CN112371168B - Zirconium phosphate loaded SAPO-34 molecular sieve catalyst, preparation method thereof and application thereof in preparation of gamma-valerolactone by catalyzing furfural - Google Patents
Zirconium phosphate loaded SAPO-34 molecular sieve catalyst, preparation method thereof and application thereof in preparation of gamma-valerolactone by catalyzing furfural Download PDFInfo
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 88
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 44
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910000166 zirconium phosphate Inorganic materials 0.000 title claims abstract description 40
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000005580 one pot reaction Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 229910019142 PO4 Inorganic materials 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 20
- 229910017677 NH4H2 Inorganic materials 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 229910006213 ZrOCl2 Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000002243 precursor Substances 0.000 abstract description 5
- 238000009901 transfer hydrogenation reaction Methods 0.000 abstract description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006136 alcoholysis reaction Methods 0.000 abstract description 4
- 238000006266 etherification reaction Methods 0.000 abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 241000269350 Anura Species 0.000 description 25
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000000725 suspension Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000002841 Lewis acid Substances 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 150000007517 lewis acids Chemical class 0.000 description 8
- 239000007848 Bronsted acid Substances 0.000 description 7
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- YEQMNLGBLPBBNI-UHFFFAOYSA-N difurfuryl ether Chemical compound C=1C=COC=1COCC1=CC=CO1 YEQMNLGBLPBBNI-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- GVIIRWAJDFKJMJ-UHFFFAOYSA-N propan-2-yl 3-oxobutanoate Chemical compound CC(C)OC(=O)CC(C)=O GVIIRWAJDFKJMJ-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000003541 multi-stage reaction Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JOOXCMJARBKPKM-UHFFFAOYSA-M 4-oxopentanoate Chemical compound CC(=O)CCC([O-])=O JOOXCMJARBKPKM-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229940058352 levulinate Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- HYNNRPKIDNLCIR-UHFFFAOYSA-N propan-2-yl 4-hydroxypentanoate Chemical compound C(C)(C)OC(CCC(C)O)=O HYNNRPKIDNLCIR-UHFFFAOYSA-N 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- GHDUNCWYKYHSHJ-VMPITWQZSA-N (e)-4-propan-2-yloxypent-3-en-2-one Chemical compound CC(C)O\C(C)=C\C(C)=O GHDUNCWYKYHSHJ-VMPITWQZSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- OCAIYHCKLADPEG-UHFFFAOYSA-N n-Valeriansaeureisopropylester Natural products CCCCC(=O)OC(C)C OCAIYHCKLADPEG-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000012688 phosphorus precursor Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- MGJRGGIHFUREHT-UHFFFAOYSA-N propan-2-yl 4-oxopentanoate Chemical compound CC(C)OC(=O)CCC(C)=O MGJRGGIHFUREHT-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a zirconium phosphate loaded SAPO-34 molecular sieve catalyst, a preparation method thereof and application thereof in catalyzing furfural to prepare gamma-valerolactone. The zirconium phosphate loaded SAPO-34 molecular sieve catalyst is obtained by simple precipitation, stirring, loading and calcination, and the catalytic activity of the catalyst can be improved by adjusting the proportion of the zirconium element precursor and the phosphorus element precursor. The zirconium phosphate loaded SAPO-34 molecular sieve has multifunctional activities of high-efficiency catalytic transfer hydrogenation, etherification, alcoholysis and the like, and can realize the one-pot synthesis of gamma-valerolactone by catalyzing furfural in isopropanol.
Description
Technical Field
The invention relates to the technical field of organic compounds, in particular to preparation of gamma-valerolactone.
Background
The development and utilization of fossil resources have greatly promoted the progress of human socioeconomic performance, but also resulted in the generation of a large amount of greenhouse gases and the destruction of the environment, so the development of sustainable clean energy resources that can replace fossil resources is attracting increasing attention. The biomass resource has abundant reserves and can be regenerated, and fuels, materials, high value-added chemicals and the like can be prepared by various utilization modes. Among various biomass-based chemicals, gamma-valerolactone can be used as a platform molecule for preparing other high value-added chemicals, materials and liquid fuels. Because of the safe and nontoxic characteristics of gamma-valerolactone, the gamma-valerolactone serving as a green solvent has wide application prospect in biomass conversion and organic synthesis. In addition, gamma-valerolactone can be an excellent fuel additive because of its lower saturated vapor pressure and higher energy density compared to ethanol. At present, the furfural production from cellulose biomass such as corncobs and the like is industrialized, so that the preparation of gamma-valerolactone by catalytic conversion of furfural is considered to be a synthesis path of gamma-valerolactone with great prospect.
The conversion of furfural into gamma-valerolactone in isopropanol involves multiple reactions such as hydrogenation, alcoholysis or etherification, and the reaction process requires the synergistic effect of Lewis acid and Bronsted acid. Specifically, as shown in fig. 1, furfural (FF) undergoes MPV transfer hydrogenation reduction using isopropanol as a hydrogen source to produce Furfuryl Alcohol (FA) under the catalysis of lewis acid ([ L ]), and then undergoes etherification with solvent alcohol under the action of lewis acid or bronsted acid ([ B ]) to produce Furfuryl Ether (FE); furfuryl Ether (FE) is catalyzed by Bronsted acid to form isopropyl acetoacetate (IPL) through alcoholysis ring-opening reaction; under the condition of taking isopropanol as a hydrogen source, the carbonyl at the 4-position in the isopropyl acetylacetonate (IPL) molecule is further transferred and hydrogenated and reduced into hydroxyl under the action of Lewis acid to obtain 4-hydroxy isopropyl valerate (IPHV); isopropyl 4-hydroxypentanoate (IPHV) readily continues to cyclize to remove one molecule of isopropanol to form more stable gamma-valerolactone (GVL). The furfural and furfuryl alcohol are easy to generate side reactions such as polycondensation and the like under the action of Bronsted acid to obtain humus, so that the selectivity of a target reaction product is low; meanwhile, stronger Lewis acid is needed for catalyzing the transfer hydrogenation of levulinate to synthesize valerolactone, so that a catalyst with stronger Lewis acid sites and proper Bronsted acid sites is needed for efficiently catalyzing furfural to convert valerolactone. However, designing and synthesizing such multifunctional acid catalysts is still a technical difficulty to be solved.
Recently, noble metal and zirconium-based catalysts are widely used for preparing gamma-valerolactone by catalytic conversion of furfural by a one-pot method with isopropanol as a solvent and a hydrogen donor. However, as mentioned above, the preparation of gamma-valerolactone by furfural one-pot hydrogenation with isopropanol as a solvent involves multi-step reaction and has a long route, so that the yield of gamma-valerolactone is generally not high at present. In addition, the use cost of the noble metal is high, and the furfural can be converted to synthesize valerolactone by the combined action of an acid catalyst and the like, so that the recovery and separation of the catalyst are not facilitated, and therefore, the design of a cheap and efficient multifunctional catalyst is extremely important.
In conclusion, because the process of preparing gamma-valerolactone by catalytic conversion of furfural involves multi-step reactions, and the requirements of each step of reaction on reaction conditions and catalytic active sites are greatly different, the development of an economical, green and efficient multifunctional catalyst and a catalytic system is urgently needed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a zirconium phosphate loaded SAPO-34 molecular sieve catalyst, a preparation method thereof and application thereof in preparing gamma-valerolactone by catalyzing furfural. The invention provides a simple and convenient method for preparing zirconium phosphate loaded SAPO-34 molecular sieve catalyst. In the method, the needed multifunctional acid catalyst can be obtained through simple precipitation, stirring, loading and calcination, and the effective regulation and control of the contents of Lewis acid and Bronsted acid can be realized by regulating the proportion of the zirconium element precursor and the phosphorus element precursor, so that the catalytic activity of the catalyst is greatly improved, and the catalyst can be promoted to realize the efficient catalytic furfural one-pot method synthesis of gamma-valerolactone in isopropanol.
One of the technical schemes adopted by the invention for solving the technical problems is as follows:
a zirconium phosphate loaded SAPO-34 molecular sieve catalyst is prepared by adding NH4H2PO4The ZrOCl is dripped into the aqueous solution2And adding SAPO-34 into the aqueous solution, stirring for 3-6 h at room temperature, standing for 7-10 h, performing solid-liquid separation, drying and grinding a solid part, and calcining for 3-5 h at 380-420 ℃ to obtain the zirconium phosphate loaded SAPO-34 molecular sieve catalyst, which is named as ZrP (x)/SAPO (y), wherein x represents the molar ratio of Zr to P, and y represents the addition amount of the SAPO-34 molecular sieve.
Further, the molar ratio of Zr to P is 0.5-2: 1.
further, NH4H2PO4The mass ratio of the SAPO-34 is 0.50-0.52: 0.5 to 2.
Under the above conditions, x is 0.5 to 2, and y is 0.5 to 2. Wherein the addition amount of the SAPO-34 molecular sieve is relative to NH4H2PO4When the addition amount of (b) is 0.50-0.52 g, the mass of the added SAPO-34 molecular sieve is calculated.
Preferably, the molar ratio of Zr to P is 0.8-1.2: 1, NH4H2PO4The mass ratio of the SAPO-34 is 0.50-0.51 g: 1.4-1.6 g. Under the condition, the zirconium phosphate loaded SAPO-34 molecular sieve catalyst has better catalytic activity.
Further, NH4H2PO4The concentration of the aqueous solution is 0.8-1.2 mol/L; ZrOCl2The concentration of the aqueous solution is 0.25-1 mol/L.
The second technical scheme adopted by the invention for solving the technical problems is as follows:
a zirconium phosphate loaded SAPO-34 molecular sieve catalyst prepared according to the preparation method. The catalyst can be named as ZrP (x)/SAPO (y), wherein x represents the molar ratio of Zr to P, and x is 0.5-2; y represents relative to NH4H2PO4When the amount of (b) is 0.50-0.52 g, the mass of the SAPO-34 molecular sieve is 0.5-2.
The third technical scheme adopted by the invention for solving the technical problems is as follows:
an application of the zirconium phosphate loaded SAPO-34 molecular sieve catalyst in preparation of gamma-valerolactone.
The fourth technical scheme adopted by the invention for solving the technical problems is as follows:
the method for preparing gamma-valerolactone by using the zirconium phosphate loaded SAPO-34 molecular sieve catalyst comprises the steps of mixing furfural and isopropanol, adding the zirconium phosphate loaded SAPO-34 molecular sieve catalyst, and reacting under a closed condition, wherein the reaction temperature is 135-175 ℃, and the reaction time is 4-22 hours.
Preferably, in the raw materials for preparing the zirconium phosphate loaded SAPO-34 molecular sieve catalyst, the molar ratio of Zr to P is 0.8-1.2: 1, NH4H2PO4The mass ratio of the SAPO-34 is 0.50-0.51 g: 1.4-1.6 g; the reaction temperature for preparing gamma-valerolactone by catalyzing furfural with the zirconium phosphate loaded SAPO-34 molecular sieve catalyst is 168-172 ℃, and the reaction time is 5.5-10 h. Under the conditions, the conversion rate of furfural is 100%, and the yield of gamma-valerolactone is about 74.7-80%. More preferably, when the reaction time is 5.8-6.2 h, the yield of the gamma-valerolactone reaches about 80%.
Preferably, in the raw materials for preparing the zirconium phosphate loaded SAPO-34 molecular sieve catalyst, the molar ratio of Zr to P is 0.8-1.2: 1, NH4H2PO4The mass ratio of the SAPO-34 is 0.50-0.51 g: 1.4-1.6 g; the reaction temperature for preparing gamma-valerolactone by catalyzing furfural with the zirconium phosphate loaded SAPO-34 molecular sieve catalyst is 148-152 ℃, and the reaction time is 17-19 h. Under the conditions, the conversion rate of the furfural is 100 percent, and the yield of the gamma-valerolactone is about 80 percent.
Preferably, in the raw materials for preparing the zirconium phosphate loaded SAPO-34 molecular sieve catalyst, the molar ratio of Zr to P is 0.8-1.2: 1, NH4H2PO4The mass ratio of the SAPO-34 is 0.50-0.51 g: 1.4-1.6 g; the reaction temperature for preparing gamma-valerolactone by catalyzing furfural with the zirconium phosphate loaded SAPO-34 molecular sieve catalyst is 138-142 ℃, and the reaction time is 13-22 h. Under the conditions, the conversion rate of furfural is 100%, and the yield of gamma-valerolactone is about 71.1-75%. More preferably, when the reaction time is 13.5-14.5 h, the yield of the gamma-valerolactone reaches about 75%.
The equipment, reagents, processes, parameters and the like related to the invention are conventional equipment, reagents, processes, parameters and the like except for special description, and no embodiment is needed.
All ranges recited herein include all point values within the range.
As used herein, "about" or "about" and the like refer to a range or value within plus or minus 20 percent of the stated range or value.
In the invention, the room temperature, namely the normal environment temperature, can be 10-30 ℃.
Compared with the background technology, the technical scheme has the following advantages:
1. the invention develops a method for loading zirconium phosphate on an SAPO-34 molecular sieve, and the supported catalyst prepared by the method can be used as a multifunctional acid catalyst; and the preparation process of the catalyst is simple, and the catalytic activity of the supported catalyst can be effectively adjusted and improved by adjusting the ratio of the zirconium precursor salt to the phosphorus precursor salt.
2. The zirconium phosphate loaded SAPO-34 molecular sieve catalyst developed by the invention can efficiently catalyze multi-step reactions such as furfural transfer hydrogenation, furfuryl alcohol etherification and ring-opening alcoholysis, and gamma-valerolactone synthesis by levulinate transfer hydrogenation, so that the catalytic furfural one-pot method can be realized to efficiently prepare gamma-valerolactone, the technical problem that the non-noble metal catalyst efficiently catalyzes furfural one-pot method to synthesize gamma-valerolactone is solved, and the defects that the conventional furfural conversion of gamma-valerolactone depends on a complex catalytic system and is low in efficiency are overcome.
Drawings
FIG. 1 is a diagram illustrating the mechanistic pathways for the catalytic hydrogenation of furfural to gamma-valerolactone in isopropanol (FF: furfural, FA: furfuryl alcohol, FE: furfuryl ether, IPL: isopropyl levulinate, IPHV: isopropyl 4-hydroxypentanoate, GVL: gamma-valerolactone, L: Lewis acid, B: Bronsted acid).
Detailed Description
The present invention will be described in detail with reference to the following examples:
examples 1 to 4
First, 0.506g NH was weighed4H2PO4Dissolved in 4.4mL of deionized water. In addition, 1.4g of ZrOCl was weighed2·8H2O in 8.8mL deionized water, and the NH was stirred4H2PO4The ZrOCl is slowly dropped into the water solution2·8H2In the aqueous O solution, a milky white precipitate suspension gradually formed. Then 0.5g, 1g, 1.5g or 2g of SAPO-34 powder is weighed into the suspension, stirred vigorously at room temperature for 4h and then allowed to stand for 8h, after which the insoluble solids are filtered and dried. And grinding the dried solid, and calcining at 400 ℃ for 4h to obtain the zirconium phosphate loaded SAPO-34 molecular sieve. The catalysts are respectively marked as: ZrP (1)/SAPO (0.5), ZrP (1)/SAPO (1), ZrP (1) </or >SAPO(1.5)、ZrP(1)/SAPO(2)。
Adding 0.096g of furfural and 20mL of isopropanol into a 50mL autoclave, adding 0.192g of ZrP (1)/SAPO (0.5), ZrP (1)/SAPO (1) or ZrP (1)/SAPO (2) serving as a catalyst, sealing the reaction kettle, introducing nitrogen to purge four times to completely remove air in the kettle, stirring vigorously (500rpm), heating to 150 ℃ and keeping for 10 hours, cooling to room temperature after the reaction is finished, sampling and detecting, wherein the detection results are listed as serial numbers 1-4 in Table 1.
Examples 5 to 8
First, 0.506g NH was weighed4H2PO4Dissolved in 4.4mL of deionized water. Separately, 0.708g, 1.4g, 2.13g or 2.83g of zirconium oxychloride (ZrOCl) was weighed2·8H2O) was dissolved in 8.8mL of deionized water, and the NH was added with stirring4H2PO4The ZrOCl is slowly dropped into the water solution2·8H2In the aqueous O solution, a milky white precipitate suspension gradually formed. 1.5g of SAPO-34 powder are subsequently weighed into the suspension and stirred vigorously at room temperature for 4 hours and then left to stand for 8 hours, after which the insoluble solids are filtered off and dried. And grinding the dried solid, and calcining at 400 ℃ for 4h to obtain the zirconium phosphate loaded SAPO-34 molecular sieve. The catalysts are respectively marked as: ZrP (0.5)/SAPO (1.5), ZrP (1)/SAPO (1.5), ZrP (1.5)/SAPO (1.5), ZrP (2)/SAPO (1.5).
Adding 0.096g of furfural and 20mL of isopropanol into a 50mL autoclave, respectively adding 0.192g of ZrP (0.5)/SAPO (1.5), ZrP (1)/SAPO (1.5), ZrP (1.5)/SAPO (1.5) or ZrP (2)/SAPO (1.5) as catalysts, sealing the reaction kettle, introducing nitrogen to purge four times to completely remove air in the kettle, violently stirring (500rpm), heating to 150 ℃ for 10 hours, cooling to room temperature after the reaction is finished, sampling and detecting, wherein the detection results are listed as serial numbers 5-8 in Table 1.
Examples 9 to 12
First, 0.506g NH was weighed4H2PO4Dissolved in 4.4mL of deionized water. In addition, 1.4g of ZrOCl was weighed2·8H2O in 8.8mL deionized water, and the NH was stirred4H2PO4Aqueous solutionZrOCl is slowly dropped2·8H2In the aqueous O solution, a milky white precipitate suspension gradually formed. 1.5g of SAPO-34 powder are subsequently weighed into the suspension and stirred vigorously at room temperature for 4 hours and then left to stand for 8 hours, after which the insoluble solids are filtered off and dried. And grinding the dried solid, and calcining at 400 ℃ for 4h to obtain the zirconium phosphate loaded SAPO-34 molecular sieve. The catalyst was labeled: ZrP (1)/SAPO (1.5).
Adding 0.096g of furfural and 20mL of isopropanol into a 50mL autoclave, adding 0.192g of ZrP (1)/SAPO (1.5) as a catalyst, sealing the reaction kettle, introducing nitrogen to purge the reaction kettle for four times to completely remove air in the kettle, violently stirring the reaction kettle (500rpm), heating the reaction kettle to 140 ℃ and keeping the reaction kettle for 10 hours, 14 hours, 18 hours and 22 hours, cooling the reaction kettle to room temperature after the reaction is finished, sampling and detecting, wherein the detection results are listed as serial numbers 9-12 in Table 1.
Examples 13 to 16
First, 0.506g NH was weighed4H2PO4Dissolved in 4.4mL of deionized water. In addition, 1.4g of ZrOCl was weighed2·8H2O in 8.8mL deionized water, and the NH was stirred4H2PO4The ZrOCl is slowly dropped into the water solution2·8H2In the aqueous O solution, a milky white precipitate suspension gradually formed. 1.5g of SAPO-34 powder are subsequently weighed into the suspension and stirred vigorously at room temperature for 4 hours and then left to stand for 8 hours, after which the insoluble solids are filtered off and dried. And grinding the dried solid, and calcining at 400 ℃ for 4h to obtain the zirconium phosphate loaded SAPO-34 molecular sieve. The catalyst was labeled: ZrP (1)/SAPO (1.5).
Adding 0.096g of furfural and 20mL of isopropanol into a 50mL autoclave, adding 0.192g of ZrP (1)/SAPO (1.5) as a catalyst, sealing the reaction kettle, introducing nitrogen to purge the reaction kettle for four times to completely remove air in the kettle, violently stirring the reaction kettle (500rpm), heating the reaction kettle to 150 ℃ and keeping the reaction kettle for 10 hours, 14 hours, 18 hours and 22 hours, cooling the reaction kettle to room temperature after the reaction is finished, sampling and detecting, wherein the detection results are listed as serial numbers 13-16 in Table 1.
Examples 17 to 20
First, 0.506g NH was weighed4H2PO4Dissolved in 4.4mL of deionized water.In addition, 1.4g of ZrOCl was weighed2·8H2O in 8.8mL deionized water, and the NH was stirred4H2PO4The ZrOCl is slowly dropped into the water solution2·8H2In the aqueous O solution, a milky white precipitate suspension gradually formed. 1.5g of SAPO-34 powder are subsequently weighed into the suspension and stirred vigorously at room temperature for 4 hours and then left to stand for 8 hours, after which the insoluble solids are filtered off and dried. And grinding the dried solid, and calcining at 400 ℃ for 4h to obtain the zirconium phosphate loaded SAPO-34 molecular sieve. The catalyst was labeled: ZrP (1)/SAPO (1.5).
Adding 0.096g of furfural and 20mL of isopropanol into a 50mL autoclave, adding 0.192g of ZrP (1)/SAPO (1.5) as a catalyst, sealing the reaction kettle, introducing nitrogen to purge the reaction kettle for four times to completely remove air in the kettle, violently stirring the reaction kettle (500rpm), heating the reaction kettle to 160 ℃ and keeping the temperature for 4, 8, 12 and 16 hours, finishing the reaction, cooling the reaction kettle to room temperature and sampling the reaction kettle, and performing qualitative and quantitative detection by using GC (Agilent 7890A), wherein the detection results are listed as serial numbers 17-20 in Table 1.
Examples 21 to 24
First, 0.506g NH was weighed4H2PO4Dissolved in 4.4mL of deionized water. In addition, 1.4g of ZrOCl was weighed2·8H2O in 8.8mL deionized water, and the NH was stirred4H2PO4The ZrOCl is slowly dropped into the water solution2·8H2In the aqueous O solution, a milky white precipitate suspension gradually formed. 1.5g of SAPO-34 powder are subsequently weighed into the suspension and stirred vigorously at room temperature for 4 hours and then left to stand for 8 hours, after which the insoluble solids are filtered off and dried. And grinding the dried solid, and calcining at 400 ℃ for 4h to obtain the zirconium phosphate loaded SAPO-34 molecular sieve. The catalyst was labeled: ZrP (1)/SAPO (1.5).
Adding 0.096g of furfural and 20mL of isopropanol into a 50mL autoclave, respectively adding 0.192g of ZrP (1)/SAPO (1.5) serving as a catalyst, sealing the reaction kettle, introducing nitrogen to purge the reaction kettle for four times to completely remove air in the kettle, violently stirring the reaction kettle (500rpm), heating the reaction kettle to 170 ℃ and keeping the reaction kettle for 4 hours, 6 hours, 8 hours and 10 hours, cooling the reaction kettle to room temperature after the reaction is finished, sampling the reaction kettle, and carrying out qualitative and quantitative detection by using GC (Agilent 7890A), wherein the detection results are listed as serial numbers 21-24 in Table 1.
TABLE 1 test results in examples
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (9)
1. A preparation method of zirconium phosphate loaded SAPO-34 molecular sieve catalyst for catalyzing furfural to prepare gamma-valerolactone by a one-pot method is characterized by comprising the following steps: reacting NH4H2PO4The ZrOCl is dripped into the aqueous solution2Adding SAPO-34 into the aqueous solution, stirring at room temperature for 3-6 h, standing for 7-10 h, performing solid-liquid separation, drying and grinding a solid part, and calcining at 380-420 ℃ for 3-5 h to obtain the zirconium phosphate loaded SAPO-34 molecular sieve catalyst; said ZrOCl2Zr in (1) and the NH4H2PO4The molar ratio of P in (1) is (0.5-2): 1; the NH4H2PO4The mass ratio of the SAPO-34 is 0.50-0.52: 0.5 to 2.
2. The method of claim 1, wherein: said ZrOCl2Zr in (1) and the NH4H2PO4The molar ratio of P in (1) is (0.8-1.2): 1, said NH4H2PO4The mass ratio of the SAPO-34 is 0.50-0.51: 1.4 to 1.6.
3. The method of claim 1, wherein: the NH4H2PO4The concentration of the aqueous solution is 0.8-1.2 mol/L; said ZrOCl2The concentration of the aqueous solution is 0.25-1 mol/L.
4. A zirconium phosphate supported SAPO-34 molecular sieve catalyst prepared according to the preparation method of any one of claims 1 to 3.
5. The application of the zirconium phosphate loaded SAPO-34 molecular sieve catalyst of claim 4 in preparing gamma-valerolactone by furfural catalysis one-pot method.
6. A method for preparing gamma-valerolactone by catalyzing furfural with the zirconium phosphate loaded SAPO-34 molecular sieve catalyst is characterized by comprising the following steps: mixing furfural and isopropanol, adding the zirconium phosphate loaded SAPO-34 molecular sieve catalyst, and reacting under a closed condition at the temperature of 135-175 ℃ for 4-22 h.
7. The method of claim 6, wherein: the zirconium phosphate supported SAPO-34 molecular sieve catalyst prepared according to the preparation method of claim 2; the reaction temperature for preparing gamma-valerolactone by catalyzing furfural with the zirconium phosphate loaded SAPO-34 molecular sieve catalyst is 168-172 ℃, and the reaction time is 5.5-10 h.
8. The method of claim 6, wherein: the zirconium phosphate supported SAPO-34 molecular sieve catalyst prepared according to the preparation method of claim 2; the reaction temperature for preparing gamma-valerolactone by catalyzing furfural with the zirconium phosphate loaded SAPO-34 molecular sieve catalyst is 148-152 ℃, and the reaction time is 17-19 h.
9. The method of claim 6, wherein: the zirconium phosphate supported SAPO-34 molecular sieve catalyst prepared according to the preparation method of claim 2; the reaction temperature for preparing gamma-valerolactone by catalyzing furfural with the zirconium phosphate loaded SAPO-34 molecular sieve catalyst is 138-142 ℃, and the reaction time is 13-22 h.
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