阅读说明：本技术 一种生物质液体燃料的制备方法 (Preparation method of biomass liquid fuel ) 是由 王伟 孙少颖 季建伟 邵先钊 张田雷 季晓晖 李志洲 于 2021-08-18 设计创作，主要内容包括：本发明公开了一种生物质液体燃料的制备方法,将双酚A溶于正丁醇中反应后加入醛,蒸出正丁醇溶剂后煅烧、研磨、过筛得到聚合物加入酸反应后得固体酸催化剂,将氢氧化铝加入磷酸溶解后加去离子水反应后过滤、烘干得前驱体煅烧得磷酸铝分子筛加入硝酸镍溶液中浸渍,然后干燥、煅烧即得镍负载的磷酸铝催化剂用于烷基化反应产物进行加氢脱氧反应获得高产率的柴油或航空煤油烷烃。本发明将双酚A衍生的酸性树脂作为固体酸用于木质纤维素基甲基呋喃与羰基化合物之间的烷烃化反应,并在这些反应中表现了很好的活性和稳定性,通过这些反应可获得一系列碳数为13～16的含氧有机化合物,这些化合物可通过加氢脱氧获得符合柴油和航空煤油结构要求的支链烷烃。(The invention discloses a preparation method of biomass liquid fuel, which comprises the steps of dissolving bisphenol A in n-butanol, reacting, adding aldehyde, evaporating n-butanol solvent, calcining, grinding and sieving to obtain a polymer, adding acid to react to obtain a solid acid catalyst, adding aluminum hydroxide into phosphoric acid, dissolving, adding deionized water, reacting, filtering and drying to obtain a precursor, calcining to obtain an aluminum phosphate molecular sieve, adding the aluminum phosphate molecular sieve into a nickel nitrate solution, soaking, drying and calcining to obtain a nickel-loaded aluminum phosphate catalyst, and performing hydrodeoxygenation reaction on an alkylation reaction product to obtain high-yield diesel oil or aviation kerosene alkane. According to the invention, the bisphenol A derived acidic resin is used as a solid acid for the alkylation reaction between lignocellulose-based methylfuran and a carbonyl compound, and the reactions show good activity and stability, a series of oxygen-containing organic compounds with the carbon number of 13-16 can be obtained through the reactions, and the compounds can be subjected to hydrodeoxygenation to obtain branched alkanes meeting the structural requirements of diesel oil and aviation kerosene.)

1. The preparation method of the biomass liquid fuel is characterized by comprising the following steps:

s1: dissolving bisphenol A in 10mL of n-butanol, reacting in a round-bottom flask with a condenser and a thermometer, adding aldehyde after the bisphenol A is completely dissolved and the solution is transparent, and controlling the mass ratio of the aldehyde to the bisphenol A to be l.0: 1.6; and (3) uniformly mixing, reacting for 6h, evaporating n-butanol solvent by using a rotary evaporator after the reaction is finished, calcining, grinding and sieving to obtain the polymer.

S2: weighing a polymer, adding an acid, stirring, reacting at room temperature for 1-12 h, then quenching with ice water, filtering, washing with deionized water until the pH value is neutral, drying to obtain a solid acid catalyst,

s3: putting aluminum hydroxide into a reaction kettle, adding a magneton, stirring, dropwise adding 85% phosphoric acid at 95 ℃, adding deionized water after complete dissolution, reacting for 12 hours, filtering, and drying for 2 hours at 120 ℃ to obtain a precursor; calcining the obtained precursor in a muffle furnace for 4 hours to obtain an aluminum phosphate molecular sieve;

s4: weighing a molecular sieve, adding the molecular sieve into a nickel nitrate solution, soaking for 12 hours, drying for 12 hours at 120 ℃, calcining for 4 hours at 500 ℃, and reducing for 2 hours at 500 ℃ in a hydrogen atmosphere before use to obtain a nickel-loaded aluminum phosphate catalyst which is used for carrying out hydrodeoxygenation reaction on an alkylation reaction product to obtain high-yield diesel oil or aviation kerosene alkane.

2. The method for producing a biomass liquid fuel according to claim 1, characterized in that: the aldehyde used in the step S1 is one or more of paraformaldehyde, formaldehyde, acetaldehyde, butyraldehyde and furfural.

3. The method for producing a biomass liquid fuel according to claim 1, characterized in that: the polymerization reaction acid in the step S2 is inorganic acid and organic acid; the inorganic acid is one or more than two of chlorosulfonic acid, phosphotungstic acid, sulfuric acid, nitric acid and phosphoric acid; the organic acid is one or more than two of trifluoroacetic acid, methanesulfonic acid and p-toluenesulfonic acid.

4. The method for producing a biomass liquid fuel according to claim 1, characterized in that: in the step S2 polymerization reaction, the dosage ratio of acid to bisphenol A is 0.01-0.15: 1, the reaction temperature is 20-100 ℃, and the reaction time is 0.5-24 hours; calcining the polymer obtained by the condensation reaction at the temperature of 100-400 ℃ for 2 hours,

5. the method for producing a biomass liquid fuel according to claim 1, characterized in that: the concentration of the acid used in the step S2 is 0.1-4 mol/L; 1.0g of polymer to 10.0mL of acid solution; the acidification condition is acidification for 1-12 hours at 20-120 ℃.

6. The method for producing a biomass liquid fuel according to claim 1, characterized in that: the solid acid catalyst synthesized in the step S2 is used for an alkylation reaction between lignocellulose-based methylfuran and a carbonyl compound; the lignocellulose-based carbonyl compound is one or a mixture of more than two of furfural, 5-hydroxymethyl furfural, acetone, 2-butanone, cyclopentanone, 2-pentanone and cyclohexanone.

7. The method for producing a biomass liquid fuel according to claim 6, characterized in that: the application of the solid acid catalyst in the alkylation reaction between lignocellulose-based methylfuran and a carbonyl compound specifically comprises the following steps: sequentially adding reaction substrates into a round-bottom flask, and controlling the molar ratio of the methylfuran to the carbonyl compound to be 2: 1; the alkylation reaction temperature is 20-100 ℃, the ratio of the catalyst amount to the furan compound is 0.01-0.5: 1, the reaction time is 0.5-12 hours, the alkylation reaction product is an oxygen-containing compound with the carbon number of 13-16, and the oxygen-containing compound is subjected to hydrodeoxygenation to prepare diesel or aviation kerosene alkane.

8. The method for producing a biomass liquid fuel according to claim 7, characterized in that: the hydrodeoxygenation reaction is carried out in an intermittent kettle type reactor, and the reaction conditions in the kettle type reactor are as follows: the reaction temperature is 150-300 ℃, the reaction time is 6-24 h, the hydrogen pressure is 0.5-10.0 MPa, and the mass concentration of the reaction raw materials in the hydrodeoxygenation reaction system is 5-15%.

Technical Field

The invention relates to the technical field of biomass energy, in particular to a preparation method of a biomass liquid fuel.

Background

Energy is an important material basis on which human society relies to survive and develop. The air transportation industry rapidly develops in the 21 st century, and plays an important role in economic development and national safety. Therefore, safe and stable supply of high quality aviation fuel is of great importance. At present, the aviation fuel oil is mainly derived from non-renewable fossil energy sources such as coal, petroleum and the like, and meanwhile, the combustion of the petrochemical-based aviation fuel can discharge a large amount of greenhouse gas carbon dioxide to cause environmental problems such as climate warming and the like, so that the long-term and sustainable development requirements of human beings can not be met. These factors have limited the development of the aerospace industry. Therefore, the search for new, clean and renewable energy sources has become the focus of research in the energy field. Biomass as a renewable organic carbon source is currently a hot research.

Bisphenol A is an important organic chemical raw material, is obtained by reacting phenol and acetone, and is mainly used for producing various high polymer materials such as polycarbonate, epoxy resin, polysulfone resin, polyphenyl ether resin and the like. Can also be used in fine chemical products such as plasticizers, flame retardants, antioxidants, heat stabilizers, rubber antioxidants, pesticides, coatings and the like, and has wide development prospect.

Disclosure of Invention

The invention aims to solve the problems and provide a preparation method of biomass liquid fuel.

The invention realizes the purpose through the following technical scheme:

the invention comprises the following steps:

s1: dissolving bisphenol A in 10mL of n-butanol, reacting in a round-bottom flask with a condenser and a thermometer, adding aldehyde after the bisphenol A is completely dissolved and the solution is transparent, and controlling the mass ratio of the aldehyde to the bisphenol A to be l.0: 1.6; and (3) uniformly mixing, reacting for 6h, evaporating n-butanol solvent by using a rotary evaporator after the reaction is finished, calcining, grinding and sieving to obtain the polymer.

S2: weighing a polymer, adding an acid, stirring, reacting at room temperature for 1-12 h, then quenching with ice water, filtering, washing with deionized water until the pH value is neutral, drying to obtain a solid acid catalyst,

s3: putting aluminum hydroxide into a reaction kettle, adding a magneton, stirring, dropwise adding 85% phosphoric acid at 95 ℃, adding deionized water after complete dissolution, reacting for 12 hours, filtering, and drying for 2 hours at 120 ℃ to obtain a precursor; calcining the obtained precursor in a muffle furnace for 4 hours to obtain an aluminum phosphate molecular sieve;

s4: weighing a molecular sieve, adding the molecular sieve into a nickel nitrate solution, soaking for 12 hours, drying for 12 hours at 120 ℃, calcining for 4 hours at 500 ℃, and reducing for 2 hours at 500 ℃ in a hydrogen atmosphere before use to obtain a nickel-loaded aluminum phosphate catalyst which is used for carrying out hydrodeoxygenation reaction on an alkylation reaction product to obtain high-yield diesel oil or aviation kerosene alkane.

The invention has the beneficial effects that:

compared with the prior art, the preparation method disclosed by the invention has the advantages that the bisphenol A derived acidic resin is used as a solid acid for the alkylation reaction between lignocellulose-based methylfuran and a carbonyl compound, the reactions show good activity and stability, a series of oxygen-containing organic compounds with the carbon number of 13-16 can be obtained through the reactions, and the compounds can be subjected to hydrodeoxygenation to obtain branched-chain alkanes meeting the structural requirements of diesel oil and aviation kerosene.

Drawings

FIG. 1 is a schematic diagram of the reaction of methylfuran with different substrates;

FIG. 2 shows the preparation of 5,5' - (furan-2, 2-diyl) bis (2-methylfuran) according to the present invention¹A HNMR map;

FIG. 3 is a reaction product of methylfuran and 2-pentanone¹A HNMR map;

FIG. 4 is a reaction product of methylfuran and cyclopentanone¹A HNMR map;

FIG. 5 is a reaction product of methylfuran with 2-butanone¹HNMR spectrogram;

FIG. 6 is a diagram of the reaction product of methylfuran and cyclohexanone¹HNMR spectrogram;

FIG. 7 is a graph of the reaction product of methylfuran with acetone¹HNMR map.

Detailed Description

The invention will be further described with reference to the accompanying drawings in which:

firstly, dissolving bisphenol A in 10mL of n-butanol, reacting in a round-bottom flask with a condenser and a thermometer until the bisphenol A is completely dissolved and the solution is transparent, adding a certain amount of aldehyde, and controlling the dosage ratio of the aldehyde to the bisphenol A to be l.0:1.6 (mass ratio). The aldehyde is one or more of paraformaldehyde, formaldehyde, acetaldehyde, butyraldehyde and furfural, preferably paraformaldehyde. And (3) uniformly mixing, reacting for 6h, evaporating n-butanol solvent by using a rotary evaporator after the reaction is finished, calcining, grinding and sieving to obtain the polymer. The polymerization acid may be an inorganic acid or an organic acid. The inorganic acid is one or more of chlorosulfonic acid, phosphotungstic acid, sulfuric acid, nitric acid and phosphoric acid; the organic acid is one or more of trifluoroacetic acid, methanesulfonic acid and p-toluenesulfonic acid. In the polymerization reaction, the dosage ratio of the acid to the bisphenol A is 0.01-0.15: 1, the reaction temperature is 20-100 ℃, and the reaction time is 0.5-24 hours; calcining the polymer obtained by the condensation reaction at the temperature of 100-400 ℃ for 2 hours, weighing a certain amount of polymer, adding chlorosulfonic acid, stirring, reacting at room temperature for 1-12 hours, then quenching with ice water, filtering, washing with deionized water until the pH is neutral, and drying to obtain the solid acid catalyst, wherein the concentration of the chlorosulfonic acid is 0.1-4 mol/L. In addition, the polymer to acid ratio is 1.0g: 1.0-10.0 mL of acid solution. The acidification condition is acidification for 1-12 hours at 20-120 ℃.

The solid acid catalyst synthesized by the method can be used for the alkylation reaction between lignocellulose-based methylfuran and carbonyl compounds. The lignocellulose-based carbonyl compound is one or a mixture of more than two of furfural, 5-hydroxymethyl furfural, acetone, 2-butanone, cyclopentanone, 2-pentanone and cyclohexanone.

The reaction substrates were added sequentially to a round bottom flask, with the molar ratio of methylfuran to carbonyl controlled at 2: 1. The alkylation reaction temperature is 20-100 ℃, the ratio of the catalyst amount to the furan compound is 0.01-0.5: 1, and the reaction time is 0.5-12 hours, preferably 2-3 hours. The alkylation reaction product is an oxygen-containing compound with the carbon number of 13-16, and the oxygen-containing compound is subjected to hydrodeoxygenation to prepare diesel oil or aviation kerosene alkane.

Putting aluminum hydroxide into a reaction kettle, adding a magneton, stirring, dropwise adding a certain amount of phosphoric acid (85%) at 95 ℃, adding a certain amount of deionized water after complete dissolution, reacting for 12 hours, filtering, and drying for 2 hours at 120 ℃ to obtain a precursor; and calcining the obtained precursor in a muffle furnace for 4 hours to obtain the aluminum phosphate molecular sieve. Weighing a certain amount of molecular sieve, adding the molecular sieve into a nickel nitrate solution with a certain concentration, soaking for 12h, drying at 120 ℃ for 12h, calcining at 500 ℃ for 4h, and reducing at 500 ℃ for 2h in a hydrogen atmosphere before use to obtain the nickel-loaded aluminum phosphate catalyst. Used for the hydrodeoxygenation reaction of the alkylation reaction product.

The hydrodeoxygenation reaction is carried out in an intermittent kettle type reactor, and the reaction conditions in the kettle type reactor are as follows: the reaction temperature is 150-300 ℃, the reaction time is 6-24 h, the hydrogen pressure is 0.5-10.0 MPa, and the mass concentration of the reaction raw materials in the hydrodeoxygenation reaction system is preferably 5-15%.

As shown in fig. 1-7:

examples 1 to 83

1. Preparation of solid acid catalyst and alkylation reaction

1) In the following examples, 3.0g of bisphenol A was dissolved in 10mL of an alcohol solvent, then 1.80g of aldehyde was added, and then 0.30g of p-toluenesulfonic acid was added to the mixture to conduct polymerization. The reaction is carried out at the set temperature and the set time. After the reaction, the solvent was evaporated by rotation, dried at 120 ℃ for 4 hours, calcined at a set temperature for 4 hours, ground, and then 1.0g of polymer was weighed and added with 1.0mL of chlorosulfonic acid to react for 4 hours. And carrying out suction filtration, washing to neutrality and drying at 80 ℃ on the acidic resin obtained by acidification to obtain the catalyst.

The alkylation reaction was carried out in a round bottom flask. To a 50mL round bottom flask were added 0.05g of catalyst, 1.64g of 2-methylfuran, and 0.96g of furfural, and the reaction was stirred for 2 hours under a constant temperature oil bath. The reaction product was quantitatively analyzed by High Performance Liquid Chromatography (HPLC).

The solid acid prepared under different conditions catalyzes the reaction of the methyl furan and the furfural, and the reaction results are shown in table 1.

TABLE 1 influence of solid acid catalysts prepared under different reaction conditions on alkylation reactions

As can be seen from table 1: bisphenol A and paraformaldehyde, formaldehyde, acetaldehyde, butyraldehyde, furfural and the like in different solvents (n-butyl alcohol, propanol, isopropanol, isobutanol, pentanol, hexanol), chlorosulfonic acid, phosphotungstic acid, sulfuric acid, nitric acid, phosphoric acid, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid and other acid catalyzed polymerization products. The obtained catalyst has certain catalytic activity when used for catalyzing the reaction of methylfuran and furfural, and the yield of 5,5' - (furan-2, 2-diyl) bis (2-methylfuran) is 28.2 to 98.3 percent.

2) In the following examples, 3.0g of bisphenol A was dissolved in 10mL of n-butanol, then 1.80g of paraformaldehyde was added, and then 0.30g of p-toluenesulfonic acid was added to the mixture to conduct polymerization. The reaction was carried out at the set temperature of 90 ℃ for 6 h. After the reaction is finished, the solvent is evaporated out by rotation, dried for 4h at 120 ℃, calcined for 4h at 180 ℃, and sulfonated by using a certain amount of chlorosulfonic acid solution after grinding. The alkylation activity of the catalyst prepared under the conditions of the dosage, the type, the temperature, the time and the like of the sulfonating acidifying agent is examined.

The alkylation reaction was carried out in a round bottom flask equipped with a condensing reflux apparatus. To a 50mL round-bottom flask, 0.05g of a catalyst, 1.64g of 2-methylfuran, and 0.96g of furfural were added and stirred in a set constant temperature oil bath for reaction for 2.0 hours. The reaction product was quantitatively analyzed by High Performance Liquid Chromatography (HPLC). The reaction results are shown in Table 2.

TABLE 2 influence of different acidification treatments on the activity of the synthesized catalyst

As can be seen from Table 2, both chlorosulfonic acid and sulfuric acid have some sulfonation ability with respect to the polymer synthesized by reacting bisphenol A with paraformaldehyde. The prepared solid acid has certain reaction activity on the alkylation of the methylfuran and the furfural. The yield of 5,5' - (furan-2, 2-diyl) bis (2-methylfuran) was from 63.3% to 98.4%.

3) In the following examples, 3.0g of bisphenol A was dissolved in 10mL of n-butanol, then 1.80g of paraformaldehyde was added, and then 0.30g of p-toluenesulfonic acid was added to the mixture to conduct polymerization. The reaction was carried out at 90 ℃ for 6 h. After the reaction, the solvent was evaporated by rotation, dried at 120 ℃ for 4 hours, calcined at 180 ℃ for 4 hours, ground, and then 1.0g of polymer was weighed, added with 1.0mL of chlorosulfonic acid, and reacted at 25 ℃ for 6 hours. The solid acid prepared under the conditions is used for the condition optimization of the alkylation reaction.

The alkylation reaction was carried out in a round bottom flask equipped with a condensing reflux apparatus. To a 50mL round-bottom flask, 0.05g of a catalyst, 1.64g of 2-methylfuran, and 0.96g of furfural were added and stirred in a set constant temperature oil bath for reaction for 2.0 hours. The reaction product was quantitatively analyzed by High Performance Liquid Chromatography (HPLC). The reaction results are shown in Table 3.

TABLE 3 influence of catalyst dosage, reaction temperature, reaction time on catalytic activity

Note: in the examples, the molar ratio of the reactant 2-methylfuran to furfural was 2:1, the amount of the catalyst used was 0.05g, and the catalyst was calcined at 180 ℃ for 2 hours.

As can be seen from examples 57 to 83, the conversion of 2-methylfuran and the yield of 5,5' - (furan-2, 2-diyl) bis (2-methylfuran) were optimized in the solvent-free reaction at a molar ratio of 2-methylfuran to furfural of 2:1, with 1.64g of reactant, 0.96g of furfural, and 0.05g of catalyst.

Under the optimized condition, the obtained solid acid is used for catalyzing the alkylation reaction of methyl furan with acetone, 2-butanone, 2-pentanone, cyclopentanone, cyclohexanone and 5-hydroxymethyl furfural. The reaction results are shown in FIG. 1.

As can be seen from FIG. 1, in the alkylation reaction of 2-methylfuran with furfural, 5-hydroxymethylfurfural, acetone, butanone, 2-pentanone, cyclopentanone and cyclohexanone, the reaction activity sequences are: furfural > 5-hydroxymethylfurfural > cyclohexanone > 2-pentanone > acetone > 2-butanone > cyclopentanone. The yield of 5,5'- (furan-2-ylmethylene) bis (2-methylfuran) was 98.5%, (the yield of 5- (bis (5-methylfuran-2-yl) methyl) furan-2-yl) methanol was 92.8%, the yield of 5,5' - (propane-2, 2-diyl) bis (2-methylfuran) was 55.1%, the yield of 5,5'- (cyclohexane-1, 1-diyl) bis (2-methylfuran) was 80.5%, the yield of 5,5' - (cyclopentane-1, 1-diyl) bis (2-methylfuran) was 79.3%, the yield of 5,5'- (pentane-2, 2-diyl) bis (2-methylfuran) was 67.5%, 5' - (butane-2, the yield of 2-diyl) bis (2-methylfuran) was 60.5%.

2. Preparation of supported metal catalyst in hydrodeoxygenation

Examples 97 to 127

3.0g of aluminum hydroxide is placed in a reaction kettle, added with a magneton and stirred, then added with 4.7g of phosphoric acid (85%) to react for 12 hours at 95 ℃, filtered, dried for 4 hours at 120 ℃, and calcined for 4 hours in a muffle furnace at a set temperature (400-900 ℃) to obtain the aluminum chlorate carrier.

The metal supported aluminum phosphate catalyst is prepared by an impregnation method. Weighing 0.50g of nickel nitrate hexahydrate, dissolving in 1.6mL of water, adding 2.0g of aluminum phosphate, stirring, standing for 12h, drying at 120 ℃ for 4h, calcining at 500 ℃ for 4h, and reducing at 500 ℃ for 2h in hydrogen atmosphere before use to obtain the catalyst Ni/AlPO₄。

Co/AlPO₄、Ru/AlPO₄、Pd/AlPO₄、Pt/AlPO₄The preparation method is the same as Ni/AlPO₄The preparation method is the same.

Typical reaction: 0.50g of the alkylation reaction product (a), 0.20g of the catalyst and 10mL of cyclohexane are put into a 50mL reaction kettle, and 5.0MPa hydrogen is filled into the reactor after 3-4 of air in the reaction kettle is replaced by hydrogen. The reaction was carried out at 220 ℃ for 24 h. After the reaction, the yield was calculated by gas chromatography analysis. The hydrodeoxygenation reaction results of parameters such as different catalysts, different reaction times, different reaction pressures, different reaction temperatures and the like are shown in the following table:

TABLE 7 Effect of different reaction conditions on the Hydrodeoxygenation reactivity

Note: the nickel loading was 5.0%, cyclohexane was used as a solvent, and the amount used was 10mL each time.

TABLE 8 application of different metals, different loadings to hydrodeoxygenation reactions

Note: cyclohexane is used as a solvent, and the dosage is 10mL each time.

From examples 97 to 127, it can be seen that 5,5' - (furan-2, 2-diyl) bis (2-methylfuran) was hydrodeoxygenated in different catalysts, C₉-C₁₅The yield of alkane can reach 96.5%. The product can be directly used as an aerospace fuel or used as an additive for improving the cetane number, and is added into the existing aerospace fuel in a certain proportion for use.

The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.