CN114181729B - Method for synthesizing diesel precursor by photocatalysis of biomass platform compound - Google Patents

Method for synthesizing diesel precursor by photocatalysis of biomass platform compound Download PDF

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CN114181729B
CN114181729B CN202010959469.3A CN202010959469A CN114181729B CN 114181729 B CN114181729 B CN 114181729B CN 202010959469 A CN202010959469 A CN 202010959469A CN 114181729 B CN114181729 B CN 114181729B
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diesel
reaction
precursor
dimethylfuran
catalyst
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CN114181729A (en
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王峰
罗能超
张健
刘诗阳
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/44—Solvents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • 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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  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention relates to a method for synthesizing a diesel precursor by photocatalysis of a biomass platform compound. Wherein the biomass raw materialIs a downstream product of lignocellulose, namely 2-methylfuran and 2, 5-dimethylfuran, and is directly synthesized into C-containing substances by illumination in the presence of a Pt-supported semiconductor photocatalyst and a small amount of water 10 ～C 12 And C 15 ～C 18 Diesel precursors in the carbon number range. The diesel oil precursor is directly converted into diesel oil through hydrodeoxygenation. The diesel oil consists of straight-chain and branched-chain alkanes and a small amount of cycloalkanes, and has a proper cetane number. And the quantum yield of the diesel precursor can be improved by 2.4 times at most by adding water. The reaction process for preparing the diesel oil is as follows: mixing 2-methylfuran, 2, 5-dimethylfuran or a mixture thereof, a catalyst, water and an acetonitrile solvent, putting the mixture into a pressure container, replacing the mixture with inert gas, stirring the mixture under normal temperature illumination for more than 1 hour, and separating the catalyst from a reaction system after the reaction. The unreacted starting material is recovered by primary distillation. The prepared diesel precursor can be prepared into high-quality diesel by the existing method.

Description

Method for photocatalytic synthesis of diesel precursor by biomass platform compound
Technical Field
The invention relates to a method for synthesizing a diesel precursor by photocatalysis of a biomass platform compound, in particular to a metal-loaded semiconductor photocatalyst and a small amount of water added into a reaction system.
Background
The liquid fuel comprises gasoline, diesel oil and aviation kerosene, is an energy substance with great demand in daily life, and is also an important energy strategic material in China. Diesel oil is a very important liquid fuel, which contains C 10 ～C 22 The mixture of alkane, cyclane, olefin and arene with carbon chain length is light diesel oil (180-370 deg.c) and heavy diesel oil (350-410 deg.c). The diesel oil has high energy density and is a power source for large vehicles, railway locomotives, ships and the like. With the increasing importance of our country on environmental protection and sustainable development, higher requirements are put forward on the quality of diesel oil. At present, diesel oil is mainly produced by petroleum refining, and thus its production greatly depends on petrochemical resources. Because of the shortage of oil in China, the production of diesel oil is extremely dependent on import. It would be highly desirable if high quality diesel fuel, particularly special purpose diesel fuel, could be produced from a renewable routeLarge market value and strategic demand.
Biomass is the only renewable carbonaceous energy source substance on earth. The conversion of biomass to produce high quality diesel is a very potential and commercially valuable diesel synthesis process. The first step of converting cellulose and hemicellulose in biomass into diesel oil is to convert the biomass into a diesel oil precursor, and the diesel oil precursor is subjected to hydrodeoxygenation to obtain the diesel oil. There are many international methods for synthesizing biomass-based diesel oil, but most of the diesel oil has low calorific value and high freezing point due to single component and high oxygen content (CN 102864024A). Therefore, most of the produced diesel oil can only be added into diesel oil of petroleum source, and has the requirement of the highest addition ratio. The addition of traditional biodiesel often results in a reduction in the properties of crude diesel (CN 1944582A). Therefore, a method for producing high-quality diesel oil from downstream products of lignocellulose, such as furfural, 5-hydroxymethylfurfural, levulinic acid, 2-methylfuran, 2, 5-dimethylfuran, and the like, as raw materials, has been developed at home and abroad (Science, 2005,308, 1446-1450). The methods generally comprise two steps, namely, firstly coupling the biomass raw materials with carbon to obtain oxygenated compounds with carbon chain lengths within the carbon number range of the diesel oil, then hydrodeoxygenating the diesel oil precursor by adopting a hydrodeoxygenation catalyst, and finally obtaining the diesel oil. The diesel oil has high cetane number, low oxygen content and high alkane ratio. These methods generally only allow to obtain linear or branched diesel precursors, and it is difficult to obtain both linear and branched diesel precursors. For this purpose, biomass-based 2-methylfuran and 2, 5-dimethylfuran are used as raw materials, and ZnIn doped with metal is used 2 S 4 On the base catalyst, a diesel precursor and hydrogen are obtained simultaneously by a dehydrogenation coupling method, and the diesel precursor simultaneously contains straight chain and branched chain components (CN 201811411728.8). The process additionally inputs light energy, and a product with higher energy density is obtained. The quantum yield of the optimal catalyst for synthesizing diesel precursors still needs to be improved.
Disclosure of Invention
The invention aims to improve the quantum yield of the diesel precursor prepared by photocatalytic conversion of biomass downstream products such as 2-methylfuran, 2, 5-dimethylfuran and the like, thereby improving the utilization rate of light energy and accelerating the generation rate of the diesel precursor. The obtained diesel oil precursor can be converted into high-quality diesel oil by the existing mature technology.
The diesel oil related to the invention can be synthesized by catalyzing metal-loaded semiconductor photocatalyst, and the quantum yield of the diesel oil precursor is improved by adding a small amount of water. The specific preparation scheme is as follows: mixing one or two of 2-methylfuran or 2, 5-dimethylfuran, metal-loaded semiconductor photocatalyst, water and acetonitrile solvent, placing the mixture into a quartz glass tube under the protection of inert gas, stirring and reacting at normal temperature under illumination for more than or equal to 1 hour, wherein the reaction product is dimer (C) capable of being used as diesel oil precursor 10 ～C 12 Containing 2 furan rings), trimerization (C) 15 ～C 18 Containing 3 furan rings) and a small amount of tetrameric product (C) 20 ～C 24 Containing 4 furan rings). The liquid mixture left after the recovery of the unreacted raw materials is the diesel precursor, which can be converted into high-quality diesel through hydrodeoxygenation.
Wherein the volume concentration of the 2-methylfuran or 2, 5-dimethylfuran in the initial reaction system is 1-100 vol%; the light source is one or more of a xenon lamp, an LED lamp or sunlight; the metal loaded semiconductor photocatalyst has Ni, au or Pt as the loaded metal and the metal loading amount is 0.01-5 wt%; the semiconductor being Zn x In 2 S 3+x 、CdS、TiO 2 、N 2 O 5 Or C 3 N 4 Wherein the value of x is 0.5-4; the dosage of the catalyst is 0.05-10 g L -1 。
The volume fraction of the added water in the initial reaction system is 0-10 vol%.
Preferably, the method comprises the following steps: the volume concentration of the 2-methylfuran or 2, 5-dimethylfuran in the initial reaction system is 10-100 vol%; the light source is one or more than two of LEDs; the metal loaded semiconductor photocatalyst has the loaded metal of Ru, pd, ni, au or Pt, and the metal loading is 0.05-0.5 wt%; the semiconductor being Zn x In 2 S 3+x 、CdS、TiO 2 Or N 2 O 5 Wherein the value of x is 0.5 to 4; the amount of the catalyst is 0.2E5g L -1 。
The volume fraction of the added water in the initial reaction system is 0.5-5 vol%.
The best is as follows: the volume concentration of the 2-methylfuran or 2, 5-dimethylfuran in the initial reaction system is 30-80 vol%; the light source is one or two of an LED and sunlight; the metal-loaded semiconductor photocatalyst is loaded with Pt with the metal loading amount of 0.08-0.2 wt%; the semiconductor being Zn x In 2 S 3+x Or TiO 2 Wherein the value of x is 1 to 3; the dosage of the catalyst is 1-2 g L -1 。
The volume fraction of the added water in the initial reaction system is 2-4 vol%.
After the reaction, the raw materials of 2-methylfuran and 2, 5-dimethylfuran with low boiling point can be separated and recovered by a flash evaporation mode, and the remaining liquid mixture with higher boiling point is the diesel precursor with carbon number of C 10 ～C 12 And C 15 ～C 18 The selectivity is greater than 97%.
Like other photocatalytic reactions, the greater the light intensity of the light source, the faster the reaction rate. The catalyst activity is reduced due to strong adsorption of reaction products on the catalyst surface. The preferred reaction time is therefore 24-72h, which gives the desired product in high quantum yields (e.g. 2, 5-dimethylfuran gives an apparent quantum yield of up to 45.6% over the preferred catalyst, suitable for industrial exploration).
Compared with the existing method for preparing diesel oil, the method has the following advantages:
1. the catalyst is simple to prepare, and the range of the selectable semiconductor photocatalyst is wide;
2. the loading capacity of the noble metal is low, and the consumption of the noble metal is low.
3. Higher quantum yield of diesel precursor can be achieved by adding a small amount of water.
Drawings
Table 1 is a summary of the results of the examples;
FIG. 1 is a gas chromatogram of example 10.
Detailed Description
In order to further explain the present invention in detail, several embodiments are given below. Examples 1 to 20 are examples of photocatalytic C-C coupling for the preparation of diesel precursors. The present invention is not limited to these examples.
Example 1
Preparation of ZnIn by solvothermal method 2 S 4 A catalyst. ZnSO is added 4 ·7H 2 O(1.0mmol，287.6mg)、InCl 3 ·4H 2 O (2.0 mmol,576.5 mg) and NaCl (211.5 mg) were put in a conical flask containing absolute ethanol, magnetically stirred at room temperature for 30min, and thioacetamide (599.9 mg) was added to the above mixture. After stirring for an additional 30min, the mixture was transferred to a 50ml clean teflon lined autoclave. After sealing, the reaction mixture was subjected to hydrothermal reaction at 160 ℃ for 20 hours. After the reaction, the autoclave was naturally cooled to room temperature. The reacted solid was separated by centrifugation and washed 3 times with absolute ethanol (25 ml), 2 times with ultra pure water (25 ml) and finally 1 time with absolute ethanol, respectively. The resulting yellow solid was dried under vacuum at 60 ℃ for 12h.
In a 5mL quartz glass reaction tube, 0.5mL 2, 5-dimethylfuran and 0.5mL acetonitrile were added, and 5mg ZnIn was weighed 2 S 4 The reaction is catalyzed, adding the catalyst relative to ZnIn 2 S 4 Ru (NO) NO with a mass fraction of 0.1wt% 3 Replacing the reaction tube with argon gas, sealing, irradiating with a normal temperature irradiation power of 1.8W LED (455 nm) for 12h to obtain a diesel precursor after the reaction is finished, and detecting the product by chromatography to obtain a dimer (containing 2 furan rings) and a trimer (containing 3 furan rings). The conversion of 2, 5-dimethylfuran was 6.0%, and the diesel precursor production rate was 0.450g Catalyst and process for preparing same -1 h -1 The selectivity of diesel precursor is 100%, and the selectivity of branched diesel precursor (see the formula in claim 3) is 37%.
Example 2
ZnIn 2 S 4 Was prepared as in example 1. In a 5mL quartz glass reaction tube, 0.5mL 2, 5-dimethylfuran, 0.463mL acetonitrile, 3.75vol% deionized water were added, and 5mg ZnIn was weighed 2 S 4 The reaction is catalyzed, adding the catalyst relative to ZnIn 2 S 4 Ru (acac) with a mass fraction of 0.1wt% 3 And replacing the reaction tube with argon gas, sealing, irradiating by a normal-temperature LED (455 nm) with the irradiation power of 1.8W for 12h, and detecting products by chromatography after the reaction is finished to obtain a dimer (containing 2 furan rings) and a trimer (containing 3 furan rings). The conversion of 2, 5-dimethylfuran was 6.9%, and the diesel precursor generation rate was 0.517g Catalyst and process for producing the same -1 h -1 The selectivity of the diesel precursor is 100%, and the selectivity of the branched diesel precursor (see the formula in claim 3) is 35%.
Example 3
ZnIn 2 S 4 Was prepared as in example 1. In a 5mL quartz glass reaction tube, 0.5mL 2, 5-dimethylfuran and 0.5mL acetonitrile were added, and 5mg ZnIn was weighed 2 S 4 The reaction is catalyzed, adding the catalyst relative to ZnIn 2 S 4 0.1wt% of Pd (acac) 2 And replacing the reaction tube with argon gas, sealing, irradiating by a normal-temperature LED (455 nm) with the irradiation power of 1.8W for 12h, and detecting products by chromatography after the reaction is finished to obtain a dimer (containing 2 furan rings) and a trimer (containing 3 furan rings). The conversion of 2, 5-dimethylfuran was 8.6% and the diesel precursor production rate was 0.650g Catalyst and process for producing the same -1 h -1 The selectivity of diesel precursor is 100%, and the selectivity of branched diesel precursor (see the formula in claim 3) is 38%.
Example 4
ZnIn 2 S 4 Was prepared as in example 1. In a 5mL quartz glass reaction tube, 0.5mL 2, 5-dimethylfuran, 0.463mL acetonitrile, 3.75vol% deionized water were added, and 5mg ZnIn was weighed 2 S 4 The reaction is catalyzed, adding the catalyst relative to ZnIn 2 S 4 0.1wt% of Pd (acac) 2 And replacing the reaction tube with argon gas, sealing, irradiating by a normal-temperature LED (455 nm) with the irradiation power of 1.8W for 12h, and detecting products by chromatography after the reaction is finished to obtain a dimer (containing 2 furan rings) and a trimer (containing 3 furan rings). The conversion of 2, 5-dimethylfuran was 12.2%, and the diesel precursor generation rate was 0.917g Catalyst and process for producing the same -1 h -1 The selectivity of diesel precursor is 100%, and the selectivity of branched diesel precursor (see the formula in claim 3) is 39%.
Example 5
ZnIn 2 S 4 Was prepared as in example 1. In a 5mL quartz glass reaction tube, 0.5mL of 2, 5-dimethylfuran and 0.5mL of acetonitrile were added, and 5mg of ZnIn was weighed 2 S 4 The reaction is catalyzed, adding the catalyst relative to ZnIn 2 S 4 Ni (acac) with a mass fraction of 0.1wt% 2 And replacing the reaction tube with argon gas, sealing, irradiating by a normal-temperature LED (455 nm) with the irradiation power of 1.8W for 12h, and detecting products by chromatography after the reaction is finished to obtain a dimer (containing 2 furan rings) and a trimer (containing 3 furan rings). The conversion of 2, 5-dimethylfuran was 11.3%, and the diesel precursor production rate was 0.850g Catalyst and process for producing the same -1 h -1 The selectivity of the diesel precursor is 100%, and the selectivity of the branched diesel precursor (see the formula in claim 3) is 39%.
Example 6
ZnIn 2 S 4 Was prepared as in example 1. In a 5mL quartz glass reaction tube, 0.5mL of 2, 5-dimethylfuran, 0.463mL of acetonitrile, 3.75vol% of deionized water were added, and 5mg of ZnIn was weighed 2 S 4 The reaction is catalyzed, adding the catalyst relative to ZnIn 2 S 4 Ni (acac) with a mass fraction of 0.1wt% 2 Replacing the reaction tube with argon gas, sealing, irradiating by a normal-temperature irradiation power 1.8W LED (455 nm) for 12h, and detecting the product by chromatography after the reaction is finished to obtain a dimer (containing 2 furan rings) and a trimer (containing 3 furan rings). The conversion of 2, 5-dimethylfuran was 16.4% and the diesel precursor production rate was 1.23g Catalyst and process for preparing same -1 h -1 The selectivity of the diesel precursor is 100%, and the selectivity of the branched diesel precursor (see the formula in claim 3) is 39%.
Example 7
ZnIn 2 S 4 Was prepared as in example 1. In a 5mL quartz glass reaction tube, 0.5mL 2, 5-dimethylfuran and 0.5mL acetonitrile were added, and 5mg ZnIn was weighed 2 S 4 The reaction is catalyzed, adding the catalyst relative to ZnIn 2 S 4 0.1wt% of HAuCl 4 Replacing the reaction tube with argon gas, sealing, irradiating with 1.8W LED (455 nm) at normal temperature for 12h, detecting the product by chromatography after the reaction is finished,dimers (containing 2 furan rings) and trimers (containing 3 furan rings) were obtained. The conversion of 2, 5-dimethylfuran was 8.6%, and the diesel precursor production rate was 0.650g Catalyst and process for preparing same -1 h -1 The selectivity of the diesel precursor is 100%, and the selectivity of the branched diesel precursor (see the formula in claim 3) is 37%.
Example 8
ZnIn 2 S 4 Was prepared as in example 1. In a 5mL quartz glass reaction tube, 0.5mL of 2, 5-dimethylfuran, 0.463mL of acetonitrile, 3.75vol% of deionized water were added, and 5mg of ZnIn was weighed 2 S 4 The reaction is catalyzed, adding the catalyst relative to ZnIn 2 S 4 0.1wt% of HAuCl 4 Replacing the reaction tube with argon gas, sealing, irradiating by a normal-temperature irradiation power 1.8W LED (455 nm) for 12h, and detecting the product by chromatography after the reaction is finished to obtain a dimer (containing 2 furan rings) and a trimer (containing 3 furan rings). The conversion of 2, 5-dimethylfuran was 16.8% and the diesel precursor production rate was 1.27g Catalyst and process for preparing same -1 h -1 The selectivity of the diesel precursor is 100%, and the selectivity of the branched diesel precursor (see the formula in claim 3) is 39%.
Example 9
ZnIn 2 S 4 Was prepared as in example 1. In a 5mL quartz glass reaction tube, 0.5mL 2, 5-dimethylfuran and 0.5mL acetonitrile were added, and 5mg ZnIn was weighed 2 S 4 The reaction is catalyzed, adding the catalyst relative to ZnIn 2 S 4 Pt (acac) with mass fraction of 0.1wt% 2 And replacing the reaction tube with argon gas, sealing, irradiating by a normal-temperature irradiation power 1.8W LED (455 nm) for 12h, and after the reaction is finished, detecting the product by chromatography to obtain a dimer (containing 2 furan rings), a trimer (containing 3 furan rings) and a small amount of tetramer (containing 4 furan rings). The conversion of 2, 5-dimethylfuran was 13.6% and the diesel precursor production rate was 1.02g Catalyst and process for preparing same -1 h -1 The selectivity of the diesel precursor is 99%, and the selectivity of the branched diesel precursor (see the formula in claim 3) is 37%.
Example 10
ZnIn 2 S 4 Was prepared as in example 1. Reaction at 5mL of silica glassIn the tube, 0.5mL of 2, 5-dimethylfuran, 0.463mL of acetonitrile, 3.75vol% of deionized water were added, and 5mg of ZnIn was weighed 2 S 4 The reaction is catalyzed, adding the catalyst relative to ZnIn 2 S 4 Pt (acac) with mass fraction of 0.1wt% 2 And replacing the reaction tube with argon gas, sealing, irradiating by a normal-temperature irradiation power 1.8W LED (455 nm) for 12h, and after the reaction is finished, detecting the product by chromatography to obtain a dimer (containing 2 furan rings), a trimer (containing 3 furan rings) and a small amount of tetramer (containing 4 furan rings). The conversion of 2, 5-dimethylfuran was 33.3% and the diesel precursor production rate was 2.48g Catalyst and process for preparing same -1 h -1 The selectivity of the diesel precursor is 99 percent, and the selectivity of the branched diesel precursor (see the formula in claim 3) is 39 percent.
Example 11
ZnIn 2 S 4 Was prepared as in example 1. In a 5mL quartz glass reaction tube, 0.5mL of 2, 5-dimethylfuran, 0.495mL of acetonitrile, 0.5vol% of deionized water were added, and 5mg of ZnIn was weighed 2 S 4 The reaction is catalyzed, adding the catalyst relative to ZnIn 2 S 4 Pt (acac) with mass fraction of 0.12wt% 2 Replacing the reaction tube with argon gas, sealing, irradiating by a normal-temperature irradiation power 1.8W LED (455 nm) for 12h, and after the reaction is finished, detecting the product by chromatography to obtain a dimer (containing 2 furan rings), a trimer (containing 3 furan rings) and a small amount of tetramer (containing 4 furan rings). The conversion of 2, 5-dimethylfuran was 18.1%, and the diesel precursor production rate was 1.35g Catalyst and process for preparing same -1 h -1 The selectivity of the diesel precursor is 99%, and the selectivity of the branched diesel precursor (see the formula in claim 3) is 37%.
Example 12
ZnIn 2 S 4 Was prepared as in example 1. In a 5mL quartz glass reaction tube, 0.5mL 2, 5-dimethylfuran, 0.480mL acetonitrile, 2.0vol% deionized water were added, and 5mg ZnIn was weighed 2 S 4 The reaction is catalyzed, adding the catalyst relative to ZnIn 2 S 4 Pt (acac) with mass fraction of 0.12wt% 2 Replacing the reaction tube with argon gas, sealing, irradiating with 1.8W LED (455 nm) at normal temperature for 12h, and detecting the product by chromatography to obtain IIA dimer (containing 2 furan rings), a trimer (containing 3 furan rings) and a minor tetramer (containing 4 furan rings). The conversion of 2, 5-dimethylfuran was 25.7%, and the diesel precursor production rate was 1.92g Catalyst and process for producing the same -1 h -1 The selectivity of the diesel precursor is 99%, and the selectivity of the branched diesel precursor (see the formula in claim 3) is 37%.
Example 13
ZnIn 2 S 4 Was prepared as in example 1. In a 5mL quartz glass reaction tube, 0.5mL 2, 5-dimethylfuran, 0.463mL acetonitrile, 3.75vol% deionized water were added, and 5mg ZnIn was weighed 2 S 4 The reaction is catalyzed, adding the catalyst relative to ZnIn 2 S 4 Pt (acac) with a mass fraction of 0.12wt% 2 And replacing the reaction tube with argon gas, sealing, irradiating by a normal-temperature irradiation power 1.8W LED (455 nm) for 12h, and after the reaction is finished, detecting the product by chromatography to obtain a dimer (containing 2 furan rings), a trimer (containing 3 furan rings) and a small amount of tetramer (containing 4 furan rings). The conversion of 2, 5-dimethylfuran was 33.3% and the diesel precursor production rate was 2.48g Catalyst and process for producing the same -1 h -1 The selectivity of the diesel precursor is 99%, and the selectivity of the branched diesel precursor (see the formula in claim 3) is 39%.
Example 14
ZnIn 2 S 4 Was prepared as in example 1. In a 5mL quartz glass reaction tube, 0.5ml of 2, 5-dimethylfuran, 0.450mL of acetonitrile, 5.0vol% of deionized water were added, and 5mg of ZnIn was weighed 2 S 4 The reaction is catalyzed, adding the catalyst relative to ZnIn 2 S 4 Pt (acac) with mass fraction of 0.12wt% 2 And replacing the reaction tube with argon gas, sealing, irradiating by a normal-temperature LED (455 nm) with the irradiation power of 1.8W for 12h, and detecting products by chromatography after the reaction is finished to obtain a dimer (containing 2 furan rings) and a trimer (containing 3 furan rings). The conversion of 2, 5-dimethylfuran was 27.4% and the diesel precursor production rate was 2.07g Catalyst and process for producing the same -1 h -1 The selectivity of diesel precursor is 100%, and the selectivity of branched diesel precursor (see the formula in claim 3) is 38%.
Example 15
ZnIn 2 S 4 Was prepared as in example 1. In a 200mL quartz glass reaction cell, 10mL of 2, 5-dimethylfuran, 19mL of acetonitrile and 3.33vol% of deionized water were added, and 100mg of ZnIn was weighed 2 S 4 The reaction is catalyzed, adding the catalyst relative to ZnIn 2 S 4 Pt (acac) with mass fraction of 0.12wt% 2 And replacing the reaction tube with argon gas, sealing, irradiating by a normal-temperature irradiation power 13.4W LED (455 nm) for 48h, and after the reaction is finished, detecting the product by chromatography to obtain a dimer (containing 2 furan rings), a trimer (containing 3 furan rings) and a small amount of tetramer (containing 4 furan rings). The conversion of 2, 5-dimethylfuran was 48.3%, and the diesel precursor generation rate was 0.892g Catalyst and process for producing the same -1 h -1 The selectivity of the diesel precursor is 98%, and the selectivity of the branched diesel precursor (see the formula in claim 3) is 39%.
Example 16
ZnIn 2 S 4 Was prepared as in example 1. In a 200mL quartz glass reaction cell, 10mL of 2, 5-dimethylfuran, 19mL of acetonitrile and 3.33vol% of deionized water were added, and 100mg of ZnIn was weighed 2 S 4 The reaction is catalyzed, adding the catalyst relative to ZnIn 2 S 4 Pt (acac) with a mass fraction of 0.12wt% 2 Replacing the reaction tube with argon gas, sealing, irradiating by a normal-temperature irradiation power 13.4W LED (455 nm) for 100h, and after the reaction is finished, detecting the product by chromatography to obtain a dimer (containing 2 furan rings), a trimer (containing 3 furan rings) and a small amount of tetramer (containing 4 furan rings). The conversion of 2, 5-dimethylfuran was 73.0% and the diesel precursor production rate was 0.634g Catalyst and process for preparing same -1 h -1 The selectivity of the diesel precursor is 96 percent, and the selectivity of the branched diesel precursor (see the formula in claim 3) is 39 percent.
Example 17
Preparation of Zn by solvothermal method 2 In 2 S 5 A catalyst. ZnSO is added 4 ·7H 2 O(1.6mmol，460.2mg)、InCl 3 ·4H 2 O (1.6 mmol, 469.1mg) and NaCl (211.5 mg) were put in a conical flask containing absolute ethanol, magnetically stirred at room temperature for 30min, and thioacetamide (599.9 mg) was added to the above mixture. After stirring for a further 30min, the mixture was transferred to 50ml of clean polymerTetrafluoroethylene lined autoclave. After sealing, the reaction mixture was subjected to hydrothermal reaction at 160 ℃ for 20 hours. After the reaction, the autoclave was naturally cooled to room temperature. The reacted solid was separated by centrifugation and washed with absolute ethanol (25 ml) 3 times, ultrapure water (25 ml) 2 times, and finally with absolute ethanol 1 time, respectively. The resulting yellow solid was dried under vacuum at 60 ℃ for 12h.
In a 200mL quartz glass reaction cell, 10mL of 2, 5-dimethylfuran, 19mL of acetonitrile and 3.33vol% of deionized water were added, and 100mg of Zn was weighed 2 In 2 S 5 The reaction is catalyzed, adding a counter Zn to 2 In 2 S 5 Pt (acac) with a mass fraction of 0.12wt% 2 Replacing the reaction tube with argon gas, sealing, irradiating by a normal-temperature irradiation power 13.4W LED (455 nm) for 48h, and after the reaction is finished, detecting the product by chromatography to obtain a dimer (containing 2 furan rings), a trimer (containing 3 furan rings) and a small amount of tetramer (containing 4 furan rings). The conversion of 2, 5-dimethylfuran was 70.7%, and the diesel precursor production rate was 1.29g Catalyst and process for preparing same -1 h -1 The selectivity of the diesel precursor was 97%, and the selectivity of the branched diesel precursor (see the formula in claim 3) was 39%.
Example 18
ZnIn 2 S 4 Was prepared as in example 1. In a 200mL quartz glass reaction cell, 10mL of 2-methylfuran, 19mL of acetonitrile and 3.33vol% of deionized water were added, and 100mg of ZnIn was weighed 2 S 4 The reaction is catalyzed, adding the catalyst relative to ZnIn 2 S 4 Pt (acac) with a mass fraction of 0.12wt% 2 And replacing the reaction tube with argon gas, sealing, irradiating by a normal-temperature irradiation power 13.4W LED (455 nm) for 48h, and detecting products by chromatography after the reaction is finished to obtain a dimer (containing 2 furan rings) and a trimer (containing 3 furan rings). The conversion of 2-methylfuran was 9.9% and the diesel precursor production rate was 0.187g Catalyst and process for preparing same -1 h -1 The selectivity of the diesel precursor is 100%, and the selectivity of the branched diesel precursor (see the formula in claim 3) is 32%.
Example 19
ZnIn 2 S 4 Was prepared as in example 1. In a 200ml quartz glass reaction tankTo this solution, 10mL of 2-methylfuran, 19mL of acetonitrile and 3.33vol% of deionized water were added, and 100mg of ZnIn was weighed 2 S 4 The reaction is catalyzed, adding the catalyst relative to ZnIn 2 S 4 Pt (acac) with mass fraction of 0.12wt% 2 Replacing the reaction tube with argon gas, sealing, irradiating with 13.4W LED (455 nm) at normal temperature for 100h, and detecting the product by chromatography after the reaction is finished to obtain dimer (containing 2 furan rings) and trimer (containing 3 furan rings). The conversion of 2-methylfuran was 18.8% and the diesel precursor production rate was 0.171g Catalyst and process for preparing same -1 h -1 The selectivity of the diesel precursor is 100 percent, and the selectivity of the branched diesel precursor (see the formula in claim 3) is 33 percent.
Example 20
ZnIn 2 S 4 Was prepared as in example 1. In a 200mL quartz glass reaction tank, 5mL of 2-methylfuran, 15mL of 2, 5-dimethylfuran, 4.5mL of acetonitrile, 2.0vol% of deionized water were added, and 100mg of ZnIn was weighed 2 S 4 The reaction is catalyzed, adding the catalyst relative to ZnIn 2 S 4 Pt (acac) with mass fraction of 0.12wt% 2 Replacing the reaction tube with argon gas, sealing, irradiating by a normal-temperature irradiation power 13.4W LED (455 nm) for 100h, and after the reaction is finished, detecting the product by chromatography to obtain a dimer (containing 2 furan rings), a trimer (containing 3 furan rings) and a small amount of tetramer (containing 4 furan rings). Co-conversion of 2, 5-dimethylfuran and 2-methylfuran by 15.3% and diesel precursor production rate of 0.275g Catalyst and process for producing the same -1 h -1 The selectivity of the diesel precursor is 99 percent, and the selectivity of the branched diesel precursor (see the formula in claim 3) is 37 percent.
Example 21
In a 200mL quartz glass reaction cell, 10mL of 2, 5-dimethylfuran, 19mL of acetonitrile and 3.33vol% of deionized water were added, and 100mg of TiO was weighed 2 (commercial Degussa P25) catalyzes the reaction, adding to TiO 2 Pt (acac) with mass fraction of 0.3wt% 2 Replacing the reaction tube with argon gas, sealing, irradiating with 2.7W LED (365 nm) at normal temperature for 48h, detecting the product by chromatography after the reaction is finished to obtain dimer (containing 2 furan rings), trimer (containing 3 furan rings) and a small amount of tetramerBody (containing 4 furan rings). The conversion of 2, 5-dimethylfuran was 31.5%, and the diesel precursor production rate was 0.571g Catalyst and process for preparing same -1 h -1 The selectivity of the diesel precursor is 96 percent, and the selectivity of the branched diesel precursor (see the formula in claim 3) is 42 percent.
Example 22
In a 200mL quartz glass reaction cell, 10mL of 2, 5-dimethylfuran, 19mL of acetonitrile, and 3.33vol% of deionized water were added, and 100mg of commercial Nb was weighed 2 O 5 Catalyzing the reaction, adding Nb 2 O 5 Pt (acac) with mass fraction of 0.3wt% 2 And replacing the reaction tube with argon gas, sealing, irradiating by a 2.7W LED (365 nm) at normal temperature for 48h, and detecting the product by chromatography after the reaction is finished to obtain a dimer (containing 2 furan rings), a trimer (containing 3 furan rings) and a small amount of tetramer (containing 4 furan rings). The conversion of 2, 5-dimethylfuran was 23.5%, and the diesel precursor production rate was 0.429g Catalyst and process for preparing same -1 h -1 The selectivity of the diesel precursor is 97%, and the selectivity of the branched diesel precursor (see the formula in claim 3) is 40%.
Example 23
Adding Cd (NO) 3 ) 2 ·4H 2 O (16.2 mmol) and thiourea (48.6 mmol) were added to a 130ml clean Teflon lined autoclave with ethylenediamine (80 ml). After stirring for 30min, the autoclave was sealed and reacted at 160 ℃ for 24h. And after the reaction is finished, naturally cooling the reaction kettle to room temperature. The resulting orange solid was dried under vacuum at 60 ℃ for 12 hours after washing 3 times with absolute ethanol (25 ml) and ultrapure water (25 ml), respectively.
Respectively adding 10mL of 2, 5-dimethylfuran, 19mL of acetonitrile and 3.33vol% of deionized water into a 200mL quartz glass reaction tank, weighing 100mg of CdS to catalyze the reaction, and adding 0.3wt% of Pt (acac) relative to the mass fraction of the CdS 2 And replacing the reaction tube with argon gas, sealing, irradiating by a normal-temperature irradiation power 13.4W LED (365 nm) for 48h, and after the reaction is finished, detecting a product by chromatography to obtain a dimer (containing 2 furan rings), a trimer (containing 3 furan rings) and a small amount of tetramer (containing 4 furan rings). The conversion of 2, 5-dimethylfuran was 18.1%, and the diesel precursor production rate was 0.342g g Catalyst and process for preparing same -1 h -1 The selectivity of diesel precursor is 96%, and the selectivity of branched diesel precursor (see the formula in claim 3) is 39%.
Example 24
Melamine (5.0 g) was placed in a quartz boat, which was then wrapped in two layers of aluminum foil. Then the quartz boat containing melamine is roasted for 4 hours at 550 ℃ (the heating rate is 2.3 ℃ for min) -1 ) To obtain yellow g-C 3 N 4 . In a 200mL quartz glass reaction cell, 10mL of 2, 5-dimethylfuran, 19mL of acetonitrile and 3.33vol% of deionized water were added, and 100mg of C was weighed 3 N 4 Catalyzing the reaction, adding relative to C 3 N 4 Pt (acac) with a mass fraction of 0.3wt% 2 And replacing the reaction tube with argon gas, sealing, irradiating by a normal-temperature irradiation power 13.4W LED (365 nm) for 48h, and after the reaction is finished, detecting a product by chromatography to obtain a dimer (containing 2 furan rings), a trimer (containing 3 furan rings) and a small amount of tetramer (containing 4 furan rings). The conversion of 2, 5-dimethylfuran was 5.9%, and the diesel precursor production rate was 0.110g Catalyst and process for preparing same -1 h -1 The selectivity of the diesel precursor is 99%, and the selectivity of the branched diesel precursor (see the formula in claim 3) is 38%.
Comparative example 1: ag/CdS-2wt% as catalyst
CdS was prepared as in example 23. Respectively adding 0.5mL of 2, 5-dimethylfuran, 0.463mL of acetonitrile and 3.75vol% of deionized water into a 5mL quartz glass reaction tube, weighing 5mg of CdS to catalyze the reaction, and adding AgNO with the mass fraction of 0.3wt% to catalyze the reaction 3 Replacing the reaction tube with argon gas, sealing, irradiating by a normal-temperature irradiation power 1.8W LED (455 nm) for 12h, and detecting the product by chromatography after the reaction is finished to obtain a dimer (containing 2 furan rings) and a trimer (containing 3 furan rings). The conversion of 2, 5-dimethylfuran was 0.66%, and the diesel precursor generation rate was 0.050g Catalyst and process for producing the same -1 h -1 The selectivity of the diesel precursor is 100%, and the selectivity of the branched diesel precursor (see the formula in claim 3) is 32%.
Comparative example 2: with Pt/In 2 S 3 0.12 wt.% of a catalyst
Adding InCl 3 ·4H 2 O (2.67mmol, 781.8 mg) and NaCl (217.2 mg) were put in a conical flask containing absolute ethanol, and after magnetic stirring at room temperature for 30min, TAA (599.9 mg) was added to the above-mentioned mixture. After stirring for a further 30min, the mixture was transferred to a 50ml clean Teflon lined autoclave. After sealing, the reaction was carried out hydrothermally at 160 ℃ for 20 hours. After the reaction, the autoclave was naturally cooled to room temperature. The reacted solid was separated by centrifugation and washed 3 times with absolute ethanol (25 ml), 2 times with ultra pure water (25 ml) and finally 1 time with absolute ethanol, respectively. The orange solid obtained was dried under vacuum at 60 ℃ for 12h.
In a 5mL quartz glass reaction tube, 0.5mL of 2, 5-dimethylfuran and 0.5mL of acetonitrile were added, and 5mg of In was weighed 2 S 3 The reaction was catalyzed, and 0.12wt% by weight of Pt (acac) was added 2 And replacing the reaction tube with argon gas, sealing, irradiating by a normal-temperature LED (455 nm) with the irradiation power of 1.8W for 12h, and detecting products by chromatography after the reaction is finished to obtain a dimer (containing 2 furan rings) and a trimer (containing 3 furan rings). The conversion of 2, 5-dimethylfuran was 1.8%, and the diesel precursor production rate was 0.133g Catalyst and process for producing the same -1 h -1 The selectivity of the diesel precursor is 100%, and the selectivity of the branched diesel precursor (see the formula in claim 3) is 35%.
TABLE 1 summary of the results of the examples
Figure BDA0002679953390000081
Figure BDA0002679953390000091
Figure BDA0002679953390000101
The results of the examples illustrate that:
1. it can be seen by comparing examples 2,4,6,8 and 10 that Pt is the optimum supported metal;
2. it can be seen by comparing examples 9 and 10 that both the conversion of the feedstock (2, 5-dimethylfuran) and the rate of diesel precursor production increase upon addition of water;
3. from comparative examples 9, 11 to 14, it can be seen that the greater the rate of production of diesel precursor with increasing water content, the greater the conversion of feedstock (2, 5-dimethylfuran);
4. it can be seen by comparing examples 14 and 15 that although the longer the reaction time, the higher the conversion of the starting material (2, 5-dimethylfuran), the lower the rate of diesel precursor production; therefore, the reaction time is optimal between 48 and 72h under the LED (455 nm) reaction condition that the raw material system is 10mL and the light source irradiation power is 13.4W. Generally, the smaller the volume of the raw material is, the higher the irradiation power of a light source is, and the higher the conversion rate of the raw material is in the same time; but the smaller the volume of the raw material is, the lower the diesel precursor generation rate is, so the light source irradiation power and the raw material volume are about large, and the higher raw material conversion rate and the diesel precursor generation rate can be obtained in the same reaction time;
5. by comparing examples 15, 17 and 21 to 24, it can be seen that Pt/Zn 2 In 2 S 5 -0.12wt% of the most preferred catalyst;
6. by comparing example 16 with example 19, it can be seen that both the reaction rate and the diesel precursor production rate are higher when 2, 5-dimethylfuran is used as a substrate;
7. comparative example 1 illustrates the use of even C 3 N 4 Semiconductors, with Ag loading, have a low rate of diesel precursor production;
8. comparative example 2 shows that even with a Pt semiconductor, but no water added, no superior catalyst was used and the rate of diesel precursor production was still low.

Claims (11)

1. A method for photocatalytic synthesis of diesel precursor by biomass platform compound is characterized in that:
the method comprises the following steps:
adding one or two of 2-methylfuran or 2, 5-dimethylfuran into a pressure vessel, adding a metal-loaded semiconductor photocatalyst, water and an acetonitrile solvent, and adding inert gasReplacing gas in the system by using a gas in a sexual atmosphere, and then performing illumination stirring reaction at normal temperature for 48-72 hours to obtain a diesel precursor; wherein the load metal is one or more of Ru, pd, ni, au or Pt, and the mass fraction range of the load metal is 0.01 to 5wt% of the semiconductor carrier; the semiconductor carrier is Zn x In 2 S 3+x 、CdS、TiO 2 、Nb 2 O 5 Or C 3 N 4 One or more than two of (1) and (4), wherein the value of x is 1 to 4; filtering out the catalyst after reaction, distilling and recovering unreacted raw materials under reduced pressure, wherein the residual liquid is a diesel precursor, and the volume fraction of water in an initial reaction system is 2-4 vol%;
the reaction formula is as follows:
Figure 300789DEST_PATH_IMAGE001
wherein the reaction substrate is one or two of 2-methylfuran or 2, 5-dimethylfuran, and R 1 And R 2 Not H at the same time.
2. The method of claim 1, wherein: water and noble metal are added in the reaction to promote one or two of 2-methylfuran and 2, 5-dimethylfuran to be converted into diesel oil precursor.
3. The method of claim 1, wherein:
the total volume concentration of the 2-methylfuran and/or the 2, 5-dimethylfuran in the initial reaction system is 1 to 99 vol%; the dosage of the metal-loaded semiconductor photocatalyst is 0.05 to 10g L -1 。
4. A method according to claim 1 or 3, characterized in that:
the metal of the metal-loaded semiconductor photocatalyst is one or more of Ni, au or Pt, the metal loading is 0.05 to 0.5wt percent of the semiconductor carrier, and the semiconductor carrier is Zn x In 2 S 3+x 、CdS、TiO 2 Or Nb 2 O 5 One or more than two of the components, and the using amount of the catalyst is 0.2 to 5g L -1 The reaction system of (1).
5. The method of claim 1, wherein:
the light source is one or more of xenon lamp, high-pressure mercury lamp, LED lamp or sunlight.
6. The method of claim 1, wherein:
the solvent for photocatalytic conversion of 2-methylfuran and 2, 5-dimethylfuran into the diesel precursor is one or more of acetonitrile, acetone, 1, 4-dioxane and tetrahydrofuran.
7. The method of claim 1, wherein:
the inert atmosphere gas is Ar or N ２ One or two of them.
8. The method of claim 3, wherein:
the total volume concentration of the 2-methylfuran and/or the 2, 5-dimethylfuran in the initial reaction system is 10 to 99 vol%.
9. The method of claim 8, wherein:
the total volume concentration of the 2-methylfuran and/or the 2, 5-dimethylfuran in the initial reaction system is 30 to 80 vol%.
10. The method of claim 4, wherein:
the metal loaded semiconductor photocatalyst is Pt, the metal loading is 0.08 to 0.2wt percent of the semiconductor carrier, and the semiconductor carrier is Zn x In 2 S 3+x And TiO 2 2 Wherein the value of x is 1 to 3; the dosage of the catalyst is 1 to 2g L -1 The reaction system of (1).
11. The method of claim 6, wherein:
the light source is one or two of a xenon lamp or an LED.
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