CN113136240B - Method for selectively preparing C5-C6 liquid alkane from cellulose biomass raw material through aqueous phase catalytic conversion - Google Patents

Method for selectively preparing C5-C6 liquid alkane from cellulose biomass raw material through aqueous phase catalytic conversion Download PDF

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CN113136240B
CN113136240B CN202110396450.7A CN202110396450A CN113136240B CN 113136240 B CN113136240 B CN 113136240B CN 202110396450 A CN202110396450 A CN 202110396450A CN 113136240 B CN113136240 B CN 113136240B
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iridium
catalyst
raw material
molecular sieve
liquid alkane
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CN113136240A (en
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张琦
李松
晋乐乐
刘琪英
张兴华
马隆龙
王晨光
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Guangzhou Institute of Energy Conversion of CAS
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • 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
    • B01J29/48—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 arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7815—Zeolite Beta
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • 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
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

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Abstract

The invention discloses a method for selectively preparing C5-C6 liquid alkane by aqueous phase catalytic conversion of a cellulose biomass raw material. A method for selectively preparing C5-C6 liquid alkane from cellulose biomass raw materials through aqueous phase catalytic conversion is characterized in that an iridium-based bimetallic catalyst composite molecular sieve catalyst is used as a catalyst, and the biomass raw materials or cellulose are added into water or a water-containing solvent to be catalytically converted into the C5-C6 liquid alkane. The method takes the biomass raw material as the substrate, avoids using fossil-based products, not only effectively realizes the effective utilization of agriculture and forestry organic solid waste resources, but also alleviates the environmental problem, is green and sustainable, has higher conversion rate of the biomass-based raw material and complete reaction, can recycle the iridium-based bimetallic catalyst used in the reaction, and can also obtain higher yield of C5-C6 liquid alkane under the method.

Description

Method for selectively preparing C5-C6 liquid alkane from cellulose biomass raw material through aqueous phase catalytic conversion
The technical field is as follows:
the invention relates to the technical field of biomass catalytic conversion, in particular to a method for selectively preparing C5-C6 liquid alkane from cellulose biomass raw materials through aqueous phase catalytic conversion.
The background art comprises the following steps:
with the gradual decrease of traditional non-renewable energy sources and the more serious environmental problems of air pollution, global warming and the like in recent years, the search for a renewable clean energy source is urgent. The biomass resource has rich reserves, and compared with novel energy sources such as wind energy, tidal energy and the like, the biomass energy is the only carbon neutral renewable energy source, and the development and the utilization of the biomass energy can not cause greenhouse effect. Lignocellulosic biomass is an inedible part of biomass resources, such as agricultural and forestry waste, municipal waste, and the like. Mainly comprises three parts of cellulose (40-50%), hemicellulose (20-40%) and lignin (20-30%). In recent years, extensive and intensive research has been conducted on the conversion of lignocellulosic biomass into transportation fuels and high value-added chemicals.
C5-C6 alkane is an important component of the existing gasoline and is indispensable in the aspects of improving the octane number of the gasoline, adjusting the steam pressure and the like, and the preparation of C5-C6 liquid fuel by using biomass-based raw materials is rapidly developed in recent years, but the yield is relatively low, the conversion condition is harsh, the product is complex, and the separation and the purification are difficult. This method, like other liquid fuel production methods, has corresponding drawbacks.
The invention content is as follows:
in order to solve the technical problem of preparing liquid alkane from biomass-based raw materials, the invention provides a method for selectively preparing C5-C6 liquid alkane from cellulose-based biomass raw materials through aqueous phase catalytic conversion.
The invention aims to provide a method for selectively preparing C5-C6 liquid alkane by aqueous phase catalytic conversion of cellulose biomass raw materials, which takes an iridium-based bimetallic catalyst composite molecular sieve catalyst as a catalyst and adds water or a water-containing solvent into the biomass raw materials or cellulose to perform catalytic conversion to the C5-C6 liquid alkane.
The iridium-based bimetallic catalyst can be used for efficiently converting biomass-based raw materials to obtain high liquid alkane yield. The invention takes the biomass-based raw material as the substrate, avoids using fossil-based products, not only effectively realizes the effective utilization of resources, but also reduces the environmental problem, and is green and sustainable. The invention has the advantages of high conversion rate of biomass-based raw materials, complete reaction, recyclable iridium-based bimetallic catalyst used in the reaction, and high yield of C5-C6 liquid alkane under the method. The catalyst is simple to separate from the product, is environment-friendly, and has important significance for establishing a sustainable energy system and protecting the ecological environment.
Preferably, the solvent is a mixed solvent of nonpolar liquid alkane and water, and the volume ratio of the nonpolar liquid alkane to the water is (1-20): (1-20).
Preferably, the method specifically comprises the following steps: adding water into an iridium-based bimetallic catalyst, placing the iridium-based bimetallic catalyst into a reaction container, sealing the reaction container, filling 2-6MPa of hydrogen into the reaction container, carrying out reduction pretreatment on the catalyst, after the pretreatment is finished, cooling the reaction container to room temperature, opening the reaction container to discharge the hydrogen, adding nonpolar liquid alkane, simultaneously placing a biomass raw material or cellulose and a molecular sieve catalyst into the reaction container, sealing the reaction container, filling 1-8MPa of hydrogen into the reaction container, stirring, heating the reaction container to 170-280 ℃, reacting for 1-24 hours, and obtaining the C5-C6 liquid alkane after the reaction is finished.
Preferably, the iridium-based bimetallic catalyst is prepared by the following steps: impregnating the silicon-based material with an iridium source and/or a tungsten source, drying and calcining to obtain the iridium-based bimetallic catalyst.
More preferably, the iridium source is iridium chloride or chloroiridic acid, the tungsten source is ammonium paratungstate, the loading amount of metal in the iridium-based bimetallic catalyst is 4-15%, and the atomic ratio of tungsten to iridium is (0-5): 1.
more preferably, the atomic ratio of tungsten to iridium is (0.03 to 0.5): 1.
preferably, the impregnation time is 1-24h, and the impregnation temperature is 10-200 ℃; the drying time is 1-24h, and the drying temperature is 40-200 ℃; the calcination time is 1-24h, and the calcination temperature is 300-700 ℃.
Preferably, in the iridium-based bimetallic catalyst composite molecular sieve catalyst, the mass ratio of the iridium-based bimetallic catalyst to the molecular sieve catalyst is (1-10): (1-10), the mass ratio of the biomass-based raw material to the iridium-based bimetallic catalyst composite molecular sieve catalyst is 1-100: 1.
preferably, the molecular sieve catalyst is selected from more than one of beta molecular sieve, ZSM molecular sieve and Y molecular sieve.
Preferably, the C5-C6 liquid alkane is a liquid mixture of n-pentane, isopentane, n-hexane and isohexane.
Compared with the prior art, the invention has the following advantages:
1. the biomass-based raw material is used as a reaction substrate, the silicon-based metal catalyst and the molecular sieve are used as catalysts, the liquid alkane is obtained in a dodecane and water two-phase solution by a one-pot method, the two-phase system enables products to be easily separated, and the process is simpler.
2. The biomass-based raw materials used in the invention are abundant in natural reserves, renewable and easily available.
3. Under the best condition, the biomass-based raw material can be completely converted, the problem of incomplete conversion in the previous catalytic conversion process of the biomass-based raw material is solved, and the main product is C5-C6 liquid alkane which is used as a liquid fuel component, is green and renewable, and has potential application value.
4. The invention uses iridium-based bimetallic catalyst, has the advantages of excellent hydrogenation performance, high thermal stability, reusability and the like, can be recycled for many times, and has simple separation and post-treatment processes.
The specific implementation mode is as follows:
the technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The equipment and reagents used in the present invention are, unless otherwise specified, conventional commercial products in the art.
The invention provides a method for preparing liquid alkane by water-phase catalytic conversion of a cellulose biomass raw material, which takes an iridium-based bimetallic catalyst composite molecular sieve catalyst as a catalyst, and adds water or a water-containing solvent into the biomass raw material or cellulose to catalytically convert the biomass raw material or the cellulose into the C5-C6 liquid alkane.
The biomass raw material used in the present invention is one or more of xylose, xylan, fructose, inulin, glucose, sucrose, starch, cellulose, corn stover, and the like, and the source of the biomass raw material is not particularly limited, and commercially available products known to those skilled in the art may be used.
The method for preparing liquid alkane by aqueous phase catalytic conversion of cellulose biomass raw material is carried out in an aqueous phase system, the solvent is a mixed solvent of nonpolar liquid alkane and water, preferably a mixed solvent of dodecane and water, and the volume ratio of the dodecane to the water is (1-20): (1 to 20), more preferably (1 to 10): (1 to 10), most preferably (1 to 5): (1-5).
The iridium-based bimetallic catalyst is prepared by the following steps: impregnating the silicon-based material with an iridium source and/or a tungsten source, drying and calcining to obtain the iridium-based bimetallic catalyst.
The silicon-based material is not limited in the present invention, and may be any compound known to those skilled in the art that can provide a silicon atom; silica is preferred in the following examples.
The iridium source is not limited in the present invention, and any compound known to those skilled in the art that can provide an iridium atom may be used; iridium chloride or chloroiridate is preferred in the following examples.
The tungsten source is not limited in the present invention, and any compound known to those skilled in the art that can provide a tungsten atom may be used; ammonium paratungstate is preferred in the examples below. The load capacity of metal in the iridium-based bimetallic catalyst is 4-15%, and the atomic ratio of tungsten to iridium is (0-5): 1. in the following examples, the atomic ratio of tungsten to iridium is preferably (0.03 to 0.5): 1.
the present invention is not limited to the specific impregnation operation, and those skilled in the art will be familiar with the impregnation operation. The dipping time is 1-24 h; preferably 1 to 12 hours; most preferably 3 to 12 hours; the dipping temperature is 10-200 ℃, and preferably 20-150 ℃; most preferably 60 ℃ to 120 ℃.
The present invention is not limited to the specific drying method, and those skilled in the art will be familiar with the drying method. The drying temperature is 40-200 ℃, and preferably 60-120 ℃; the drying time is 1 to 24 hours, preferably 3 to 15 hours, and most preferably 9 to 15 hours.
The present invention is not limited to the particular manner of calcination, and is well known to those skilled in the art. The calcining temperature is 300-700 ℃, preferably 400-600 ℃, and most preferably 450-550 ℃; the calcination time is 1-24 h; preferably 1 to 12 hours; most preferably 2 to 5 hours.
In the iridium-based bimetallic catalyst composite molecular sieve catalyst, the mass ratio of the iridium-based bimetallic catalyst to the molecular sieve catalyst is (1-10): (1 to 10), preferably (1 to 7): (1-7); more preferably (1 to 5): (1-5); most preferably (1 to 3): (1-3). The mass ratio of the biomass raw material or the cellulose to iridium-based bimetallic catalyst composite molecular sieve catalyst is 1-100: 1, preferably 1 to 10 in the following examples: 1.
the molecular sieve catalyst is selected from more than one of beta molecular sieve, ZSM molecular sieve and Y molecular sieve.
The depolymerization temperature of the biomass-based raw material is 170-230 ℃, preferably 210-230 ℃, the pressure of depolymerized hydrogen is 1-8MPa, preferably 2-6MPa, and the reaction time is 1-24h, more preferably 2-24 h; most preferably 6 to 24 hours. The heating rate of the invention is 1-10 ℃/min.
The present invention is not limited to reaction vessels, and those skilled in the art are familiar with the art; may be an autoclave. Hydrogen is preferably introduced into the reaction and sealed. After the reaction is completed, cooling is preferably performed, and cooling is preferably performed to a temperature close to the temperature of the ice-water mixture. The cooling method of the present invention is not limited.
After cooling, the reaction solution was collected, and the organic phase and water were addedSeparating the phases, separating out catalyst and residue, and separating the organic phase into liquid alkane in the gas phase measuring part. The liquid alkane provided by the invention is C 5 /C 6 Straight and branched chain alkanes, preferred liquid alkanes in the examples below include n-pentane, isopentane, n-hexane and isohexane.
The following examples use an organic phase external standard GC to detect liquid alkane content. The detection conditions are as follows: SHIMADZU GC-2010, agilent HP-5 capillary column, FID as detector, 50 deg.C for 3min, heating to 250 deg.C at 10 deg.C/min, and keeping the temperature for 3min, with nitrogen as carrier gas.
Example 1
Putting 5g of silicon dioxide powder in a beaker, dissolving 0.57g of chloroiridic acid in 30mL of double distilled water to obtain a chloroiridic acid aqueous solution, adding the iridium-containing solution into the silicon dioxide powder, stirring at 70 ℃ for 6h, putting the mixture into a 120 ℃ oven overnight for 12h to obtain Ir/SiO with the load of 4% 2 Precursor, ir/SiO 2 Calcining the precursor for 3 hours at 500 ℃ to obtain Ir/SiO with the load capacity of 4 percent 2 A catalyst.
Example 2
Putting 5g of silicon dioxide powder in a beaker, dissolving 0.57g of chloroiridic acid in 30mL of double distilled water to obtain a chloroiridic acid aqueous solution, adding the chloroiridic acid aqueous solution into the silicon dioxide powder, stirring at 70 ℃ for 6h, putting the mixture into a 120 ℃ oven overnight for 12h to obtain Ir/SiO with the load of 4% 2 A precursor; then, ammonium paratungstate was dissolved in 30mL of double distilled water at a tungsten to iridium molar ratio of 0.03:1, and added to 4% of Ir/SiO supported on the solution 2 Fully stirring at the medium temperature of 70 ℃, and then baking in an oven at the temperature of 120 ℃ overnight for 12 hours to obtain Ir-WO x /SiO 2 A catalyst precursor; ir-WO x /SiO 2 Calcining the catalyst precursor for 3 hours at 500 ℃ to obtain Ir-WO x (W/Ir＝0.03)/SiO 2 A catalyst.
Example 3
Putting 5g of silicon dioxide powder in a beaker, dissolving 0.37g of iridium chloride in 30mL of double distilled water to obtain an aqueous solution of chloroiridic acid, adding the aqueous solution of chloroiridic acid into the silicon dioxide powder, stirring for 3h at 120 ℃, and putting the mixture in a 60 ℃ oven overnight for 15h to obtain a negative loadIr/SiO with loading capacity of 4% 2 A precursor; then, according to the molar ratio of ammonium paratungstate to iridic chloride of 0.03 2 Stirring for 3h at 120 ℃, then putting the mixture into a 60 ℃ oven overnight for 15h to obtain Ir-WO x /SiO 2 A catalyst precursor; ir-WO x /SiO 2 Calcining the catalyst precursor for 2 hours at 550 ℃ to obtain Ir-WO x (W/Ir＝0.03)/SiO 2 A catalyst.
Example 4
Putting 5g of silicon dioxide powder into a beaker, then dissolving 0.37g of iridium chloride in 30mL of double distilled water to obtain an iridic chloride aqueous solution, adding the iridic chloride aqueous solution into the silicon dioxide powder, stirring at 60 ℃ for 12h, and then putting the silicon dioxide powder into a 200 ℃ oven for 6h to obtain Ir/SiO with the load of 4% 2 A precursor; then, according to the molar ratio of ammonium paratungstate to chloroiridic acid being 0.03 2 Stirring for 12h at the medium temperature of 60 ℃, and then putting into an oven with the temperature of 200 ℃ for 6h to obtain Ir-WO x /SiO 2 A catalyst precursor; ir-WO x /SiO 2 Calcining the catalyst precursor for 5 hours at 450 ℃ to obtain Ir-WO x (W/Ir＝0.03)/SiO 2 A catalyst.
Example 5
As in example 2, except that: iridium-based bimetallic catalyst (Ir-WO) x /SiO 2 Catalyst) the metal loading was 15%, the W/Ir molar ratio was 0.03.
Example 6
As in example 2, except that: ir-WO is prepared according to the molar ratio of W/Ir of 0.06 x (W/Ir＝0.06)/SiO 2 A catalyst.
Example 7
As in example 2, except that: ir-WO is prepared according to a molar W/Ir ratio of 0.13 x (W/Ir＝0.13)/SiO 2 A catalyst.
Example 8
As in example 2, except that: ir-WO is prepared according to a molar W/Ir ratio of 0.25 x (W/Ir＝0.25)/SiO 2 A catalyst.
Example 9
As in example 2, except that: ir-WO is prepared according to a molar W/Ir ratio of 0.5 x (W/Ir＝0.5)/SiO 2 A catalyst.
Example 10
As in example 2, except that: ir-WO is prepared according to the molar ratio of W/Ir 2:1 x (W/Ir＝2)/SiO 2 A catalyst.
Example 11
0.25g of the Ir/SiO obtained in example 1 above are taken 2 Adding the mixture into 8mL of double distilled water, placing the mixture into a 50mL high-pressure kettle, sealing the high-pressure kettle, and filling 4MPa of hydrogen into the high-pressure kettle; and heating the reaction kettle to 200 ℃ under the stirring state, and carrying out reduction pretreatment on the catalyst for 3 hours.
After the pretreatment is finished, after the reaction kettle is cooled to room temperature, hydrogen is discharged, the reaction kettle is opened, 19mL of dodecane is added, 0.5g of cellulose and 0.06g of purchased HZSM-5 are placed in the reaction kettle, and the reaction kettle is sealed and filled with 4MPa of hydrogen; stirring, heating the reaction kettle to 210 ℃, reacting for 24 hours, and cooling in an ice bath after the reaction is finished. The reacted solution was collected and the organic and aqueous phases were separated.
And detecting the content of the liquid alkane by GC (gas chromatography) by using an organic phase external standard method. The detection conditions are as follows: SHIMADZU GC-2010, agilent HP-5 capillary column, FID as detector, 50 deg.C maintaining for 3min, heating to 250 deg.C at 10 deg.C/min and maintaining for 3min, and nitrogen as carrier gas.
And filtering and separating the residual aqueous solution and the catalyst, drying and weighing the collected catalyst and the collected residues, and calculating the conversion rate of the cellulose. The results show that the yield of liquid alkane, which can be determined under the experimental conditions, is 46.4% and the conversion of cellulose is 93.1%.
Example 12
0.25g of Ir-WO prepared in example 2 above was taken x (W/Ir＝0.03)/SiO 2 Adding the mixture into 8mL of double distilled water, placing the mixture into a 50mL high-pressure kettle, sealing the high-pressure kettle, and filling 4MPa of hydrogen into the high-pressure kettle; stirring and heating the reaction kettle to 200 ℃, and carrying out reduction pretreatment on the catalyst for 3 hours.
After the pretreatment is finished, after the reaction kettle is cooled to room temperature, hydrogen is discharged, the reaction kettle is opened, 19mL of dodecane is added, 0.5g of cellulose and 0.06g of purchased HZSM-5 are placed in the reaction kettle, and the reaction kettle is sealed and filled with 4MPa of hydrogen; stirring, heating the reaction kettle to 210 ℃, reacting for 24 hours, and cooling in an ice bath after the reaction is finished. The reacted solution was collected, and the organic and aqueous phases were separated and quantitatively analyzed, respectively.
And filtering the aqueous solution and the catalyst for separation, drying and weighing the collected catalyst and the collected residues, and calculating the conversion rate of the cellulose. The results show that the yield of liquid alkane, which can be determined under the experimental conditions, is 65.2% and the conversion of cellulose is 99.9%.
Example 13
0.18g of Ir-WO prepared as described in example 2 above was taken x (W/Ir＝0.03)/SiO 2 Adding the mixture into 8mL of double distilled water, placing the mixture into a 50mL high-pressure kettle, sealing the high-pressure kettle, and filling 2MPa of hydrogen into the high-pressure kettle; heating the reaction kettle to 190 ℃ under the stirring state, and carrying out reduction pretreatment on the catalyst for 4 hours.
After the pretreatment is finished, after the reaction kettle is cooled to room temperature, hydrogen is discharged, the reaction kettle is opened, 40mL of dodecane is added, 0.24g of cellulose and 0.06g of purchased beta molecular sieve are placed in the reaction kettle, and hydrogen with the pressure of 4MPa is filled after sealing; stirring, heating the reaction kettle to 210 ℃, reacting for 24 hours, and cooling in an ice bath after the reaction is finished.
Example 14
0.06g of the Ir-WO prepared in example 2 above was taken x (W/Ir＝0.03)/SiO 2 Adding the mixture into 8mL of double distilled water, placing the mixture into a 50mL high-pressure kettle, sealing the high-pressure kettle, and filling 6MPa of hydrogen into the high-pressure kettle; and heating the reaction kettle to 210 ℃ under the stirring state, and carrying out reduction pretreatment on the catalyst for 2 hours.
After the pretreatment is finished, after the reaction kettle is cooled to room temperature, hydrogen is discharged, the reaction kettle is opened, 8mL of dodecane is added, meanwhile, 1.20g of cellulose and 0.06g of purchased Y molecular sieve are placed in the reaction kettle, and hydrogen with the pressure of 4MPa is filled after sealing; stirring, heating the reaction kettle to 210 ℃, reacting for 24 hours, and cooling in an ice bath after the reaction is finished.
Example 15
As in example 12, except that: the iridium-based catalyst is Ir-WO x (W/Ir＝0.06)/SiO 2 。
The results show that the yield of liquid alkane that can be determined under this experimental condition is 78.3% and the conversion of cellulose is greater than 99.9%.
Example 16
As in example 12, except that: the iridium-based catalyst is Ir-WO x (W/Ir＝0.13)/SiO 2 。
The results show that the yield of liquid alkane that can be determined under this experimental condition is 78.7% and the conversion of cellulose is greater than 99.9%.
Example 17
As example 12, wherein the iridium-based catalyst used is Ir-WO x (W/Ir＝0.25)/SiO 2 。
The results show that the yield of liquid alkane that can be determined under this experimental condition is 77.9% and the conversion of cellulose is greater than 99.9%.
Example 18
As in example 12, except that: the iridium-based catalyst is Ir-WO x (W/Ir＝0.5)/SiO 2 。
The results show that the yield of liquid alkane that can be determined under this experimental condition is 37.9% and the conversion of cellulose is greater than 97.8%.
Example 19
As in example 12, except that: the iridium-based catalyst is Ir-WO x (W/Ir＝2)/SiO 2 。
The results show that the yield of liquid alkane which can be determined under the experimental conditions is 3.2 percent, and the conversion rate of the cellulose is more than 92.1 percent
As shown in table 1, table 1 shows the reaction conditions and results described in examples 11, 12 and 15 to 19 of the present invention.
TABLE 1 reaction conditions and results of examples 11, 12 and 15 to 19 of the present invention
Figure BDA0003018758540000111
The results in Table 1 show that the catalyst Ir-WO prepared in example 7 is used without further modification x (W/Ir＝0.13)/SiO 2 The catalytic conversion effect on cellulose is better, and the yield of liquid alkane is highest.
Examples 20 to 23
The specific reaction process and detection method were the same as in example 15, except that the reaction temperature was different from example 15, and the reaction temperatures were 190 ℃,200 ℃,220 ℃, and 230 ℃. The liquid alkane yields determined were 38.0%,60.4%,77.5% and 65.7%, respectively, with cellulose conversions of 59.0%,95.7%, >99.9%, respectively.
The reaction conditions and results of example 15 and examples 20 to 23 are shown in table 2, and table 2 shows the reaction conditions and results of example 15 and examples 20 to 23 according to the present invention.
TABLE 2 reaction conditions and results of examples 15 and 20 to 23 according to the present invention
Figure BDA0003018758540000121
The results of example 15 and examples 20 to 23 show that the yield of liquid alkanes is higher at a temperature of 210 ℃ without changing other conditions.
Examples 24 to 26
Except that the reaction time was different from that of example 15, the specific reaction process and detection method were the same as those of example 15, the reaction times were respectively 2h,6h and 12h, and the yields of liquid alkanes were determined to be 16.2%,38.6% and 62.4%, the cellulose conversions were respectively 47.1%,82.3% and 98.9%, and the reaction conditions and results of example 15 and examples 24 to 26 are shown in table 3, and table 3 shows the reaction conditions and results of example 15 and examples 24 to 26 of the present invention.
TABLE 3 reaction conditions and results of examples 15 and 24 to 26 according to the invention
Figure BDA0003018758540000122
Figure BDA0003018758540000131
The results in Table 3 show that when other conditions are not changed, the reaction is facilitated by extending the reaction time, and the longer the reaction time, the higher the liquid alkane yield and the cellulose conversion in the present invention are.
Examples 27 to 28
The specific reaction process and detection method were the same as in example 15, except that the hydrogen pressure of the reaction was different from that of example 15, and the hydrogen pressures were respectively 2mpa and 6mpa, and it was determined that the yields of liquid alkane were 63.9% and 85.1%, respectively, and the cellulose conversion rates were greater than 99.9%. The reaction conditions and results of example 15 and examples 27 to 28 are shown in table 4, and table 4 shows the reaction conditions and results of example 15 and examples 27 to 28 of the present invention:
TABLE 4 reaction conditions and results of examples 15 and 27 to 28 of the present invention
Figure BDA0003018758540000132
The results in Table 4 show that, while other conditions were unchanged, increasing the hydrogen pressure was favorable for the reaction, but too high a hydrogen pressure also affected the yield of liquid alkane.
Example 29
The specific reaction process and detection method are the same as those in example 15, and the difference from example 15 is that the cellulose raw material is replaced by the same amount of corn stalk raw material, and the initial hydrogen pressure for conversion is 6MPa. The liquid alkane yields were determined to be 73.7% each. The conversion rates of cellulose and hemicellulose in the corn straw raw material are both more than 99.9 percent.
Example 30
The specific reaction process and detection method were the same as in example 15, except that the reaction temperature for cellulose conversion was 2 hours, as in example 15. The liquid alkane yields were determined to be 11.6% each. The cellulose conversion was 48.8%.
Example 31
The specific reaction process and detection method are the same as those in example 15, and the difference from example 15 is that no molecular sieve is added in the cellulose conversion, and the catalyst is Ir-WO x /SiO 2 (0.06) catalyst, ir-WO x /SiO 2 (0.06) the amount of the catalyst added was 0.31g. The liquid alkane yields were determined to be 1.1% each. The cellulose conversion was 21.3%.
Example 32
The specific reaction process and detection method were the same as in example 15, except that Ir-WO was not added for cellulose conversion, as in example 15 x /SiO 2 (0.06), the catalyst is HZSM-5 molecular sieve, and the addition amount of the HZSM-5 molecular sieve is 0.31g. The liquid alkane yields were determined to be 0.1% each. The cellulose conversion was 72.7%.
From examples 15, 31 and 32, it is shown that the iridium tungsten bimetallic catalyst and the molecular sieve catalyst have synergistic effect, and the combination of the two greatly improves the yield of liquid alkane and the conversion rate of cellulose.
The embodiment shows that the method for preparing the liquid alkane by catalytically converting the biomass-based raw material by using the specific catalyst has the advantages of higher yield, simple operation and mild conditions.
The above embodiments are only for the purpose of helping understanding the technical solution of the present invention and the core idea thereof, and it should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims (4)

1. A method for selectively preparing C5-C6 liquid alkane by aqueous phase catalytic conversion of a cellulose biomass raw material is characterized in that an iridium-based bimetallic catalyst composite molecular sieve is used as a catalyst, and the method specifically comprises the following steps: adding iridium-based bimetallic catalyst into water, placing the iridium-based bimetallic catalyst into a reaction container, sealing the reaction container, filling 2-6MPa of hydrogen into the reaction container, carrying out reduction pretreatment on the catalyst, after the pretreatment is finished, cooling the reaction container to room temperature, opening the reaction container to discharge the hydrogen, adding nonpolar liquid alkane, simultaneously placing a cellulose biomass raw material and a molecular sieve catalyst into the reaction container, sealing the reaction container, filling 1-8MPa of hydrogen into the reaction container, stirring, heating the reaction container to 210-280 ℃, and reacting for 12-24 h to obtain the liquid alkane after the reaction is finished, wherein the volume ratio of the nonpolar liquid alkane to the water is (1-20): (1 to 20); the iridium-based bimetallic catalyst is prepared by the following steps: impregnating a silicon-based material with an iridium source and a tungsten source, drying and calcining to obtain an iridium-based bimetallic catalyst, wherein the iridium source is iridium chloride or chloroiridic acid, the tungsten source is ammonium paratungstate, the loading capacity of metal in the iridium-based bimetallic catalyst is 1-15 wt%, and the atomic ratio of tungsten to iridium is 0.03-0.5: 1, in the iridium-based bimetallic catalyst composite molecular sieve catalyst, the mass ratio of the iridium-based bimetallic catalyst to the molecular sieve catalyst is (1 to 10): (1 to 10), wherein the mass ratio of the cellulose biomass raw material to the iridium-based bimetallic catalyst composite molecular sieve catalyst is 1 to 100:1, the molecular sieve catalyst is selected from more than one of beta molecular sieve, ZSM molecular sieve and Y molecular sieve.
2. The method for selectively preparing the C5-C6 liquid alkane from the cellulose biomass raw material through aqueous phase catalytic conversion according to claim 1, wherein the soaking time is 1-24h, and the soaking temperature is 10-200 ℃; the drying time is 1 to 24 hours, and the drying temperature is 40 to 200 ℃; the calcination time is 1 to 24 hours, and the calcination temperature is 300 to 700 ℃.
3. The method for selectively producing C5-C6 liquid alkanes of claim 1, wherein said C5-C6 liquid alkanes are liquid mixtures of n-pentane, isopentane, n-hexane, and isohexane.
4. The method for selectively producing C5-C6 liquid alkane from cellulosic biomass raw material by aqueous catalytic conversion according to claim 1, wherein the cellulosic biomass raw material is cellulose or corn stover.
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