃.
Optionally, the crystallization in the step 2) is performed for 60-96 hours at 150-200 ℃.
Optionally, the crystallization in the step 2) is carried out for 70-80 hours at 160-190 ℃.
Optionally, step 2) includes: crystallizing the xerogel in the atmosphere containing water vapor under a closed condition, and washing, drying and roasting after crystallization to obtain the hierarchical pore ZSM-5 molecular sieve.
Optionally, the drying condition in the step 2) is that the drying is carried out at 110 ℃ for 2-4 hours.
Optionally, the roasting condition in the step 2) is that the roasting is carried out for 5-12 hours at 550 ℃.
Optionally, the metal in the metal precursor in step 3) is selected from at least one of Sn, mg, zn;
the impregnation is an isovolumetric impregnation method, and the metal loading is 0.1-10wt%.
Optionally, the metal element precursor is selected from at least one of Sn chloride, sn sulfate, sn nitrate, mg chloride, mg sulfate, mg nitrate, zn chloride, zn sulfate, zn nitrate.
Optionally, the metal element precursor is selected from at least one of stannous chloride dihydrate, magnesium nitrate hexahydrate and zinc nitrate hexahydrate.
Alternatively, the metal loading in step 3) is 1wt% to 5wt%.
Optionally, the drying condition in the step 3) is that the drying is carried out at 110 ℃ for 2-4 hours.
Optionally, the roasting condition in the step 3) is that the roasting is carried out at 550 ℃ for 5-12 h.
According to another aspect of the present application, there is provided a catalyst having high activity and selectivity and excellent stability, the hierarchical pore structure of which and suitable surface acidity can improve the efficiency of the target product.
The catalyst is characterized by comprising a metal-supported hierarchical pore ZSM-5 molecular sieve;
the metal-supported multistage-pore ZSM-5 molecular sieve is at least one selected from the metal-supported multistage-pore ZSM-5 molecular sieve and the metal-supported multistage-pore ZSM-5 molecular sieve prepared according to the method.
Optionally, the particle size of the catalyst is 20-40 mesh.
According to another aspect of the application, a synthesis method of 2, 5-furandimethanol dialkyl ether is provided, and the catalyst of the reaction method has the characteristics of high conversion rate, high target product yield and good stability.
The synthesis method of the 2, 5-furandimethanol dialkyl ether is characterized in that a reaction raw material containing 2, 5-furandimethanol and alkyl alcohol is introduced into a fixed bed reactor filled with a catalyst, and the reaction raw material reacts with the catalyst in a contact way to prepare the 2, 5-furandimethanol dialkyl ether;
the alkyl alcohol has a structural formula shown in a formula I: R-OH formula I; wherein R is C 2 ~C 10 Alkyl of (a);
the catalyst is selected from at least one of the metal supported multistage hole ZSM-5 molecular sieve, the metal supported multistage hole ZSM-5 molecular sieve prepared according to the method and the catalyst.
Optionally, the alkyl alcohol is ethanol.
Alternatively, the synthesis method of the 2, 5-furandimethanol dialkyl ether is characterized in that a reaction raw material containing 2, 5-furandimethanol and alkyl alcohol is introduced into a fixed bed reactor filled with a catalyst, and the reaction raw material reacts with the catalyst in a contact manner to continuously prepare the 2, 5-furandimethanol dialkyl ether;
the alkyl alcohol has a structural formula shown in a formula I: R-OH formula I; wherein R is C 1 ~C 10 Alkyl of (a);
the catalyst is selected from at least one of the metal supported multistage hole ZSM-5 molecular sieve, the metal supported multistage hole ZSM-5 molecular sieve prepared according to the method and the catalyst.
Optionally, the alkyl alcohol is ethanol.
Optionally, the concentration of 2, 5-furandimethanol in the reaction raw material is 1-50 g/L.
Optionally, the concentration of 2, 5-furandimethanol in the feed is 5g/L.
Optionally, the upper concentration limit of 2, 5-furandimethanol in the reaction raw material is selected from 2g/L, 3g/L, 4g/L, 5g/L, 10g/L, 15g/L, 20g/L, 30g/L, 40g/L or 50g/L; the lower limit is selected from 1g/L, 2g/L, 3g/L, 4g/L, 5g/L, 10g/L, 15g/L, 20g/L, 30g/L or 40g/L.
Optionally, the mass airspeed of the 2, 5-furandimethanol is 0.1-3 h -1 。
Optionally, the upper limit of the mass space velocity of the 2, 5-furandimethanol is selected from 0.2h -1 、0.3h -1 、0.5h -1 、1h -1 、1.5h -1 、2h -1 、2.5h -1 Or 3h -1 The method comprises the steps of carrying out a first treatment on the surface of the The lower limit is selected from 0.1h -1 、0.2h -1 、0.3h -1 、0.5h -1 、1h -1 、1.5h -1 、2h -1 Or 2.5h -1 。
Optionally, the mass space velocity of the 2, 5-furandimethanol is 0.3h -1 。
Optionally, the mass space velocity of the 2, 5-furandimethanol is 0.2h -1 。
Alternatively, the reaction temperature of the contact reaction of the reaction raw material containing 2, 5-furandimethanol and monohydric alcohol with the catalyst is 100-160 ℃.
Alternatively, the upper limit of the reaction temperature of the reaction raw material containing 2, 5-furandimethanol and monohydric alcohol for the contact reaction with the catalyst is selected from 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ or 160 ℃; the lower limit is selected from 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃.
Alternatively, the reaction temperature of the reaction raw material containing 2, 5-furandimethanol and monohydric alcohol and the catalyst are 140 ℃.
Alternatively, the reaction pressure of the contact reaction of the reaction raw material containing 2, 5-furandimethanol and monohydric alcohol with the catalyst is 0.1-3 MPa.
Alternatively, the upper limit of the reaction pressure of the contact reaction of the 2, 5-furandimethanol and monohydric alcohol containing reaction raw materials with the catalyst is selected from 0.5MPa, 1MPa, 1.5MPa, 2MPa, 2.5MPa or 3MPa; the lower limit is selected from 0.1MPa, 0.5MPa, 1MPa, 1.5MPa, 2MPa or 2.5MPa.
Alternatively, the reaction pressure of the contact reaction of the reaction raw material containing 2, 5-furandimethanol and monohydric alcohol with the catalyst is 2MPa.
Optionally, the catalyst after the reaction is roasted to obtain a regenerated catalyst.
As an implementation mode, the synthesis method of the 2, 5-furandimethanol diethyl ether is provided, and the catalyst of the reaction method has the characteristics of high conversion rate, high target product yield and good stability.
The synthesis method of the 2, 5-furandimethanol diethyl ether is characterized in that a catalyst is placed in a fixed bed reactor, then a mixed solution of 2, 5-furandimethanol and ethanol is added by a high-pressure constant flow pump, and the 2, 5-furandimethanol diethyl ether is prepared after a reactant and the catalyst are in contact reaction under certain reaction conditions.
Optionally, the concentration of 2, 5-furandimethanol in the material is 1-50 g/L.
Optionally, the concentration of 2, 5-furandimethanol in the feed is 5g/L.
Optionally, the mass airspeed of the 2, 5-furandimethanol is 0.1-3 h -1 。
Optionally, the mass space velocity of the 2, 5-furandimethanol is 0.3h -1 。
Optionally, the reaction temperature of the contact reaction of the mixed solution and the catalyst is 100-160 ℃.
Optionally, the reaction pressure of the contact reaction of the mixed solution and the catalyst is 0.1-3 MPa.
In the present application, tetrapropylammonium hydroxide is abbreviated to TPAOH.
In the present application, hexadecyltrimethoxysilane is abbreviated as HTS.
In the present application, 2, 5-furandimethanol diethyl ether is abbreviated as BEMF.
In the present application, 2, 5-furandimethanol is abbreviated as BHMF.
In the application, C 2 ~C 10 Refers to the number of carbon atoms contained. Such as "C 2 ~C 10 The term "alkyl group" means an alkyl group having 2 to 10 carbon atoms.
In the present application, an "alkyl group" is a group formed by losing any one of hydrogen atoms on an alkane compound molecule. The alkane compound comprises straight-chain alkane, branched alkane, cycloparaffin and cycloparaffin with branched chains.
The application has the beneficial effects that:
1) The metal supported multistage pore ZSM-5 molecular sieve provided by the application has mesopores and micropores, has excellent catalytic performance, can effectively improve the utilization rate of acid sites of a catalyst and promote the diffusion of macromolecular products, and has good application prospects in the field of catalysts;
2) The preparation method of the metal-supported hierarchical pore ZSM-5 molecular sieve provided by the application has the characteristics of simplicity, low energy consumption and suitability for industrial production.
3) The metal supported multistage hole ZSM-5 molecular sieve catalyst provided by the application can effectively inhibit the occurrence of side reactions such as ring opening, polymerization and the like in the process of catalyzing molecular etherification of 2, 5-furandimethanol and the like.
4) The method for etherification reaction of 2, 5-furandimethanol and ethanol provided by the application has high 2, 5-furandimethanol conversion activity, high 2, 5-furandimethanol diethyl ether yield and excellent stability; the metal supported multistage hole ZSM-5 molecular sieve catalyst of the reaction method is not easy to deactivate and can be roasted and regenerated.
Drawings
FIG. 1 is a sample CAT-2 # Is a XRD pattern of (C).
FIG. 2 is a sample CAT-2 of example 9 # Is a result of the catalytic performance test of (2).
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, the feedstock, solvent, and microporous molecular sieve catalyst in the examples of the present application were all purchased commercially, wherein the microporous molecular sieve catalyst was purchased from the university of south opening catalyst plant.
In the examples, the sample was subjected to X-ray powder diffraction using a Bruker D8ADVANCE powder diffractometer using a Cu K.alpha.radiation source
In the examples, the products of the 2, 5-furandimethanol diethyl ether synthesis were analyzed using an Agilent model 1260 high performance liquid chromatograph.
The conversion and yield in the 2, 5-furandimethanol diethyl ether synthesis reaction were calculated as follows:
the purity of the 2, 5-furandimethanol diethyl ether product is the weight percentage of the target product 2, 5-furandimethanol dimethyl ether in the reaction product. BHMF conversion and BMMF yield were all calculated based on carbon moles:
example 1 sample 1 # Preparation
0.12g aluminum isopropoxide, 12g tetrapropylammonium hydroxide, 14mL ethyl orthosilicate, 1.6mL hexadecyltrimethoxysilane, and 50mL ethanol were mixed in a beaker and stirred at 25℃until a gel formed; drying the gel at 25 ℃ for 48 hours, placing the gel in 50mL of lining, transferring the lining into a 250mL stainless steel water heating kettle containing polytetrafluoroethylene lining, adding 60mL deionized water between the two linings to provide a water vapor atmosphere required for crystallization, and crystallizing at 180 ℃ for 72 hours; filtering, washing, drying at 110deg.C for 3h, and calcining at 550deg.C for 7h to obtain the multi-stage pore ZSM-5 molecular sieve sample, which is denoted as sample 1 # 。
Example 2 sample 2 # Preparation
0.12g aluminum isopropoxide, 12g tetrapropylammonium hydroxide, 14mL ethyl orthosilicate, 1.6mL hexadecyltrimethoxysilane, and 50mL ethanol were mixed in a beaker and stirred at 25℃until a gel formed; the gel was dried at 25 ℃ for 48 hours and placed in a 50mL liner, which was then transferred to a 250mL stainless steel hot pot containing a polytetrafluoroethylene liner with 60mL deionized water added between the liners to provide the desired steaming for crystallizationCrystallizing for 72h at 180 ℃ in a gas atmosphere; filtering, washing, drying at 110 ℃ for 3h, roasting at 550 ℃ for 7h to obtain the multistage hole ZSM-5 molecular sieve 1 # And (3) a sample. 0.1g stannous chloride dihydrate is added to 4g deionized water, and then 4g hierarchical pore ZSM-5 molecular sieve 1 is added # Impregnating for 48h, drying and roasting at 550 ℃ for 7h to obtain the metal tin supported hierarchical pore ZSM-5 molecular sieve sample, namely sample 2 # 。
Example 3 sample 3 # Is prepared from
0.10g aluminum isopropoxide, 12g tetrapropylammonium hydroxide, 14mL ethyl orthosilicate, 1.6mL hexadecyltrimethoxysilane, and 50mL ethanol were mixed in a beaker and stirred at 25℃until a gel formed; drying the gel at 25 ℃ for 48 hours, placing the gel in 50mL of lining, transferring the lining into a 250mL stainless steel water heating kettle containing polytetrafluoroethylene lining, adding 50mL of deionized water between the two linings to provide a water vapor atmosphere required for crystallization, and crystallizing at 175 ℃ for 72 hours; filtering, washing, drying at 110deg.C for 2h, and calcining at 550deg.C for 6h to obtain the multi-stage pore ZSM-5 molecular sieve sample, which is denoted as sample 3 # 。
Example 4 sample 4 # Is prepared from
0.10g aluminum isopropoxide, 12g tetrapropylammonium hydroxide, 14mL ethyl orthosilicate, 1.6mL hexadecyltrimethoxysilane, and 50mL ethanol were mixed in a beaker and stirred at 25℃until a gel formed; drying the gel at 25 ℃ for 48 hours, placing the gel in 50mL of lining, transferring the lining into a 250mL stainless steel water heating kettle containing polytetrafluoroethylene lining, adding 50mL of deionized water between the two linings to provide a water vapor atmosphere required for crystallization, and crystallizing at 175 ℃ for 72 hours; filtering, washing, drying at 110 ℃ for 2h, roasting at 550 ℃ for 6h to obtain the multistage hole ZSM-5 molecular sieve 3 # And (3) a sample. 0.85g of magnesium nitrate hexahydrate is added into 3g of deionized water, and then 3g of multi-level pore ZSM-5 molecular sieve 3 is added # Soaking for 24h, drying at 110 ℃ for 2h, and roasting at 550 ℃ for 8h to obtain the metal magnesium supported hierarchical pore ZSM-5 molecular sieve sample, namely sample 4 # 。
Example 5 sample 5 # Is prepared from
0.06g aluminum isopropoxide, 12g tetrapropylammonium hydroxide, 14mL ethyl orthosilicate, 1.6mL octadecyltrimethoxysilane and 50mL ethanol were mixed in a beaker and stirred at 25℃until a gel formed; drying the gel at 25 ℃ for 72 hours, placing the gel in 50mL of lining, transferring the lining into a 250mL stainless steel water heating kettle containing polytetrafluoroethylene lining, adding 40mL deionized water between the two linings to provide a water vapor atmosphere required for crystallization, and crystallizing at 180 ℃ for 70 hours; filtering, washing, drying at 110deg.C for 4h, and calcining at 550deg.C for 8h to obtain the final product, namely sample 5 # 。
Example 6 sample 6 # Is prepared from
0.06g aluminum isopropoxide, 12g tetrapropylammonium hydroxide, 14mL ethyl orthosilicate, 1.6mL octadecyltrimethoxysilane and 50mL ethanol were mixed in a beaker and stirred at 25℃until a gel formed; drying the gel at 25 ℃ for 72 hours, placing the gel in 50mL of lining, transferring the lining into a 250mL stainless steel water heating kettle containing polytetrafluoroethylene lining, adding 40mL deionized water between the two linings to provide a water vapor atmosphere required for crystallization, and crystallizing at 180 ℃ for 70 hours; filtering, washing, drying at 110 ℃ for 4 hours, and roasting at 550 ℃ for 8 hours to obtain the hierarchical ZSM-5 molecular sieve 5 # And (3) a sample. 0.1g of zinc nitrate hexahydrate is added into 4g of deionized water, and then 4g of multi-level pore ZSM-5 molecular sieve 5 is added # Soaking for 36h, drying at 110 ℃ for 2h, roasting at 550 ℃ for 6h to obtain the metal zinc supported hierarchical pore ZSM-5 molecular sieve sample, namely sample 6 # 。
Example 7 sample 7 # ~9 # Is prepared from
Sample 7 # The preparation method of (2) was the same as in example 1 except that the amount of aluminum isopropoxide added was 0.4g.
Sample 8 # The preparation method of (2) was the same as in example 2 except that stannous chloride dihydrate was added in an amount of 0.5g.
Sample 9 # The preparation method of (2) was the same as in example 6 except that zinc nitrate hexahydrate was added in an amount of 0.5g.
Example 8 characterization of samples
Sample 1 was subjected to X-ray powder diffraction # ~9 # And CAT-1 # ~CAT-9 # Characterization was performed and the results showed that sample 1 # ~9 # And CAT-1 # ~CAT-9 # Are ZSM-5 molecular sieves and CAT-2 molecular sieves # As a representative, its XRD pattern is shown in FIG. 1, sample 1 # ~9 # And CAT-1 # 、CAT-3 # ~CAT-9 # The peak positions of the diffraction peaks are substantially the same as those of fig. 1, and the peak intensities of the respective diffraction peaks vary within a range of ±10% depending on the preparation conditions.
Sample 1 of the example was obtained using X-ray fluorescence spectroscopy (XRF) and a fully automated specific surface area and porosity analyzer # ~9 # The molecular sieve has the silicon-aluminum atomic ratio of 30-200, the mesoporous aperture of 2-20 nm and the mesoporous volume of 0.2-0.6 mL/g.
Sample 1 of the example was examined using a Scanning Electron Microscope (SEM) # ~9 # The molecular sieve has the particle size of 100-400 nm.
Sample 1 of the example was subjected to a full-automatic specific surface analyzer # ~9 # Characterized in that the specific surface area of the molecular sieve is 400-700 m 2 /g。
Example 9 CAT-1 # ~CAT-9 # Is prepared from
Sample 1 obtained # ~9 # Grinding, tabletting, crushing and sieving, taking 20-40 mesh particle size as catalyst sample, and respectively marking as CAT-1 # ~CAT-9 # 。
Comparative example 1 DCAT-1 # And DCAT-2 # Is prepared from
ZSM-5 (Si/Al=50), MCM-22 (Si/Al=25) and Mordenite (Si/Al=11) molecular sieves purchased from a Nanking catalyst factory are respectively placed at 550 ℃ and calcined for 8 hours, the calcined catalyst is ground, pressed, crushed and sieved, and the particle size of 20-40 meshes is taken as a catalyst sample and respectively recorded as DCAT-1 # 、DCAT-2 # And DCAT-3 # 。
Example 10 use of catalyst samples in 2, 5-furandimethanol diethyl ether Synthesis
CAT-1 respectively # ~CAT-9 # 、DCAT-1 # 、DCAT-2 # 、DCAT-3 # The method is used for the synthesis reaction of the 2, 5-furandimethanol diethyl ether, and comprises the following specific steps:
5g of 2, 5-furandimethanol are weighed and the volume is fixed to 1L by ethanol. Weighing 2g of catalyst, placing the catalyst in a fixed bed reactor, introducing hydrogen as carrier gas, heating to 140 ℃ for 30min under the pressure of 2 Mpa; then the raw materials are pumped into a fixed bed reactor by a high-pressure constant flow pump, and the mass airspeed of the 2, 5-furandimethanol is 0.3h -1 The method comprises the steps of carrying out a first treatment on the surface of the Sampling was started after 1h of reaction, then every 1h of sampling was performed, and feeding was stopped after 6h of reaction. The concentration of the reactants and products was analyzed by high performance liquid chromatography after the samples were diluted with methanol, thereby calculating the conversion of 2, 5-furandimethanol and the yield of 2, 5-furandimethanol diethyl ether as shown in table 1. Sample 1 # ,3 # ,5 # Is a metal-free hierarchical pore molecular sieve, sample 2 # ,4 # ,6 # Then the metal loading was performed on the corresponding unsupported hierarchical pore molecular sieve, and as can be seen from Table 1, the performance of the supported catalyst was superior to that of the unsupported catalyst. In the application, a metal-supported hierarchical pore ZSM-5 molecular sieve is adopted, 2, 5-furandimethanol and methanol are used as raw materials to synthesize the 2, 5-furandimethanol dialkyl ether, the conversion rate of the 2, 5-furandimethanol reaches 100%, and the yield of the 2, 5-furandimethanol diethyl ether reaches 90%.
TABLE 1 catalytic Properties of microporous ZSM-5 and multistage pore ZSM-5 molecular sieves
BHMF:2, 5-furandimethanol; BEMF:2, 5-Furandimethanol diethyl ether
Example 11 stability of catalyst samples
Catalyst sample CAT-2 # The catalyst was used for the synthesis of 2, 5-furandimethanol diethyl ether, the specific procedure and conditions were the same as in example 10, except that the reaction was continued after 6 hours of reaction, with one hour intervalsThe reaction was stopped after 100 hours. Fig. 2 is a graph of catalytic activity and stability data for a 100 hour continuous feed reaction using a fixed bed reactor, and fig. 2 shows that the catalyst maintained good catalytic activity and stability over the reaction time examined. When a fixed bed reactor is adopted, the catalyst is fixedly filled in a reaction tube, the reaction materials are continuously pumped by a high-pressure constant-flow pump, the reaction products can be continuously obtained, and the yield of the target products is kept above 90% after the continuous feeding for 100h in the stability investigation, and even reaches 96% in the later stage. Therefore, the application adopts the metal-loaded hierarchical porous molecular sieve to realize continuous production on the fixed bed reactor.
Catalyst CAT-1 # 、CAT-3 # ~CAT-9 # With catalyst CAT-2 # Has similar stability effect.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (13)
1. A synthesis method of 2, 5-furan dimethanol dialkyl ether is characterized in that a reaction raw material containing 2, 5-furan dimethanol and alkyl alcohol is introduced into a fixed bed reactor filled with a catalyst, and the reaction raw material reacts with the catalyst in a contact way to prepare the 2, 5-furan dimethanol dialkyl ether;
the alkyl alcohol has a structural formula shown in a formula I: R-OH formula I;
wherein R is C 2 ~ C 10 Alkyl of (a);
the catalyst comprises a metal-supported hierarchical pore ZSM-5 molecular sieve;
the metal-loaded hierarchical-pore ZSM-5 molecular sieve contains mesopores;
the average pore diameter of the mesopores is 2-20 nm, and the volume of the mesopores is 0.2-0.6 mL/g;
the metal element in the metal-loaded hierarchical pore ZSM-5 molecular sieve is at least one of Sn, mg and Zn, and the metal element loading amount is 0.1-10wt%;
the metal load is calculated according to the load of the metal element;
the particle size of the multistage hole ZSM-5 molecular sieve is 100-400 nm, and the specific surface area is 400-700 m 2 And/g, wherein the atomic ratio of silicon to aluminum is 10-500.
2. The method for synthesizing 2, 5-furandimethanol dialkyl ether according to claim 1, wherein the method for preparing the molecular sieve comprises the following steps:
1) Preparing a raw material containing a silicon source, an aluminum source, a template agent and an alcohol compound into xerogel;
2) Crystallizing the xerogel in an atmosphere containing water vapor under a closed condition to obtain a hierarchical pore ZSM-5 molecular sieve;
3) Immersing the hierarchical pore ZSM-5 molecular sieve in a solution containing a metal element precursor, and then drying and roasting to obtain the metal-loaded hierarchical pore ZSM-5 molecular sieve.
3. The method for synthesizing 2, 5-furandimethanol dialkyl ether according to claim 1, wherein step 1) is to mix a silicon source, an aluminum source, a template agent and an alcohol compound to obtain a raw material gel; drying the obtained raw material gel at 20-40 ℃ for at least 24 hours to obtain the xerogel;
the molar ratio of the silicon source, the aluminum source, the template agent and the alcohol compound in the raw materials is as follows:
silicon source: aluminum source: template agent: alcohol compound=1.01 to 1.1: 0.002-0.1: 0.1 to 0.3: 10-1000;
wherein the mole number of the silicon source is SiO 2 Calculated in terms of mole number of aluminum source and Al 2 O 3 The mole number of the template agent is calculated by the mole number of the template agent per se, and the mole number of the alcohol compound is calculated by the mole number of the alcohol compound per se.
4. The method for synthesizing 2, 5-furandimethanol dialkyl ether according to claim 1, wherein the crystallization time in the step 2) is 48-120 hours, and the crystallization temperature is 150-200 ℃.
5. The method for synthesizing 2, 5-furandimethanol dialkyl ether according to claim 1, wherein the crystallization time in the step 2) is 60-96 h; the crystallization temperature is 160-190 ℃.
6. The method for synthesizing 2, 5-furandimethanol dialkyl ether according to claim 1, wherein the metal element in the step 3) is at least one selected from Sn, mg, zn.
7. The method for synthesizing 2, 5-furandimethanol dialkyl ether according to claim 2, wherein the metal element precursor is selected from at least one of Sn chloride, sn sulfate, sn nitrate, mg chloride, mg sulfate, mg nitrate, zn chloride, zn sulfate, zn nitrate;
the impregnation in the step 3) is an isovolumetric impregnation method, and the metal loading is 0.1-wt% -10-wt%; the metal loading is calculated as the loading of the metal element.
8. The method for synthesizing 2, 5-furandimethanol dialkyl ether according to claim 1, wherein the metal loading in step 3) is 1wt% -5 wt%; the metal loading is calculated as the loading of the metal element.
9. The method for synthesizing 2, 5-furandimethanol dialkyl ether according to claim 1, wherein the alkyl alcohol is ethanol.
10. The method for synthesizing 2, 5-furandimethanol dialkyl ether according to claim 1, wherein the concentration of 2, 5-furandimethanol in the reaction raw material is 1-50 g/L.
11. The method for synthesizing 2, 5-furandimethanol dialkyl ether according to claim 1, wherein the mass space velocity of the 2, 5-furandimethanol is 0.1-3 h -1 。
12. The method for synthesizing 2, 5-furandimethanol dialkyl ether according to claim 1, wherein the reaction temperature of the reaction raw material containing 2, 5-furandimethanol and alkyl alcohol and the catalyst in the contact reaction is 100-160 ℃.
13. The method for synthesizing 2, 5-furandimethanol dialkyl ether according to claim 1, wherein the reaction pressure of the reaction raw material containing 2, 5-furandimethanol and alkyl alcohol and the catalyst in the contact reaction is 0.1-3 mpa.
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2462872A1 (en) * | 2012-10-25 | 2014-05-26 | Consejo Superior De Investigaciones Científicas (Csic) | Catalyst and catalytic process for the etherification/reduction of furfuryl derivatives to tetrahydrofurfuryl ethers |
CN104226357A (en) * | 2013-06-21 | 2014-12-24 | 中国石油天然气股份有限公司 | Multistage pore molecular sieve catalyst, preparation and application |
CN104628682A (en) * | 2015-02-16 | 2015-05-20 | 大连大学 | Method for preparing alkoxymethyl furfural by catalyzing 5-hydroxymethylfurfural |
WO2016043589A1 (en) * | 2014-09-19 | 2016-03-24 | Rijksuniversiteit Groningen | Method for reducing hydroxymethylfurfural (hmf) |
CN106866332A (en) * | 2017-02-08 | 2017-06-20 | 大连理工大学 | A kind of benzene and methanol alkylation catalyst and application |
CN106946820A (en) * | 2017-03-29 | 2017-07-14 | 厦门大学 | The synthetic method of 2,5 furyl dimethyl carbinols and its etherification product |
CN107303497A (en) * | 2016-04-22 | 2017-10-31 | 中国石油化工股份有限公司 | A kind of multi-stage porous dehydrogenation and preparation method thereof |
CN107903225A (en) * | 2017-12-13 | 2018-04-13 | 厦门大学 | A kind of method that 5 hydroxymethylfurfurals are prepared with glucose |
CN108178164A (en) * | 2018-02-11 | 2018-06-19 | 四川润和催化新材料股份有限公司 | A kind of multi-stage porous ZSM-5 molecular sieve and preparation method thereof prepares the method for PX catalyst with it |
WO2018182948A1 (en) * | 2017-03-27 | 2018-10-04 | Exxonmobil Chemical Patents Inc. | Methane conversion |
-
2019
- 2019-01-31 CN CN201910097614.9A patent/CN111495419B/en active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2462872A1 (en) * | 2012-10-25 | 2014-05-26 | Consejo Superior De Investigaciones Científicas (Csic) | Catalyst and catalytic process for the etherification/reduction of furfuryl derivatives to tetrahydrofurfuryl ethers |
CN104226357A (en) * | 2013-06-21 | 2014-12-24 | 中国石油天然气股份有限公司 | Multistage pore molecular sieve catalyst, preparation and application |
WO2016043589A1 (en) * | 2014-09-19 | 2016-03-24 | Rijksuniversiteit Groningen | Method for reducing hydroxymethylfurfural (hmf) |
CN104628682A (en) * | 2015-02-16 | 2015-05-20 | 大连大学 | Method for preparing alkoxymethyl furfural by catalyzing 5-hydroxymethylfurfural |
CN107303497A (en) * | 2016-04-22 | 2017-10-31 | 中国石油化工股份有限公司 | A kind of multi-stage porous dehydrogenation and preparation method thereof |
CN106866332A (en) * | 2017-02-08 | 2017-06-20 | 大连理工大学 | A kind of benzene and methanol alkylation catalyst and application |
WO2018182948A1 (en) * | 2017-03-27 | 2018-10-04 | Exxonmobil Chemical Patents Inc. | Methane conversion |
CN106946820A (en) * | 2017-03-29 | 2017-07-14 | 厦门大学 | The synthetic method of 2,5 furyl dimethyl carbinols and its etherification product |
CN107903225A (en) * | 2017-12-13 | 2018-04-13 | 厦门大学 | A kind of method that 5 hydroxymethylfurfurals are prepared with glucose |
CN108178164A (en) * | 2018-02-11 | 2018-06-19 | 四川润和催化新材料股份有限公司 | A kind of multi-stage porous ZSM-5 molecular sieve and preparation method thereof prepares the method for PX catalyst with it |
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