CN115448832A - Biomass derivative gamma-valerolactone double-guide conversion method - Google Patents
Biomass derivative gamma-valerolactone double-guide conversion method Download PDFInfo
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- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000002028 Biomass Substances 0.000 title claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 107
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 74
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 50
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 36
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000010457 zeolite Substances 0.000 claims abstract description 36
- 239000007787 solid Substances 0.000 claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229940005605 valeric acid Drugs 0.000 claims abstract description 13
- 239000000047 product Substances 0.000 claims description 44
- 239000007789 gas Substances 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 238000011068 loading method Methods 0.000 claims description 24
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 9
- 239000000446 fuel Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 description 34
- 238000002360 preparation method Methods 0.000 description 18
- 239000002994 raw material Substances 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 11
- 239000012263 liquid product Substances 0.000 description 11
- 239000011949 solid catalyst Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000011049 filling Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- 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
- B01J29/42—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 iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
- C07C1/213—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by splitting of esters
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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
- 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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention relates to the technical field of energy catalysis, in particular to a method for double-guide conversion of a biomass derivative gamma-valerolactone, which is characterized in that gamma-valerolactone gas is subjected to gas-solid heterogeneous reaction in the presence of a Ni/HZSM-5 catalyst, and the double-guide selective switching of the gamma-valerolactone to a pentanoic acid product and a pentane product is realized by adjusting the silica-alumina ratio of an HZSM-5 zeolite carrier in the Ni/HZSM-5 catalyst. The invention can realize the catalytic reaction performance of highly flexible and accurately controllable double-guide selective switching of gamma-valerolactone to valeric acid (the selectivity is as high as 97.3%) and pentane fuel (the selectivity is as high as 93.6%) mainly by simply adjusting the silica-alumina ratio of an HZSM-5 zeolite carrier in the Ni/HZSM-5 catalyst and assisting the modulation of metallic nickel load.
Description
Technical Field
The invention relates to the technical field of energy catalysis, in particular to a method for double-guide conversion of a biomass derivative gamma-valerolactone.
Background
With the transition from fossil-based consumer products to alternative energy carriers based on renewable biomass resources, there is a wide range of interest in designing highly selective catalytic systems to efficiently convert sustainable biomass-derived compounds into high-value-for-use fuels and chemicals [ annu. Currently, researchers have focused on controlling the complex reaction pathways in the catalytic conversion of biomass by various methods to optimize the selectivity of the target product. For example, (1) the active metal component is modified to take advantage of its unique intrinsic selectivity; (2) Changing the size of the metal nanoparticles to adjust their surface electronic and geometric properties; (3) Changing the reaction conditions (temperature, pressure or solvent, etc.) to adjust the product selectivity, etc. However, few studies report multifunctional catalytic systems with switchable product selectivity characteristics to achieve flexible control over the synthesis of various high value-added biomass-based products.
As a versatile biomass-based platform compound, gamma valerolactone can be used as an energy molecule for the synthesis of various fuels and chemicals. At present, in the process of catalytic conversion of gamma-valerolactone, reaction systems of traditional strategies such as high-temperature pyrolysis, phosphoric acid homogeneous catalysis or noble metal hydrogenation and the like lack sufficient functionality to realize accurate regulation and control of gamma-valerolactone series reaction channels, so that the problems of more byproducts, unsatisfactory selectivity control and the like are caused. Whereas, the gamma-valerolactone multistage catalytic system based on the "break-up-to-zero" reaction decoupling strategy suffers from the problems of tedious multi-step process, high-energy-consumption product separation/purification, selective control of only a single product, and the like [ Green chem.2010,12,992-999 ]. Therefore, a novel multifunctional catalytic system is designed, and a cascade reaction channel of gamma-valerolactone is driven in a multi-guide manner in the catalytic conversion process of the gamma-valerolactone by a simple operation method, so that flexible selective switching of various high-value products is realized, and the method is a target which has a great prospect but has a great challenge.
Disclosure of Invention
The invention aims to provide a method for double-guide conversion of biomass derivative gamma-valerolactone, which can realize the highly flexible and accurately controllable catalytic reaction performance of the gamma-valerolactone on valeric acid (the selectivity is as high as 97.3%) and pentane fuel (the selectivity is as high as 93.6%) by simply adjusting the silicon-aluminum ratio of an HZSM-5 zeolite carrier in a Ni/HZSM-5 catalyst under the mild reaction condition and assisting the modulation of metal nickel loading.
The scheme adopted by the invention for realizing the purpose is as follows: a method for double-guide conversion of biomass derivative gamma-valerolactone is characterized in that gamma-valerolactone gas is subjected to gas-solid heterogeneous reaction in the presence of a Ni/HZSM-5 catalyst, and double-guide selective switching of the gamma-valerolactone to a pentanoic acid product and a pentane product is realized by adjusting the silica-alumina ratio of an HZSM-5 zeolite carrier in the Ni/HZSM-5 catalyst.
Preferably, the Si/Al ratio of the HZSM-5 zeolite carrier in the Ni/HZSM-5 catalyst is in a range of 15-300, and when the Si/Al ratio of the HZSM-5 zeolite carrier is gradually increased from 15 to 300, the main product generated by the conversion of gamma-valerolactone is gradually switched from pentanoic acid to pentane.
Preferably, the loading amount of the metallic nickel in the Ni/HZSM-5 catalyst accounts for 0.5 wt% to 40 wt% of the mass of the HZSM-5 zeolite carrier.
Preferably, the preferred reaction conditions for the conversion of gamma valerolactone to pentanoic acid product are: the temperature is 110-240 ℃, the pressure is 0.5-3.0 MPa, and the space velocity is 0.2-0.1 h -1 。
Preferably, the preferred reaction conditions for the conversion of gamma valerolactone to pentane product are: the temperature is 200-260 ℃, the pressure is 0.5-2.0 MPa, and the space velocity is 0.1-0.9 h -1 。
Preferably, the Ni/HZSM-5 catalyst is prepared by the following method: preparing nickel salt aqueous solution with certain concentration, adding HZSM-5 zeolite with certain mass into the solution, stirring at room temperature until the mixture is uniformly mixed, drying, roasting at 500-520 ℃ for 4-6 hours in air atmosphere, and finally reducing at 400-450 ℃ in hydrogen atmosphere to obtain the Ni/HZSM-5 catalyst.
Preferably, the nickel salt is at least one of nickel nitrate, nickel chloride, nickel sulfate, nickel acetate and nickel acetylacetonate.
Preferably, the preparation method of the HZSM-5 zeolite carrier is as follows: firstly, adding a certain amount of tetraethyl orthosilicate into a certain amount of tetrapropyl ammonium hydroxide aqueous solution, stirring at 30-35 ℃ until the tetraethyl orthosilicate and the aluminum isopropoxide are uniformly mixed, then adding deionized water and aluminum isopropoxide into the mixed solution, then carrying out hydrothermal crystallization on the obtained mixed solution at 170-110 ℃ for 60-10 hours, carrying out centrifugal separation on a product after crystallization is finished, washing the obtained solid product to be neutral, drying, and roasting at 520-550 ℃ in the air atmosphere to remove tetrapropyl ammonium hydroxide in zeolite, thus obtaining the HZSM-5 zeolite carrier.
Preferably, the molar ratio of the tetraethyl orthosilicate to the aluminum isopropoxide to the tetrapropylammonium hydroxide to the water is 30 (0.1-2.0) to 1.1.
The invention has the following advantages and beneficial effects:
according to the method for the double-guide conversion of the biomass derivative gamma-valerolactone, disclosed by the invention, under a mild reaction condition through a multifunctional catalytic system based on an HZSM-5 zeolite-loaded nickel-based catalyst, the highly flexible and accurately controllable catalytic reaction performance of the gamma-valerolactone on the valeric acid (the selectivity is up to 97.3%) and the pentane fuel (the selectivity is up to 93.6%) by simply adjusting the silica-alumina ratio of an HZSM-5 zeolite carrier in the Ni/HZSM-5 catalyst and assisting the modulation of the metal nickel loading amount can be realized, and the method has wide industrial application prospects in the fields of energy and catalysis.
The nickel-based catalyst used in the invention has the advantages of simple preparation method and low cost, and can be produced, transported and stored in a large scale.
The invention innovatively provides a reaction route of gamma-valerolactone double-guide conversion, and flexibly realizes the double-guide selective switching performance of gamma-valerolactone on valeric acid and pentane fuel.
In the reaction system, valeric acid and pentane are two main products generated by converting gamma-valerolactone, and almost no other byproducts are contained, so that the high efficiency of the designed Ni/HZSM-5 catalyst for double-guide catalysis of the gamma-valerolactone is reflected.
Drawings
FIG. 1 is a graph of the catalytic performance of 10Ni/HZSM-5 (SAR) series of catalysts prepared in example 1 of the present invention;
FIG. 2 is a TEM image of 0.5Ni/HZSM-5 (15) catalyst, no. 3, according to example 2 of the present invention;
FIG. 3 is a graph of the catalytic performance of a sample of a series of xNi/HZSM-5 (15) catalysts of example 1 of the present invention co-produced by numbering 1 and example 2;
FIG. 4 is a TEM micrograph of 40Ni/HZSM-5 (300) catalyst numbered 3 in example 3 of the present invention;
FIG. 5 is a graph of the catalytic performance of a sample of the xNi/HZSM-5 (300) series of catalysts of example 1 of the present invention co-produced by numbering 4 and example 3;
FIG. 6 is the catalytic stability results for 0.5Ni/HZSM-5 (15) catalyst under the best mode of operation in example 10 of the present invention;
FIG. 7 shows the results of catalytic stability of the 40Ni/HZSM-5 (300) catalyst under the best mode of the invention in example 11.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
The catalyst in the invention is marked as xNi/HZSM-5 (SAR), wherein x represents the loading (wt.%) of metallic nickel, and SAR is the molar ratio of silicon element to aluminum element (Si/Al) in the HZSM-5 zeolite carrier.
Example 1
In this embodiment, the γ -valerolactone raw material passes through a continuous flow fixed bed reactor filled with a Ni/HZSM-5 solid catalyst, and performs a gas-solid heterogeneous reaction under a certain working condition, taking a 10Ni/HZSM-5 (15) catalyst sample as an example, the preparation steps are as follows: firstly preparing nickel nitrate aqueous solution with a certain concentration, adding a proper amount of HZSM-5 (15) Zeolite support, so that the mass of metallic nickel is 10wt.% of the mass of the Zeolite support, and stirring at room temperature for 20 hours. And then drying the obtained mixture at the temperature of 100 ℃ for 12 hours, roasting the mixture at the temperature of 500 ℃ for 5 hours in the air atmosphere, and finally reducing the mixture for 4 hours in the hydrogen atmosphere at the temperature of 400 ℃ to obtain a 10Ni/HZSM-5 (15) catalyst sample, wherein the number of the catalyst sample is 1. Wherein, the preparation steps of the HZSM-5 (15) zeolite carrier are as follows: an amount of tetraethyl orthosilicate (TEOS) was first added to an amount of tetrapropylammonium hydroxide (TPAOH) aqueous solution and stirred in a 35 ℃ water bath for 3 hours. To the mixed solution, deionized water and aluminum isopropoxide (Al (OPri) 3 ) The molar composition of each material in the mixture was 30TEOS 3 :1.1TPAOH:1110H 2 And O. The resulting mixed solution was then transferred to a polytetrafluoroethylene-lined 100mL hydrothermal kettle and hydrothermally crystallized at a temperature of 170 ℃ for 72 hours. After crystallization is finished, the obtained solid product is centrifugally washed to be neutral by desalted water, then dried for 12 hours at the temperature of 100 ℃, and roasted for 6 hours in the air atmosphere of 540 ℃ to obtain the HZSM-5 (15) zeolite carrier. In addition, similar to the above synthesis method of the 10Ni/HZSM-5 (15) catalyst sample (No. 1), the silica-alumina ratio of the HZSM-5 zeolite support in the prepared Ni/HZSM-5 catalyst was adjusted while adjusting the amount of aluminum isopropoxide added during the preparation of the HZSM-5 zeolite support without changing the remaining preparation steps. For this reason, in this example, when the molar ratio of each substance in the zeolite support synthesis mother liquor was 30TEOS 3 :1.1TPAOH:1110H 2 When O is needed, a 10Ni/HZSM-5 (50) catalyst sample can be prepared and is numbered as 2; when the molar ratio of each substance in the zeolite carrier synthesis mother solution is 30TEOS 3 :1.1TPAOH:1110H 2 When O is needed, a 10Ni/HZSM-5 (150) catalyst sample can be prepared and is numbered as 3; when the mole ratio of each substance in the zeolite carrier synthesis mother liquor is 30TEOS 3 :1.1TPAOH:1110H 2 O, a 10Ni/HZSM-5 (300) catalyst sample was prepared, numbered 4.
0.5g of 10Ni/HZSM-5 (SAR) catalyst samples (numbered 1, 2, 3 and 4 respectively) prepared as described above and having different silica to alumina ratios (15, 50, 150 and 300) were weighed and charged into a fixed bed reactor, and the catalyst system was subjected toIntroducing hydrogen to the system pressure of 1.0MPa, heating the catalyst to 200 ℃ in the hydrogen flow atmosphere, introducing gamma-valerolactone into the reactor by using a high-pressure constant flow pump, and adjusting the constant flow pump to ensure that the mass airspeed of the gamma-valerolactone is 0.6h -1 . After 5 hours of reaction, the liquid product was collected by a cold trap and analyzed by an off-line gas chromatograph, and the gas product was analyzed by an on-line gas chromatograph, and the results are shown in table 1, as shown in fig. 1, which is a graph of the catalytic performance of the 10Ni/HZSM-5 (SAR) series catalyst samples prepared in this example, and it can be seen from the graph: under the same working conditions, the 10Ni/HZSM-5 (SAR) series catalyst has selectivity switching performance of 'eliminating long one another' for two products of valeric acid and pentane. The selectivity of both products is highly dependent on the silica to alumina ratio (SAR) of the HZSM-5 support, i.e., lower SAR favors the formation of the pentanoic acid product, while higher SAR favors the formation of the pentane product.
Example 2
In the embodiment, the gamma-valerolactone raw material passes through a continuous flow type fixed bed reactor filled with a Ni/HZSM-5 solid catalyst and performs gas-solid multiphase reaction under certain working conditions. Wherein, HZSM-5 (15) is used as zeolite carrier, and the loading of metallic nickel in the corresponding Ni/HZSM-5 catalyst can be adjusted by adjusting the adding amount of nickel nitrate in the preparation process of the Ni/HZSM-5 catalyst. Based on this, this example employed similar preparation procedures as the catalyst sample numbered 1 in example 1 to separately prepare a 5Ni/HZSM-5 (15) catalyst sample having a metallic nickel loading of 5wt.% which was numbered 1; a 1Ni/HZSM-5 (15) catalyst sample was prepared with a metallic nickel loading of 1wt.%, numbered 2; a transmission electron micrograph of a 0.5Ni/HZSM-5 (15) catalyst sample having a metallic nickel loading of 0.5wt.% is shown in fig. 2, which shows that: for the 0.5Ni/HZSM-5 (15) catalyst sample with lower nickel loading, the surface nickel nanoparticles were uniformly dispersed and the metallic nickel particle size was about 3.5nm.
0.5g of the above prepared xNi/HZSM-5 (15) catalyst samples (numbered 1, 2 and 3 respectively) having different metallic nickel loadings (5 wt.%, 1wt.% and 0.5 wt.%) were weighed into a fixed bed reactor and the catalyst was chargedIntroducing hydrogen into the chemical system until the system pressure is 1.0MPa, heating the catalyst to 200 ℃ in the hydrogen flow atmosphere, introducing gamma-valerolactone into the reactor by using a high-pressure constant flow pump, and adjusting the constant flow pump to ensure that the mass space velocity of the gamma-valerolactone is 0.6h -1 . After 5 hours of reaction, the liquid product was collected by a cold trap and analyzed by an offline gas chromatograph, and the gaseous product was analyzed by an online gas chromatograph, and the results are listed in table 1. The catalytic performance of the xNi/HZSM-5 (15) series of catalyst samples with different metallic nickel loadings (10 wt.%, 5wt.%, 1wt.% and 0.5 wt.%) is shown in figure 3, from which it can be seen that: the xNi/HZSM-5 (15) catalyst system with a specific silica to alumina ratio of 15 always showed higher catalytic synthesis capacity for the pentanoic acid product, and in addition, although the selectivity of pentanoic acid and pentane products in the conversion process of gamma-valerolactone is influenced to some extent by the nickel loading, the metallic nickel loading does not have the catalytic performance of switching the pentanoic acid/pentane selectivity.
Example 3
In the embodiment, the gamma-valerolactone raw material passes through a continuous flow type fixed bed reactor filled with a Ni/HZSM-5 solid catalyst and carries out gas-solid multiphase reaction under certain working conditions. Wherein, HZSM-5 (300) is used as zeolite carrier, and the loading of metallic nickel in the corresponding Ni/HZSM-5 catalyst can be adjusted by adjusting the adding amount of nickel nitrate in the preparation process of the Ni/HZSM-5 catalyst. Based on this, this example employed similar preparation procedures as the catalyst sample numbered 4 in example 1, to separately prepare a 20Ni/HZSM-5 (300) catalyst sample having a metallic nickel loading of 20wt.%, which was numbered 1; a 30Ni/HZSM-5 (300) catalyst sample was prepared with a metallic nickel loading of 30wt.%, numbered 2; a transmission electron micrograph of a 40Ni/HZSM-5 (300) catalyst sample, numbered 3, with a 40Ni/HZSM-5 (300) catalyst having a metallic nickel loading of 40wt.% is shown in fig. 4, from which it can be seen that: for a 40Ni/HZSM-5 (300) catalyst sample with higher nickel loading, the surface of the catalyst sample has obvious metal nickel agglomeration phenomenon, and the particle size of the metal nickel can reach 50nm.
Weigh 0.5g of the above prepared powders with different metal nickel loadings (20 wt.%, 30wt.% and 40wt. -%)) Filling xNi/HZSM-5 (300) catalyst samples (the serial numbers are 1, 2 and 3 respectively) into a fixed bed reactor, introducing hydrogen into a catalytic system until the system pressure is 1.0MPa, heating the catalyst to 200 ℃ under the hydrogen flow atmosphere, then introducing gamma-valerolactone into the reactor by using a high-pressure constant flow pump, and simultaneously adjusting the constant flow pump to ensure that the mass space velocity of the gamma-valerolactone is 0.6h -1 . After 5 hours of reaction, the liquid product was collected by a cold trap and analyzed by an off-line gas chromatograph, and the gaseous product was analyzed by an on-line gas chromatograph, and the results obtained are listed in table 1. The catalytic performance of the xNi/HZSM-5 (300) series of catalyst samples with different metallic nickel loadings (10 wt.%, 20wt.%, 30wt.%, and 40 wt.%) is shown in fig. 5, from which it can be seen that: the xNi/HZSM-5 (300) catalyst system with a specific silica to alumina ratio of 300 always exhibited a higher catalytic synthesis capacity for the pentane product and, in addition, similar to the xNi/HZSM-5 (15) catalyst system (fig. 3), the metallic nickel loading did not have catalytic properties to switch the pentanoic acid/pentane selectivity, although the selectivity of pentanoic acid and pentane products during the conversion of gamma valerolactone would be affected to some extent by the nickel loading.
Example 4
In this example, the γ -valerolactone feedstock passed through a continuous flow fixed bed reactor packed with a solid catalyst and was subjected to a gas-solid heterogeneous reaction under certain operating conditions, and the preparation procedure of the 0.5Ni/HZSM-5 (15) catalyst used was the same as that of the catalyst sample numbered 3 in example 2.
Weighing 0.5g of 0.5Ni/HZSM-5 (15) catalyst sample, filling the sample into a fixed bed reactor, introducing hydrogen into a catalytic system until the system pressure is 1.0MPa, respectively heating the catalyst to 110 ℃ (number 1), 220 ℃ (number 2) and 240 ℃ (number 3) in the hydrogen flow atmosphere, introducing gamma-valerolactone raw material into the reactor by using a high-pressure constant flow pump, and simultaneously adjusting the constant flow pump to enable the mass space velocity of the gamma-valerolactone to be 0.6h -1 . After 5 hours of reaction, the liquid product was collected by a cold trap and analyzed by an offline gas chromatograph, and the gaseous product was analyzed by an online gas chromatograph, and the results are listed in table 1.
Example 5
In this example, the γ -valerolactone raw material passed through a continuous flow fixed bed reactor packed with a solid catalyst and underwent a gas-solid heterogeneous reaction under a certain working condition, and the preparation procedure of the 0.5Ni/HZSM-5 (15) catalyst used was the same as that of the catalyst sample numbered 3 in example 2.
Weighing 0.5g of 0.5Ni/HZSM-5 (15) catalyst sample, filling the sample into a fixed bed reactor, introducing hydrogen into a catalytic system until the system pressure is respectively 0.5MPa (number 1), 2.0MPa (number 2) and 3.0MPa (number 3), heating the catalyst to 220 ℃ in the hydrogen flow atmosphere, introducing a gamma-valerolactone raw material into the reactor by using a high-pressure constant flow pump, and simultaneously adjusting the constant flow pump to ensure that the mass space velocity of the gamma-valerolactone is 0.6h -1 . After 5 hours of reaction, the liquid product was collected by a cold trap and analyzed by an offline gas chromatograph, and the gaseous product was analyzed by an online gas chromatograph, and the results are listed in table 1.
Example 6
In this example, the γ -valerolactone raw material passed through a continuous flow fixed bed reactor packed with a solid catalyst and underwent a gas-solid heterogeneous reaction under a certain working condition, and the preparation procedure of the 0.5Ni/HZSM-5 (15) catalyst used was the same as that of the catalyst sample numbered 3 in example 2.
Weighing 0.5g of 0.5Ni/HZSM-5 (15) catalyst sample, filling the sample into a fixed bed reactor, introducing hydrogen into a catalytic system until the system pressure is 2.0MPa, heating the catalyst to 220 ℃ in the hydrogen flow atmosphere, introducing a gamma-valerolactone raw material into the reactor by using a high-pressure constant flow pump, and simultaneously adjusting the constant flow pump to ensure that the mass space velocity of the gamma-valerolactone is 0.2h respectively -1 (number 1) 0.4h -1 (number 2) and 0.1h -1 (No. 3). After 5 hours of reaction, the liquid product was collected by a cold trap and analyzed by an offline gas chromatograph, and the gaseous product was analyzed by an online gas chromatograph, and the results are listed in table 1.
Example 7
In this example, the γ -valerolactone raw material passed through a continuous flow fixed bed reactor packed with a solid catalyst and underwent a gas-solid heterogeneous reaction under a certain working condition, and the preparation procedure of the 40Ni/HZSM-5 (300) catalyst used was the same as that of the catalyst sample numbered 3 in example 3.
Weighing 0.5g of 40Ni/HZSM-5 (300) catalyst sample, filling the sample into a fixed bed reactor, introducing hydrogen into a catalytic system until the system pressure is 1.0MPa, respectively heating the catalyst to 220 ℃ (number 1), 240 ℃ (number 2) and 260 ℃ (number 3) in the hydrogen flow atmosphere, introducing gamma-valerolactone raw material into the reactor by using a high-pressure constant flow pump, and simultaneously adjusting the constant flow pump to enable the mass airspeed of the gamma-valerolactone to be 0.6h -1 . After 5 hours of reaction, the liquid product was collected by a cold trap and analyzed by an offline gas chromatograph, and the gaseous product was analyzed by an online gas chromatograph, and the results are listed in table 1.
Example 8
In this example, the γ -valerolactone raw material passed through a continuous flow fixed bed reactor packed with a solid catalyst and underwent a gas-solid heterogeneous reaction under a certain working condition, and the preparation procedure of the 40Ni/HZSM-5 (300) catalyst used was the same as that of the catalyst sample numbered 3 in example 3.
Weighing 0.5g of 40Ni/HZSM-5 (300) catalyst sample, filling the sample into a fixed bed reactor, introducing hydrogen into a catalytic system until the system pressure is respectively 0.5MPa (number 1), 1.5MPa (number 2) and 2.0MPa (number 3), heating the catalyst to 240 ℃ in the hydrogen flow atmosphere, introducing a gamma-valerolactone raw material into the reactor by using a high-pressure constant flow pump, and simultaneously adjusting the constant flow pump to ensure that the mass space velocity of the gamma-valerolactone is 0.6h -1 . After 5 hours of reaction, the liquid product was collected by a cold trap and analyzed by an offline gas chromatograph, and the gaseous product was analyzed by an online gas chromatograph, and the results are listed in table 1.
Example 9
In this example, the γ -valerolactone feedstock passed through a continuous flow fixed bed reactor packed with a solid catalyst and was subjected to a gas-solid heterogeneous reaction under certain operating conditions, and the preparation procedure of the 40Ni/HZSM-5 (300) catalyst used was the same as that of the catalyst sample numbered 3 in example 3.
0.5g of 40Ni/HZSM-5 (300) catalyst sample was weighed and charged into a fixed bed reactor, and hydrogen was introduced into the catalytic system until the system pressure was 1.0MPa, heating the catalyst to 240 ℃ in the hydrogen flow atmosphere, introducing the gamma-valerolactone raw material into the reactor by using a high-pressure constant flow pump, and adjusting the constant flow pump to ensure that the mass space velocity of the gamma-valerolactone is 0.1h respectively -1 (number 1) 0.3h -1 (number 2) and 0.9h -1 (No. 3). After 5 hours of reaction, the liquid product was collected by a cold trap and analyzed by an off-line gas chromatograph, and the gaseous product was analyzed by an on-line gas chromatograph, and the results obtained are listed in table 1.
TABLE 1
As can be seen from the data in Table 1, for the gas-solid heterogeneous catalytic system, the Ni/HZSM-5 catalyst has high efficiency in catalytic conversion of gamma-valerolactone and also has unique double-direction selectivity switching capability. The selectivity of the valeric acid product is in negative correlation with the silica-alumina ratio of the HZSM-5 zeolite carrier, and the selectivity of the pentane product is in positive correlation with the silica-alumina ratio of the HZSM-5 zeolite carrier, so that the valeric acid/pentane double-direction selectivity switching performance depending on the silica-alumina ratio of the Ni/HZSM-5 zeolite carrier in the gamma-valerolactone conversion process is formed, and the modulation metal nickel loading capacity and the reaction working condition do not have the catalytic performance of switching the valeric acid/pentane selectivity.
Example 10
In this example, the γ -valerolactone feedstock passed through a continuous flow fixed bed reactor packed with a solid catalyst and was subjected to a gas-solid heterogeneous reaction under certain operating conditions, and the preparation procedure of the 0.5Ni/HZSM-5 (15) catalyst used was the same as that of the catalyst sample numbered 3 in example 2.
Weighing 1.0g of 0.5Ni/HZSM-5 (15) catalyst sample, filling the sample into a fixed bed reactor, introducing hydrogen into a catalytic system until the system pressure is 2.0MPa, heating the catalyst to 220 ℃ under the hydrogen flow atmosphere, and then utilizing high pressure and constant pressureThe gamma-valerolactone raw material is led into the reactor by the flow pump, and the constant flow pump is adjusted to lead the mass space velocity of the gamma-valerolactone to be 0.4h -1 . The catalytic reaction was continuously run for 70 hours to investigate the catalytic stability of the 0.5Ni/HZSM-5 (15) catalyst, the liquid product was collected every 5 hours by a cold trap and analyzed by an off-line gas chromatograph, the gas product was analyzed by an on-line gas chromatograph, and the results are shown in fig. 6, from which it can be seen that: the 0.5Ni/HZSM-5 (15) catalyst system always shows higher gamma-valerolactone conversion rate in the reaction process of up to 70 hours, the selectivity of a valeric acid product is in a slightly increased trend along with the passage of reaction time, and the selectivity of valeric acid after 70 hours of reaction can reach 97.3 percent, which shows that the 0.5Ni/HZSM-5 (15) catalyst has excellent selectivity control capability of valeric acid and good catalytic stability in the conversion process of gamma-valerolactone.
Example 11
In this example, the γ -valerolactone raw material passed through a continuous flow fixed bed reactor packed with a solid catalyst and underwent a gas-solid heterogeneous reaction under a certain working condition, and the preparation procedure of the 40Ni/HZSM-5 (300) catalyst used was the same as that of the catalyst sample numbered 3 in example 3.
Weighing 1.0g of 40Ni/HZSM-5 (300) catalyst sample, filling the sample into a fixed bed reactor, introducing hydrogen into a catalytic system until the system pressure is 1.0MPa, heating the catalyst to 240 ℃ in the hydrogen flow atmosphere, introducing a gamma-valerolactone raw material into the reactor by using a high-pressure constant flow pump, and simultaneously adjusting the constant flow pump to ensure that the mass space velocity of the gamma-valerolactone is 0.3h -1 . The catalytic reaction was continuously run for 70 hours to investigate the catalytic stability of the 40Ni/HZSM-5 (300) catalyst, the liquid product was collected every 5 hours by a cold trap and analyzed by an off-line gas chromatograph, the gas product was analyzed by an on-line gas chromatograph, and the results are shown in fig. 7, from which it can be seen that: the 40Ni/HZSM-5 (300) catalyst system always shows higher gamma-valerolactone conversion rate in the reaction process of up to 70 hours, the selectivity of pentane products has a slight trend of increasing along with the reaction time, and the selectivity of pentane after 70 hours of reaction can reach 93.6%, which shows that the 40Ni/HZSM-5 (300) catalyst is used for converting gamma-valerolactoneThe catalyst has excellent pentane selectivity control capability and good catalytic stability in the chemical process.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (9)
1. A method for double-guide conversion of biomass derivative gamma-valerolactone is characterized in that gamma-valerolactone gas is subjected to gas-solid heterogeneous reaction in the presence of a Ni/HZSM-5 catalyst, and double-guide selective switching of the gamma-valerolactone to a pentanoic acid product and a pentane product is realized by adjusting the silica-alumina ratio of an HZSM-5 zeolite carrier in the Ni/HZSM-5 catalyst.
2. The method for the dual-direction conversion of the biomass derivative gamma-valerolactone according to claim 1, wherein the Si/Al ratio of the HZSM-5 zeolite carrier in the Ni/HZSM-5 catalyst ranges from 15 to 300, and the main product generated by the conversion of the gamma-valerolactone is gradually switched from valeric acid to pentane when the Si/Al ratio of the HZSM-5 zeolite carrier is gradually increased from 15 to 300.
3. The method for the dual-directed conversion of the biomass derivative gamma-valerolactone according to claim 1, wherein the Ni/HZSM-5 catalyst has a metal nickel loading of 0.5wt.% to 40wt.% based on the weight of the HZSM-5 zeolite support.
4. The method for the bi-directional conversion of a biomass derivative, gamma-valerolactone, according to claim 1, wherein the preferred reaction conditions for the conversion of gamma-valerolactone to a pentanoic acid product are: the temperature is 110-240 ℃, the pressure is 0.5-3.0 MPa, and the space velocity is 0.2-0.1 h -1 。
5. The method for the double-directed conversion of a biomass derivative, gamma-valerolactone, according to claim 1, wherein the preferred reaction conditions for the conversion of gamma-valerolactone to pentane product are: the temperature is 200-260 ℃, the pressure is 0.5-2.0 MPa, and the space velocity is 0.1-0.9 h -1 。
6. The method for the double-directed conversion of the biomass derivative gamma-valerolactone according to claim 1, wherein the Ni/HZSM-5 catalyst is prepared by a method comprising: preparing nickel salt aqueous solution with certain concentration, adding HZSM-5 zeolite with certain mass into the solution, stirring at room temperature until the mixture is uniformly mixed, drying, roasting at 500-520 ℃ for 4-6 hours in air atmosphere, and finally reducing at 400-450 ℃ in hydrogen atmosphere to obtain the Ni/HZSM-5 catalyst.
7. The method for the dual-directional conversion of the biomass derivative gamma-valerolactone according to claim 6, wherein the nickel salt is at least one of nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, nickel acetylacetonate.
8. The method for the double-directed conversion of the biomass derivative gamma-valerolactone according to claim 6, characterized in that the HZSM-5 zeolite support used is prepared by the following steps: firstly, adding a certain amount of tetraethyl orthosilicate into a certain amount of tetrapropyl ammonium hydroxide aqueous solution, stirring at 30-35 ℃ until the tetraethyl orthosilicate and the aluminum isopropoxide are uniformly mixed, then adding deionized water and aluminum isopropoxide into the mixed solution, then carrying out hydrothermal crystallization on the obtained mixed solution at 170-110 ℃ for 60-10 hours, carrying out centrifugal separation on a product after crystallization is finished, washing the obtained solid product to be neutral, drying, and roasting at 520-550 ℃ in the air atmosphere to remove tetrapropyl ammonium hydroxide in zeolite, thus obtaining the HZSM-5 zeolite carrier.
9. The method for the double-guide conversion of the biomass derivative gamma-valerolactone according to claim 1, wherein the molar ratio of tetraethyl orthosilicate, aluminum isopropoxide, tetrapropylammonium hydroxide and water is 30 (0.1-2.0) to 1.1.
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