CN111320231A - System and method for upgrading algae bio-oil based on CdS ultrasonic coupling photocatalysis - Google Patents
System and method for upgrading algae bio-oil based on CdS ultrasonic coupling photocatalysis Download PDFInfo
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Images
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a system and a method for upgrading algae bio-oil based on CdS ultrasonic coupling photocatalysis. The system and the upgrading method designed by the invention have the advantages of mild upgrading conditions, simple operation, high product selectivity and simple catalyst separation, conform to the concept of environmental protection and have important application prospects.
Description
Technical Field
The invention belongs to the technical field of biomass energy, and particularly relates to a system and a method for upgrading algae bio-oil based on CdS ultrasonic coupling photocatalysis.
Background
The traditional fossil energy is in shortage and brings serious environmental pollution problem, and the development of clean energy is urgent. Biomass energy has received more and more attention as a renewable clean energy source, and algae biomass has become a hot point of research due to the characteristics of high growth speed, strong reproductive capacity, wide distribution, high biofuel yield and the like. The main components of algal biomass are water-soluble polysaccharides, proteins and lipids, and can be converted into biodiesel, biomethane, bioethanol, bio-oil and hydrogen biofuel respectively by an ester exchange method, an anaerobic digestion method, a fermentation method, a thermochemical conversion method and a biological decomposition method. The bio-oil produced by algae under rapid high-temperature cracking is closest to crude oil produced by submarine sediments, but the bio-oil has the characteristics of high oxygen content, high water content, low stability and the like, cannot be directly used for combustion, and needs to further improve the quality.
The algae bio-oil contains alcohols, ketones, nitrogen-containing compounds and phenolic compounds, and also contains carboxylic acid with larger molecular weight and derivatives thereof, the conversion of the carboxylic acid into esters through esterification reaction is an effective way for effectively improving the quality of the bio-crude oil, and the traditional catalytic system mainly adopts a homogeneous catalyst and a thermal catalysis method, so that the problems of high catalyst price, harsh reaction conditions, difficult separation and reutilization of catalytic products and the like exist.
The photocatalysis technology can realize various oxidation and reduction processes under mild conditions, and is a green technology with application prospect. Sunlight is an inexhaustible energy source, and visible light accounts for 50% and 3% of the total solar radiation. The ultrasonic technology can promote the chemical reaction, the solution can generate tiny cavitation bubbles under the action of ultrasonic, and the reaction which is not easy to complete under normal temperature and normal pressure can be promoted along with high temperature and high pressure in the cavitation bubble collapse process. Hydroxyl in carboxylic acid is easy to fall off in the cavitation process to form hydroxyl free radicals to participate in the next reaction, so that the efficiency of upgrading the bio-oil is effectively improved. In addition, the surface of the photocatalyst can be cleaned, so that the catalyst can keep higher photocatalytic performance; and the catalyst is uniformly dispersed in the solution. Therefore, the ultrasonic technology and the photocatalysis coupling have wide application prospect.
Therefore, a photocatalyst responding to visible light is developed and utilized to realize high-efficiency conversion of the algae bio-oil. The currently reported methods still have the problems of severe reaction conditions, difficult recovery of homogeneous catalysts, difficult separation and the like, so that the development of efficient solid photocatalysts for catalyzing algae bio-oil under visible light is still needed.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a system and a method for upgrading algae bio-oil based on CdS ultrasonic coupling photocatalysis, and the system and the method adopt ultrasonic photocatalysis combination and use a cadmium sulfide (CdS) photocatalyst to realize a new method for converting carboxylic acid and derivatives thereof in the bio-oil into ester substances. The reaction condition of the quality-improved algae bio-oil is mild, the operation is simple, the product selectivity is high, the catalyst separation is simple, the energy consumption is low, and the method has an important application prospect.
The technical scheme adopted by the invention is as follows:
a system for improving algae bio-oil based on CdS photocatalysis comprises a closed outer shell, wherein a quartz photochemical reaction tube is arranged inside the outer shell, the inside of the quartz photochemical reaction tube is connected with a gas source outside the outer shell through a pipeline, and algae bio-oil and a CdS photocatalyst are proportionally added into the quartz photochemical reaction tube; the top of the outer shell is provided with a light source; an ultrasonic vibration rod is arranged on the inner wall surface of the outer shell; a certain amount of cooling water is filled in the outer shell, and the ultrasonic vibration rod and the quartz photochemical reaction tube are immersed in the cooling water.
Further, the light source adopts a xenon lamp or an LED lamp combination, and the xenon lamp emits light with different wave bands and is used for simulating natural light with the wavelength of 260-800 nm; the LED lamp has a single wavelength and a wavelength range of 365-500 nm.
A CdS photocatalysis-based algae bio-oil quality-improving method comprises the following steps:
adding algae bio-crude, cadmium sulfide (CdS) catalyst and solvent into a quartz photochemical reaction tube in proportion; and placing the quartz photochemical reaction tube in a photoreaction device, opening an ultrasonic vibration rod, carrying out dark adsorption for half an hour, irradiating by using visible light, keeping the reaction temperature constant at 35 ℃ by using a water bath method, reacting for 3 hours, and centrifugally collecting a catalyst after the reaction is finished to realize the quality improvement of the bio-oil.
Further, the algae bio-crude oil and the cadmium sulfide (CdS) catalyst are in a volume ratio of 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1 or 8: 1;
further, the preparation method of the cadmium sulfide (CdS) catalyst comprises the following steps: in a fume hood, 0.22836g of CdCl was used2.2.5H2Dissolving O and 0.056ml of 3-mercaptopropionic acid in 30ml of deionized water, adjusting the pH of the solution to 11 with 1M NaOH solution, stirring the solution continuously, and adding N2Deoxidizing the solution for half an hour, dropwise adding 0.079g of sodium thiosulfate solution, deoxidizing for 4 hours by using nitrogen, transferring the mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting for one hour at 180 ℃, cooling to room temperature after the reaction is finished, and centrifugally collecting the final product; washing with deionized water and ethanol for three times, and drying in vacuum at 60 ℃ for 12 hours to obtain CdS product; preparing the cadmium sulfide (CdS) catalyst by a hydrothermal method.
Further, the solvent is selected from methanol, ethanol, acetonitrile, tetrahydrofuran, N, N-dimethylformamide, dimethyl sulfoxide, toluene, xylene dichloroethane, acetone, ethyl acetate, chlorobenzene, n-octane, and dioxane, and one of the above solvents or a mixture of two or more thereof is used.
The invention has the beneficial effects that:
1. the ultrasonic coupling photocatalysis technology is mild, convenient, efficient and excellent in application prospect, can improve the quality of the bio-oil at normal temperature and normal pressure, avoids the danger possibly brought by high temperature and high pressure, and can be better applied to practice.
2. The cadmium sulfide catalyst is a solid catalyst, the preparation method is simple, the cadmium sulfide catalyst can be quickly separated from a reaction system, the problem that the homogeneous catalyst is difficult to separate is solved, the cadmium sulfide catalyst can be recycled, and the economic cost is reduced.
3. The catalyst has better response absorption and higher specific surface area in an ultraviolet visible light region, and can realize catalytic reaction under natural light conditions.
4. The used biological oil is generated by fast pyrolysis of Enteromorpha prolifera, has short reaction time, is convenient and easy to obtain, and can be produced in large batch.
5. The method effectively reduces the content of carboxylic acid substances in the algae bio-oil, improves the proportion of ester substances, and improves the quality of the bio-oil
6. In conclusion, the ultrasonic coupling photocatalysis technology is utilized, and the cadmium sulfide catalyst is used for improving the quality of the bio-oil produced by the fast pyrolysis of the Enteromorpha prolifera, so that the content of ester substances in the bio-oil is improved, and the oil yield and the stability are improved. The catalytic system is cheap and efficient, the separation is convenient, the operation is simple and safe, and the method has important application prospect.
Drawings
FIG. 1 is a block diagram of a system for photocatalytic upgrading of algal bio-oil based on CdS;
FIG. 2 is a flow diagram of a method for photocatalytic upgrading of algal bio-oil based on CdS;
FIG. 3 is a CdS photocatalyst solid ultraviolet diffuse reflection diagram;
FIG. 4 is a nitrogen adsorption and desorption isotherm graph of a CdS photocatalyst;
in the figure, 1, an outer shell, 2, an ultrasonic vibration rod, 3, a light source, 4, a gas source, 5, a quartz photochemical reaction tube, 6, a substrate and a catalyst, 7 and cooling water.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The system for improving the algae bio-oil based on the CdS photocatalysis comprises a closed outer shell 1, wherein a quartz photochemical reaction tube 5 is arranged inside the outer shell 1, the inside of the quartz photochemical reaction tube 5 is connected with a gas source 4 outside the outer shell 1 through a pipeline, the gas source 4 is oxygen-containing gas, the oxygen-containing gas is pure oxygen, air or mixed gas consisting of oxygen (air) and inert atmosphere gas, the oxygen concentration in the oxygen-containing gas is 20% -100%, and the inert atmosphere gas is one or two of nitrogen or argon, and the gas pressure is 0.1 MPa. The oxygen-containing gas is fed into the system because the reaction requires oxygen to generate superoxide radical under the catalysis of the catalyst, and the free radical further reacts with the seaweed bio-oil. Algae bio-oil and CdS photocatalyst are added into the quartz photochemical reaction tube 5 in proportion; the top of the outer shell 1 is provided with a light source 3; an ultrasonic vibration stick 2 is arranged on the inner wall surface of the outer shell 1; a certain amount of cooling water 7 is contained in the interior of the outer case 1, and the ultrasonic vibrator 2 and the quartz photochemical reaction tube 5 are immersed in the cooling water. The light source 3 adopts a xenon lamp or an LED lamp combination, and the xenon lamp emits light with the wavelength of 260-800 nm and is used for simulating natural light; the LED lamp has a single wavelength and a wavelength range of 365-500 nm.
As shown in FIG. 2, the method for improving algae bio-oil based on CdS photocatalysis comprises the following steps:
adding algae bio-crude, cadmium sulfide (CdS) catalyst and solvent into a quartz photochemical reaction tube 5 in proportion; and placing the quartz photochemical reaction tube 5 in a photoreaction device, introducing a certain amount of oxygen or air into the quartz photochemical reaction tube 5 through a pipeline, opening an ultrasonic vibration rod, carrying out dark adsorption for half an hour, then opening a light source for reaction, keeping the reaction temperature constant at 35 ℃ by a water bath method, reacting for 3 hours, and centrifugally collecting a catalyst after the reaction is finished to realize the quality improvement of the bio-oil-like substance.
In this example, the preparation process of the algae bio-crude oil is as follows: drying 20g of enteromorpha prolifera in the air, crushing into algae powder with the particle size of less than 0.25mm, drying at 100 ℃ for 4 hours, removing free water, and performing rapid thermal cracking experiments. Firstly, heating a reactor to the working condition of 600 ℃, introducing nitrogen, opening a feeding device to feed materials rapidly, and performing rapid pyrolysis on algae to obtain the biological crude oil of the algae.
The preparation method of the cadmium sulfide (CdS) catalyst comprises the following steps: in a fume hood, 0.22836g of CdCl was used2.2.5H2Dissolving O and 0.056ml of 3-mercaptopropionic acid in 30ml of deionized water, adjusting the pH value of the solution to 11 by using 1M NaOH solution (1M sodium hydroxide solution preparation method: 1g of NaOH solid is added in 25ml of deionized water), stirring continuously, and adding N2Deoxidizing the solution for half an hour, dropwise adding 0.079g of sodium thiosulfate solution, deoxidizing for 4 hours by using nitrogen, transferring the mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting for one hour at 180 ℃, cooling to room temperature after the reaction is finished, and centrifugally collecting the final product. Washing with deionized water and ethanol for three times, and drying in vacuum at 60 deg.C for 12 hr to obtain CdS product. The cadmium sulfide (CdS) catalyst prepared by a hydrothermal method has absorption in both ultraviolet and visible light regions as shown in figures 3 and 4.
The volume ratio of algae biocrude to cadmium sulfide (CdS) catalyst during upgrading may be selected from 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, or 8: 1.
To verify the effectiveness of the method of the present invention in upgrading algal bio-oil, the following data was combined for further verification.
The first embodiment is as follows: adding 0.1g of CdS photocatalyst, 0.1g of algae bio-oil and 10ml of acetonitrile into a photoreaction bottle, sealing, introducing air, inserting a thermometer, placing the bottle into a photoreaction device, opening an ultrasonic vibration rod, carrying out dark adsorption for half an hour, irradiating by a xenon lamp, keeping the temperature constant at 35 ℃, reacting for 3 hours, centrifugally collecting the catalyst after the reaction is finished, and detecting a product by using gas chromatography-mass spectrometry. The content of carboxylic acid and its derivatives is reduced to 3% and the content of ester is increased to 47%.
Example two: adding 0.1g of CdS photocatalyst, 0.1g of algae bio-oil and 10ml of acetonitrile into a photoreaction tube, sealing, introducing air, inserting a thermometer, placing in a photoreaction device, performing dark adsorption for half an hour without opening an ultrasonic vibration rod, irradiating by a xenon lamp at a constant temperature of 35 ℃ for 3 hours, performing centrifugal collection on the catalyst after the reaction is finished, and detecting the product by using gas chromatography-mass spectrometry. The content of carboxylic acid and its derivatives is reduced to 5% and the content of ester is increased to 25%.
Example three: adding 0 into a photoreaction tube.1g TiO2The method comprises the following steps of sealing a photocatalyst, 0.1g of algae bio-oil and 10ml of acetonitrile, introducing air, inserting a thermometer, placing the mixture into a photoreaction device, opening an ultrasonic vibration rod, carrying out dark adsorption for half an hour, irradiating the mixture by a xenon lamp, reacting the mixture for 3 hours at a constant temperature of 35 ℃, centrifugally collecting the catalyst after the reaction is finished, and detecting a product by using gas chromatography-mass spectrometry. The content of carboxylic acid and its derivatives is reduced to 6%, and the content of ester is increased to 22%.
Example four: adding 0.1g of CdS photocatalyst, 0.1g of algae bio-oil and 10ml of acetonitrile into a photoreaction tube, sealing, introducing air, inserting a thermometer, placing the sealed tube into a photoreaction device, opening an ultrasonic vibration rod, carrying out dark adsorption for half an hour, irradiating by a 450nm LED lamp, reacting for 3 hours at a constant temperature of 35 ℃, centrifugally collecting the catalyst after the reaction is finished, and detecting a product by using gas chromatography-mass spectrometry. The content of carboxylic acid and its derivatives is reduced to 6.5%, and the content of ester is increased to 26%.
From the above examples 1 and 2, according to the detection results, when other conditions of the raw materials are consistent, the content of the product ester can be obviously improved by using the ultrasonic vibration rod, and the content of the carboxylic acid and the derivative thereof can be reduced, compared with the example 1 from the example 3, under the condition that other variables are consistent, the CdS photocatalyst has higher selectivity on the generation of the product ester; example 4 compared with example 1, light with a single wavelength can still excite the CdS catalytic esterification reaction. In the four embodiments, the system and the method for improving the bio-oil of the algae based on the CdS photocatalysis provided by the invention can accelerate the esterification reaction process, improve the photocatalysis efficiency, enable the catalyst to absorb more strongly in the visible light range, improve the content of ester substances in the bio-oil of the algae after the reaction is finished, and effectively improve the quality of the bio-oil. The four embodiments show that the method for upgrading algae bio-oil based on CdS photocatalysis and the ultrasonic technology are added, so that the esterification reaction process is accelerated, the photocatalysis efficiency is improved, the catalyst is more strongly absorbed in the visible light range, the content of ester substances in the algae bio-oil is improved after the reaction is finished, and the quality of the bio-oil can be effectively improved.
The above embodiments are only used for illustrating the design idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention accordingly, and the protection scope of the present invention is not limited to the above embodiments. Therefore, all equivalent changes and modifications made in accordance with the principles and concepts disclosed herein are intended to be included within the scope of the present invention.
Claims (6)
1. The system for improving the algae bio-oil based on the CdS photocatalysis is characterized by comprising a closed outer shell (1), wherein a quartz photochemical reaction tube (5) is arranged inside the outer shell (1), the inside of the quartz photochemical reaction tube (5) is connected with an air source (4) outside the outer shell (1) through a pipeline, and the algae bio-oil and the CdS photocatalyst are added into the quartz photochemical reaction tube (5) in proportion; the top of the outer shell (1) is provided with a light source (3); an ultrasonic vibration stick (2) is arranged on the inner wall surface of the outer shell (1); a certain amount of cooling water (7) is filled in the outer shell (1), and the ultrasonic vibration rod (2) and the quartz photochemical reaction tube (5) are immersed in the cooling water.
2. The system for improving the quality of algae bio-oil based on CdS photocatalysis as claimed in claim 1, wherein the light source (3) adopts a xenon lamp or a combination of LED lamps, and the xenon lamp emits light of different wave bands for simulating natural light with a wavelength of 260-800 nm; the LED lamp has a single wavelength and a wavelength range of 365-500 nm.
3. A method for upgrading algae bio-oil based on the CdS photocatalytic upgrading algae bio-oil based system according to claim 1 or 2, wherein algae bio-crude oil, cadmium sulfide catalyst and solvent are proportionally added into a quartz photochemical reaction tube (5); and placing the quartz photochemical reaction tube (5) in a photoreaction device, opening an ultrasonic vibration rod, carrying out dark adsorption for half an hour, irradiating by using visible light, keeping the reaction temperature constant at 35 ℃ by using a water bath method, reacting for 3 hours, and centrifugally collecting a catalyst after the reaction is finished to realize the quality improvement of the bio-oil.
4. The CdS photocatalytic algae bio-oil upgrading method of claim 3, wherein the volume ratio of the algae bio-crude oil to the cadmium sulfide catalyst is 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1 or 8: 1.
5. The algae bio-oil quality improving method based on CdS photocatalysis as claimed in claim 4, wherein the preparation method of said cadmium sulfide catalyst is as follows: in a fume hood, 0.22836g of CdCl was used2.2.5H2Dissolving O and 0.056ml of 3-mercaptopropionic acid in 30ml of deionized water, adjusting the pH value of the solution to 11 by using a 1M NaOH solution, continuously stirring, deoxidizing the solution for half an hour by using nitrogen, dropwise adding 0.079g of sodium thiosulfate solution, deoxidizing for 4 hours by using nitrogen, transferring the mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting for one hour at 180 ℃, cooling to room temperature after the reaction is finished, and centrifugally collecting a final product; washing with deionized water and ethanol for three times, and drying in vacuum at 60 ℃ for 12 hours to obtain a product cadmium sulfide; the cadmium sulfide catalyst is prepared by a hydrothermal method.
6. The CdS photocatalytic algae bio-oil quality improvement method as claimed in claim 5, wherein the solvent is selected from methanol, ethanol, acetonitrile, tetrahydrofuran, N, N-dimethylformamide, dimethyl sulfoxide, toluene, xylene dichloroethane, acetone, ethyl acetate, chlorobenzene, n-octane, and dioxane, and one or more of the above solvents are used in combination.
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Application publication date: 20200623 |