Preparation method of biological ship fuel and applied catalyst

Abstract

The invention relates to a renewable energy technology, in particular to a catalyst applied to a preparation method of biological ship fuel, and the catalyst is a sulfonated carbon catalyst. The sulfonated carbon catalyst is prepared by the following steps: S1, soaking biodiesel waste in n-hexane, standing overnight, and dissolving grease; s2, filtering the dissolved biodiesel waste to obtain an oil-solvent mixture and residues; s3, separating and recovering the solvent and oil from the oil-solvent mixture through a rotary evaporator, and pyrolyzing residues in a tubular rotating bed reactor to obtain a carbonized product and pyrolysis gas; and S4, mixing the carbonized product with concentrated sulfuric acid for reaction to generate the sulfonated carbon catalyst. According to the method, efficient resource utilization of waste is achieved, the produced recycled oil is used for preparing the biological ship fuel, a high-performance catalyst with high adaptability is provided for sustainable biological ship fuel production, the cost is low, the conversion efficiency is high, and the economic benefit is good.

Description

Technical Field

[0001] The invention relates to renewable energy technology, and in particular to a method for preparing biofuel for ships and a catalyst used therein. Background Art

[0002] With the rapid growth of global shipping, energy consumption has increased significantly, and over-reliance on traditional fossil fuels has led to major environmental problems such as energy shortages and climate change. As a renewable energy source derived from vegetable oil or animal fat, biofuel is considered an ideal substitute for traditional fossil diesel due to its plug-and-play nature, biodegradability, low toxicity, and reduced greenhouse gas emissions. However, the production of biofuel still faces challenges in terms of economy and sustainability, such as high raw material costs, inefficient production catalysts, and environmental problems caused by improper resource utilization.

[0003] Biodiesel is an alternative energy source for automotive diesel. Its main component is fatty acid methyl ester. Its waste is a lipid-rich residue produced in the fatty acid methyl ester extraction process, accounting for about 10-20% of the mass of the raw materials (animal and plant oils). Traditional treatment methods usually discard it, resulting in resource waste and environmental pollution. There is an urgent need for a preparation method for bio-ship fuel and the catalyst used to solve the waste of biodiesel waste and the pollution to the environment, and improve the utilization rate of biodiesel. Summary of the invention

[0004] In order to solve the high cost of bio-ship fuel, low production catalyst efficiency and environmental problems caused by improper resource utilization, biodiesel waste is now used to prepare catalysts that can improve the catalytic efficiency of bio-ship fuel production, and catalysts and new raw materials are used to generate bio-ship fuel.

[0005] In order to achieve the above purpose, the present invention provides the following technical solutions: A catalyst used in a method for preparing biofuel for ships, the catalyst being a sulfonated carbon catalyst; The sulfonated carbon catalyst is prepared by the following method: S1: Biodiesel waste was soaked in n-hexane and left overnight to dissolve the oil; S2: filtering the dissolved biodiesel waste to obtain an oil-solvent mixture and a residue; S3: The oil-solvent mixture is separated into the recovered solvent and the recovered oil by a rotary evaporator, and the residue is pyrolyzed in a tubular rotating bed reactor to obtain a carbonized product and pyrolysis gas; S4: The carbonized product is mixed with concentrated sulfuric acid to react to generate a sulfonated carbon catalyst.

[0006] Preferably, in step S3, the recovered solvent is used to dissolve biodiesel waste, and the recovered oil is used as a raw material for bio-ship fuel.

[0007] Preferably, in step S3, the pyrolysis temperature is 300° C. and the pyrolysis time is 1 hour.

[0008] Preferably, in step S3, the pyrolysis gas is condensed at a condensation temperature of 60° C., and the pyrolysis oil formed after condensation is collected as the first component of the biomass ship fuel.

[0009] Preferably, in step S3, the pyrolysis gas is condensed at a condensation temperature of 60° C., and the uncondensed pyrolysis gas is used as fuel for the heat source of the tubular rotating bed.

[0010] Preferably, in step S4, in the mixed reaction of the carbonized product and concentrated sulfuric acid, the mass ratio of the carbonized product and concentrated sulfuric acid is 1:1, and the reaction conditions are 150° C. for at least 6 hours to obtain the reaction product; The product after the reaction was washed with distilled water for several times until it was neutral, and dried at 100° C. for at least 2 hours to obtain a sulfonated carbon catalyst.

[0011] A method for preparing biofuel for ship using sulfonated carbon catalyst, the method for preparing biofuel for ship is as follows: SS1: Recycled oil is mixed with new raw materials to form a mixed material; SS2: adding methanol and sulfonated carbon catalyst to the mixture to carry out catalytic reaction; SS3: After the catalytic reaction is completed, the sulfonated carbon catalyst is separated using a filter, the glycerol layer is removed, and the crude biomass fuel is obtained; SS4: The crude bio-ship fuel is subjected to a rotary evaporator to remove residual methanol and water, and then distilled to obtain the bio-ship fuel component 2; SS5: The bio-ship fuel component 1 formed by condensing the pyrolysis gas in step S3 is mixed with the bio-ship fuel component 2 to obtain the bio-ship fuel.

[0012] Preferably, the novel raw material is one of palmitic acid oil, peanut oil fatty acid, and rice bran acid oil.

[0013] Preferably, in the process of preparing bio-ship fuel, the molar ratio of methanol to oil is 15:1-4:1, and the mass proportion of sulfonated carbon catalyst is 1-5%; The catalytic reaction conditions are: react at 40-70°C and 500 rpm for 1-6 hours.

[0014] Beneficial effects of the present invention: 1. Using biodiesel waste to prepare sulfonated carbon catalyst, this sulfonated carbon catalyst has good stability and reusability. This reusability greatly reduces the production cost.

[0015] 2. Use new raw materials such as rice bran acidified oil, palmitic acidified oil, and peanut oil fatty acid to obtain high-quality bio-ship fuel through catalysis with sulfonated carbon catalyst. The flash point of the bio-ship fuel product obtained by catalysis is higher than 60°C, with good transportation and storage safety, low cost, suitable for green replacement of ship fuel, low sulfur content, and meets the requirements of international standard EN14214.

[0016] 3. The present invention not only realizes the efficient resource utilization of waste and produces recycled oil for the preparation of bio-ship fuel, but also provides a highly adaptable high-performance catalyst for sustainable bio-ship fuel production, further improving the efficiency and economic benefits of bio-ship fuel production, with low cost, high conversion efficiency and good economic benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is a process flow chart of the present invention. DETAILED DESCRIPTION

[0018] The following examples are given to further illustrate the present invention. It is necessary to point out that the following examples cannot be understood as limiting the scope of protection of the present invention. If a person skilled in the art makes some non-essential improvements and adjustments to the present invention based on the above content of the present invention, it still belongs to the scope of protection of the present invention.

[0019] Biodiesel is an alternative energy source for automotive diesel. Its main component is fatty acid methyl ester. Biodiesel waste is a lipid-rich residue produced in the process of fatty acid methyl ester extraction, accounting for about 10-20% of the mass of the raw materials (animal and plant oils and fats). Its main components include oils (60-70%), polymerized oils (25-35%), mineral particles (2%) and organic matter (2.5-3%). The lipid part is rich in oleic acid (about 75%), followed by palmitic acid, linoleic acid and stearic acid. Other organic matter such as sugar (3%), protein (1.5%), polyphenols (0.2%) and volatile fatty acids (1%) provide the necessary chemical active ingredients for catalyst preparation and are ideal raw materials for catalyst preparation. Traditional treatment methods usually discard it, resulting in resource waste and environmental pollution.

[0020] Based on the current situation that biodiesel waste cannot be fully utilized, the present invention provides a method for preparing sulfonated carbon catalyst from biodiesel waste and its application, the purpose of which is to achieve efficient resource utilization of biodiesel waste, provide high-performance catalyst with strong raw material adaptability for sustainable bio-ship fuel production, and further improve the production efficiency and economic benefits of new raw materials for biomass pyrolysis catalyst. The specific scheme is as follows: A catalyst used in a method for preparing biofuel for ships, the catalyst being a sulfonated carbon catalyst; The sulfonated carbon catalyst is prepared by the following method: S1: Biodiesel waste was soaked in n-hexane and left overnight to dissolve the oil; S2: filtering the dissolved biodiesel waste to obtain an oil-solvent mixture and a residue; S3: The oil-solvent mixture is separated into the recovered solvent and the recovered oil by a rotary evaporator, and the residue is pyrolyzed in a tubular rotating bed reactor to obtain a carbonized product and pyrolysis gas; S4: The carbonized product is mixed with concentrated sulfuric acid to react to generate a sulfonated carbon catalyst.

[0021] In step S3, the recovered solvent is used to dissolve biodiesel waste, and the recovered oil is used as a raw material for bio-ship fuel. In step S3, the pyrolysis temperature is 300°C and the pyrolysis time is 1 hour. In step S3, the pyrolysis gas is condensed at a condensation temperature of 60°C, and the pyrolysis oil formed after condensation is collected as a component of bio-ship fuel, and the bio-ship fuel is a mixture of one or more of alkanes, cycloalkanes, and aromatic hydrocarbons. In step S3, the pyrolysis gas is condensed at a condensation temperature of 60°C, and the uncondensed pyrolysis gas is used as a fuel for the heat source of the tubular rotating bed. In step S4, in the mixed reaction of the carbonized product and concentrated sulfuric acid, the mass ratio of the carbonized product and concentrated sulfuric acid is 1:1, and the reaction conditions are 150°C for at least 6 hours to obtain the reaction product; the product after the reaction is washed with distilled water several times until it is neutral, and dried at 100°C for at least 2 hours to obtain a sulfonated carbon catalyst.

[0022] A method for preparing biofuel for ship using sulfonated carbon catalyst, the method for preparing biofuel for ship is as follows: SS1: Recycled oil is mixed with new raw materials to form a mixed material; SS2: adding methanol and sulfonated carbon catalyst to the mixture to carry out catalytic reaction; SS3: After the catalytic reaction is completed, the sulfonated carbon catalyst is separated using a filter, the glycerol layer is removed, and the crude biomass fuel is obtained; SS4: The crude bio-ship fuel is subjected to a rotary evaporator to remove residual methanol and water, and then distilled to obtain the bio-ship fuel component 2, which is fatty acid methyl ester; SS5: The bio-ship fuel component 1 formed by condensing the pyrolysis gas in step S3 is mixed with the bio-ship fuel component 2 to obtain the bio-ship fuel.

[0023] The new raw material is one of palmitic acid oil, peanut oil fatty acid, and rice bran acid oil. In the preparation process of bio-ship fuel, the molar ratio of methanol to oil is 15:1-4:1, and the mass proportion of sulfonated carbon catalyst is 1-5%; the catalytic reaction conditions are: reaction at 40-70℃ and 500rpm for 1-6 hours.

[0024] During the implementation of the present invention: The sulfonated carbon catalyst (SC) obtained by the reaction was subjected to X-ray diffraction (XRD), and the results showed that the catalyst was amorphous, showing surface area and catalytic activity, with good stability and catalytic performance. The reusability of the sulfonated carbon catalyst in biodiesel production was verified by 10 consecutive reactions. The results showed that the performance of the catalyst decreased by only 4% after 10 cycles, indicating that it has good stability and reusability. This reusability significantly reduces production costs.

[0025] When the solvent was recovered by a rotary evaporator (60°C), the yield of recovered oil was 85%. The physicochemical properties of the recovered oil were tested using the ASTM standard method. The test results showed that the acid value of the recovered oil was 1.7 mgKOH / g, the saponification value was 177 mgKOH / g, and the density was 0.8994 g / cm³. The test results showed that the recovered oil was an ideal raw material for the production of bio-ship fuel. The new raw material and the recovered oil were mixed as a reaction mixture for bio-ship fuel II. The new raw material here was one of palmitic acid oil, peanut oil fatty acid, rice bran acid oil, etc.

[0026] The following is a detailed description of the preparation method of bio-ship fuel and the application of catalyst in the preparation of bio-ship fuel with specific examples: Example 1, when the sulfonated carbon catalyst is used to prepare bio-ship fuel, the novel raw material is rice bran acidified oil, and the method for preparing the bio-ship fuel is as follows: Rice bran acidified oil was mixed with recycled oil, and then mixed with methanol and sulfonated carbon catalyst in proportion, with a methanol to oil ratio of 15:1-5:1, a catalyst dosage of 1-5%, and a reaction time of 1-6 hours at 40-70℃ and 500 rpm. The single factor optimization conditions were: a methanol to oil ratio of 5:1, a reaction temperature of 55℃, a reaction time of 5 hours, and a catalyst dosage of 4%. The conditions were then further optimized using optimization and response surface methodology (RSM) analysis. The process conditions were designed using Box-Behnken. The quadratic polynomial model established by regression analysis accurately predicted the optimal reaction conditions. The results showed that the optimal parameter combination was a methanol to oil ratio of 17:3, a reaction time of 5.6 hours, a temperature of 54.9℃, and a catalyst concentration of 4.1%. The yield of crude bio-ship fuel reached 94%. This high conversion rate was attributed to the excellent performance of the sulfonated carbon catalyst. The catalyst was separated using a filter, and the glycerol layer was removed using density difference. The residual methanol and water were removed by rotary evaporator, and the bio-ship fuel component II was obtained by distillation with a yield of 90%. The final product, bio-ship fuel, is blended with bio-ship fuel component 2 and bio-ship fuel component 1. The flash point of the obtained bio-ship fuel product is higher than 60°C, and it is safe for transportation and storage. It is low-cost and suitable for green replacement of ship fuel. The sulfur content is 7PPM, which meets the requirements of the most stringent international standard EN14214.

[0027] Example 2: When the sulfonated carbon catalyst is used to prepare bio-ship fuel, the novel raw material is palmitic acid oil, and the method for preparing the bio-ship fuel is as follows: Rice palm acidified oil was mixed with recycled oil, and then mixed with methanol and sulfonated carbon catalyst in proportion. The conditions were further optimized by optimization and response surface methodology (RSM) analysis. The Box-Behnken design process conditions were used, and the quadratic polynomial model established by regression analysis accurately predicted the optimal reaction conditions. The results showed that the optimal parameter combination was a methanol to oil ratio of 16:3, a reaction time of 5.1 hours, a temperature of 55.2°C, and a catalyst concentration of 4.4%. The yield of bio-ship fuel reached 92%. The catalyst was separated by a filter, and the glycerol layer was removed by density difference. The residual methanol and water were removed by rotary evaporator, and the bio-ship fuel component 2 was obtained by distillation. The bio-ship fuel component 2 was blended with the bio-ship fuel component 1 to obtain the final product bio-ship fuel with a sulfur content of 5PPM.

[0028] Example 3: When the sulfonated carbon catalyst is used to prepare bio-ship fuel, the novel raw material is peanut oil fatty acid. The method for preparing the bio-ship fuel is as follows: Peanut oil fatty acids were mixed with recycled oil, and then mixed with methanol and sulfonated carbon catalyst in proportion. The conditions were further optimized using optimization and response surface methodology (RSM) analysis. The Box-Behnken design process conditions were used, and the quadratic polynomial model established by regression analysis accurately predicted the optimal reaction conditions. The results showed that the optimal parameter combination was a methanol to oil ratio of 4:1, a reaction time of 5.4 hours, a temperature of 55.7°C, and a catalyst concentration of 4.3%. The biofuel yield for ships reached 93%.

[0029] The catalyst is separated by a filter, and the glycerol layer is removed by density difference. The residual methanol and water are removed by rotary evaporator, and the bio-ship fuel component 2 is obtained by distillation. The bio-ship fuel component 2 is blended with the bio-ship fuel component 1 to obtain the final product bio-ship fuel, and the sulfur content is 9PPM.

[0030] The optimal parameters for generating bio-ship fuel after mixing the three new raw materials and recovering oil are as follows:

[0031] From the above, it can be seen that the sulfonated carbon catalyst is used to catalyze the production of bio-ship fuel from palmitic acid oil, peanut oil fatty acid, and rice bran acid oil, and the yield is significantly improved, the sulfur content is low, and high-quality bio-ship fuel is obtained.

[0032] The preparation method of this bio-ship fuel and the catalyst used in it realize the efficient resource utilization of biodiesel waste, and provide a highly adaptable high-performance catalyst for sustainable bio-ship fuel production, further improving the efficiency and economic benefits of biomass pyrolysis catalysts in bio-ship fuel production.

[0033] The above-mentioned embodiments only express several implementation methods of the present invention, and the description is relatively specific and detailed, but it cannot be understood as limiting the scope of the invention patent. It should be pointed out that for ordinary technicians in this field, several modifications and improvements can be made without departing from the concept of the present invention, which are all protected by the present invention. scope.

Claims

1. A catalyst used in a method for preparing biofuel for ships, characterized in that: The catalyst is a sulfonated carbon catalyst; The sulfonated carbon catalyst is prepared by the following method: S1: Biodiesel waste was soaked in n-hexane and left overnight to dissolve the oil; S2: filtering the dissolved biodiesel waste to obtain an oil-solvent mixture and a residue; S3: The oil-solvent mixture is separated into the recovered solvent and the recovered oil by a rotary evaporator, and the residue is pyrolyzed in a tubular rotating bed reactor to obtain a carbonized product and pyrolysis gas; S4: The carbonized product is mixed with concentrated sulfuric acid to react to generate a sulfonated carbon catalyst.

2. The catalyst used in the method for preparing biofuel for ships according to claim 1, characterized in that: In step S3, the recovered solvent is used to dissolve the biodiesel waste, and the recovered oil is used as the raw material of bio-ship fuel.

3. The catalyst used in the method for preparing biofuel for ships according to claim 1, characterized in that: In step S3, the pyrolysis temperature is 300° C. and the pyrolysis time is 1 hour.

4. The catalyst used in the method for preparing biofuel for ships according to claim 1, characterized in that: In step S3, the pyrolysis gas is condensed at a condensation temperature of 60° C. The pyrolysis oil formed after condensation is collected as the first component of the biomass ship fuel.

5. The catalyst used in the method for preparing biofuel for ships according to claim 1, characterized in that: In step S3, the pyrolysis gas is condensed at a condensation temperature of 60° C. The uncondensed pyrolysis gas is used as fuel for the heat source of the tubular rotating bed.

6. The catalyst used in the method for preparing biofuel for ships according to claim 1, characterized in that: In the step S4, the carbonized product and concentrated sulfuric acid are mixed in a reaction at a mass ratio of 1:1, and the reaction conditions are 150° C. for at least 6 hours to obtain a reaction product; The product after the reaction was washed with distilled water for several times until it was neutral, and dried at 100° C. for at least 2 hours to obtain a sulfonated carbon catalyst.

7. A method for preparing biofuel for ships using the catalyst of claim 1, characterized in that: The preparation method of biofuel for ships is as follows: SS1: Recycled oil is mixed with new raw materials to form a mixed material; SS2: adding methanol and sulfonated carbon catalyst to the mixture to carry out catalytic reaction; SS3: After the catalytic reaction is completed, the sulfonated carbon catalyst is separated using a filter, the glycerol layer is removed, and the crude biomass fuel is obtained; SS4: The crude bio-ship fuel is subjected to a rotary evaporator to remove residual methanol and water, and then distilled to obtain the bio-ship fuel component 2; SS5: The bio-ship fuel component 1 formed by condensing the pyrolysis gas in step S3 is mixed with the bio-ship fuel component 2 to obtain the bio-ship fuel.

8. The method for preparing biomass fuel according to claim 7, characterized in that: The novel raw material is one of palmitic acid oil, peanut oil fatty acid and rice bran acid oil.

9. The method for preparing biomass fuel according to claim 7, characterized in that: In the process of preparing bio-ship fuel, the molar ratio of methanol to oil is 15:1-4:1, and the mass proportion of sulfonated carbon catalyst is 1-5%; The catalytic reaction conditions are: react at 40-70°C and 500 rpm for 1-6 hours.

Images