CN114891529A - Method for preparing high-quality bio-oil by catalyzing algae microwave hydrolysis through heterogeneous composite molecular sieve - Google Patents
Method for preparing high-quality bio-oil by catalyzing algae microwave hydrolysis through heterogeneous composite molecular sieve Download PDFInfo
- Publication number
- CN114891529A CN114891529A CN202210420087.2A CN202210420087A CN114891529A CN 114891529 A CN114891529 A CN 114891529A CN 202210420087 A CN202210420087 A CN 202210420087A CN 114891529 A CN114891529 A CN 114891529A
- Authority
- CN
- China
- Prior art keywords
- algae
- catalyst
- hzsm
- oil
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing high-quality bio-oil by catalyzing algae through microwave hydrolysis by using a heterogeneous composite molecular sieve, which comprises the following steps: 1) loading Ni ions on an alkali modified HZSM-5 catalyst; 2) adding the algae and the Ni/HZSM-5 catalyst prepared in the previous step into a polytetrafluoroethylene reaction tank to hydrolyze the algae; 3) after the reaction was completed, the solid was washed with ethyl acetate several times until the washing solution became colorless and transparent, and bio-oil was obtained by rotary evaporation. The invention discloses two technical means of coupling catalytic hydrolysis and microwave heating, and aims to convert algae biomass into high-quality bio-oil rich in hydrocarbons through catalysis, so that the high-quality bio-oil becomes a low-cost and high-benefit fossil fuel substitute, and the problems of energy crisis and carbon emission reduction are solved. Compared with the traditional heating mode, the microwave heating mode is more uniform, and the heating rate is higher. And the algae is hydrolyzed without drying and other treatments, thereby simplifying fussy treatment and reducing energy consumption.
Description
Technical Field
The invention relates to the field of biomass energy chemical industry, in particular to a method for preparing high-quality bio-oil by catalyzing algae microwave hydrolysis through a heterogeneous composite molecular sieve.
Background
The method has the advantages of promoting clean, low-carbon, safe and efficient utilization of energy, accelerating industrial development of new energy, green and environment protection and the like, and promoting comprehensive green transformation of economic and social development. The biomass is expected to become a substitute of fossil fuel as a renewable energy source with zero net carbon emission in the whole life cycle. The algae is called third generation biomass energy, the photoautotrophic growth process of the algae is higher in photosynthetic carbon fixation efficiency compared with other biomass, and the photosynthetic productivity of the algae can reach 50g/(m2 d) to the maximum under the same condition, which is equivalent to 10-50 times of the carbon fixation capacity of forests. The growth process does not compete with the crops for land and water. Algae are mainly composed of carbohydrates (8-30 wt.%), proteins (40-60 wt.%), and lipids (5-60 wt.%). Carbohydrates mainly consist of saccharides, and the cracking, ring opening and branch chain breaking of glycosidic bonds in the thermochemical conversion process are three main reactions in the pyrolysis process of the carbohydrates to generate products such as pyran, furan, acid, ketone, aldehyde and the like. Up to 70 wt.% of N in algae is converted to liquid oil, the content of N and O in bio-oil is up to 8.75 and 14.10 wt.%, respectively, and high content of nitrogen and oxygen causes bio-oil instability. However, algal biomass contains a significant amount of lipid components compared to cellulosic biomass, and thermochemical conversion efficiently converts lipids to hydrocarbons, so algal biomass produces higher bio-oil yields than thermochemical conversion of lignocellulosic biomass. The east of Qingdao Ling yellow sea often has large-scale green tide and red tide outbreaks in summer, namely algae grows explosively on a large scale, so that the water quality is deteriorated, foul smell is emitted, the environment is seriously damaged, and oxygen in water is exhausted to cause death of fishes. Therefore, the algae biomass has great development potential, and energy utilization is beneficial to solving the environmental problem, saving energy and reducing emission, and economic, social and ecological benefits can be created.
Pyrolysis and hydrolysis are two common thermochemical conversion methods that can promote efficient utilization of algal biomass and convert algae into liquid fuels that are convenient to store and transport. However, the seaweed is used as a reaction raw material with high water content, and a large amount of heat energy is consumed in the pyrolysis process. From the energy saving point of view, hydrothermal liquefaction has numerous advantages over pyrolysis: (1) the raw materials do not need to be dried and dehydrated; (2) lower reaction temperature; (3) because substances such as protein, grease, saccharides and the like which form algae cells can be converted into bio-oil and related compounds in the hydrothermal liquefaction process, the oil yield is high; (4) the bio-oil obtained by the algae hydrothermal liquefaction has high heat value, low oxygen content and water content and more stable property, so the hydrolysis liquefaction is a promising comprehensive algae utilization technology. In the experimental process of hydrothermal depolymerization of seaweed, the defects of high energy consumption, long time, low thermal efficiency and the like exist in the conventional electric heating mode to reach the experimental conditions. Microwave heating is a novel heating mode for biomass hydrolysis, and the essence of microwave heating is energy dissipation of microwaves in materials. Compared with the defects of the traditional heating mode, the microwave heating mode has the following advantages: (1) the heating is rapid and uniform: the microwave heating has high energy utilization rate, rapid material temperature rise and strong microwave penetrability, can uniformly heat the inside and the outside of the material, and does not need to crush the material; (2) energy consumption is saved: the microwave generator and the microwave heater are not in direct contact with the materials, and the materials do not need to be fluidized and the like; (3) no hysteresis effect: after the microwave emission source is closed, no energy conversion is carried out; (4) the operation is convenient: the microwave heating response is quick, the material temperature can be accurately controlled, and the automatic control is convenient; (5) is safe and pollution-free. However, the application of microwaves to the catalytic hydrolysis of biomass is not currently common.
The existing methods for preparing the bio-oil by the biomass mainly comprise a rapid pyrolysis method, a direct liquefaction method, a supercritical extraction method and a biological method. At present, the method for preparing liquid fuel by direct liquefaction of algae researched by researchers at home and abroad mainly comprises 4 technologies of direct liquefaction, pyrolysis, extraction esterification and biological fermentation. Recently, as the bio-oil is prepared by co-pyrolysis catalytic hydrogenation of algae and waste rubber provided by chinese patent 201510793073.5, and the bio-oil is prepared by vacuum pyrolysis of microalgae in chinese patent 201610159451.9 through on-line layered catalytic hydrogenation, although the liquid dye obtained by pyrolysis of algae has good prospects, the above techniques still have many problems in the application process, such as high energy consumption, low bio-oil quality, and the like. For example, in the Chinese patent 201510793073, the biological oil is prepared by co-pyrolyzing algae and waste rubber and performing catalytic hydrogenation, the preparation process is complex, and the algae needs to be dried, so that the energy consumption is high.
The catalysts used at present mainly comprise metal oxides, salts and molecular sieves. In the process of biomass catalytic hydrolysis, the catalyst has an important influence effect, and is mainly a heterogeneous catalyst. The heterogeneous catalyst refers to a catalytic process in which reactants and a catalyst are not completely (or completely) in the same phase in a reaction of different phases, and the heterogeneous catalyst at the present stage can improve the quality of bio-oil to a certain extent, but has the disadvantages of coking, poor reuse rate, low catalytic activity, high price and the like. Considering that the use of catalysts increases the cost, particularly noble metal catalysts, and the reduction of the catalyst utilization cost, the improvement of the catalytic activity of the catalyst is an important direction of research. The HZSM-5 used at the present stage has the problems of coking, poor reuse rate and low catalytic activity. Research shows that the organic base modified HZSM-5 has a mesoporous structure, so that the anti-coking capacity can be obviously improved, and the selectivity of the organic base modified HZSM-5 to aromatic hydrocarbon is improved. Besides the noble metal as the load metal, the transition zone metal has the characteristics of low price, good catalytic activity and the like, and is widely applied and researched in the catalytic pyrolysis process of the biomass. Meanwhile, researches show that the existence of the metal element can activate C-H bonds in the biomass structure, and further promote the subsequent breakage of connecting bonds such as ether bonds and the like between basic units in the dimer. The Ni metal element reduces the decomposition temperature, the carbon yield, the activation energy and the like of the biomass, thereby having a remarkable influence on the thermal conversion process of the biomass. HZSM-5 is used as a catalyst to improve the selectivity of hydrocarbon, namely the quality of the bio-oil. The HZSM-5 can have a central control structure only by organic base modification. So that in the reaction process, macromolecular substances are cracked into small molecules, and the small molecules are changed into hydrocarbons through aromatization, deoxidation and the like. In addition, organic base modification allows a portion of the strong acid sites to disappear, providing attachment sites for Ni, which also has catalytic ability. The HZSM-5 has a lot of reports on improving the quality of the bio-oil, and the inventor modifies the HZSM-5 on the basis of the report, so that the quality of the bio-oil becomes better.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for preparing high-quality bio-oil by catalyzing algae through microwave hydrolysis by using a heterogeneous composite molecular sieve, which uses algae as a raw material, selects a microporous molecular sieve HZSM-5 with a high silica-alumina ratio, uses an organic alkali tetrapropylammonium hydroxide solution for modification, carries out an impregnation method to load a metal element Ni, finally prepares an alkali-modified Ni/HZSM-5 catalyst, and places the algae and the catalyst in an acid solution for microwave-assisted hydrolysis.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing high-quality bio-oil by catalyzing microwave hydrolysis of algae by using heterogeneous composite molecular sieve, comprising the following steps:
1) loading Ni ions on an alkali modified HZSM-5 catalyst;
2) adding algae and the Ni/HZSM-5 catalyst prepared in the previous step into a polytetrafluoroethylene reaction tank, adding a rotor, stirring and preheating for 80 ℃, wherein the preheating time is 20-30 minutes, then raising the temperature to 160-210 ℃, the reaction time is 20-30 minutes, and the pressure is 2-3 MPa, and hydrolyzing the algae under the conditions;
3) and after the reaction is finished, cooling to room temperature, washing with sufficient ethyl acetate and ethanol, transferring all the reactants, the washing liquid and the solid into a beaker, performing suction filtration by using a solvent filtering device, washing the solid for multiple times by using ethyl acetate until the washing liquid becomes colorless and transparent, and obtaining the bio-oil by using a rotary evaporation method.
Further, in the step 1), a specific method for loading Ni ions on the alkali-modified HZSM-5 catalyst is as follows: dissolving a proper amount of nickel nitrate in deionized water, adding an alkali modified HZSM-5 catalyst into the solution, stirring for 4-5 hours in a water bath at 80-90 ℃, filtering the reaction mixture after finishing the exchange, drying the filtered solid matter for 10-12 hours at 80-90 ℃, calcining for 4 hours at 500-550 ℃, and grinding, tabletting, crushing and screening the sample into particles of 20-40 meshes after the sample is cooled; wherein the weight ratio of the nickel nitrate to the alkali modified HZSM-5 catalyst is 1: 6.
further, in the step 2), magnetic stirring is selected, and the specific method of magnetic stirring is as follows: and adding a rotor with a proper size into the reaction kettle, and adjusting the rotating speed of a motor in the microwave reaction furnace to be 300-400 r/min.
Further, in the step 2), the method for adding the catalyst is as follows: firstly, adding algae, an acidic solution and a magnetic stirring rotor into a reaction kettle, heating to a preheating temperature, keeping the temperature for a period of time, then adding a catalyst, and continuing to heat for reaction.
Further, in the step 2), the seaweeds are collected from the Qingdao coastal areas.
Further, in the step 2), the specific method for microwave hydrolysis of algae comprises:
weighing algae and a catalyst Ni/HZSM-5 respectively, pouring the algae and the catalyst Ni/HZSM-5 into a reaction tank, and stirring to uniformly mix the algae and the catalyst Ni/HZSM-5; wherein the weight ratio of the algae organisms to the catalyst Ni/HZSM-5 is 1-2: 1-2;
pouring 6-10% v/v acid solution into a reaction tank, and adding a rotor;
thirdly, placing the reaction tank into a microwave device, raising the temperature to 80 ℃ at a temperature rise rate of 25-30 ℃/min, and preserving the temperature for 20-30 minutes; then raising the temperature to 160-210 ℃ at a temperature raising rate of 15-30 ℃/min, preserving the temperature for 20-30 minutes, keeping the pressure at 1.8-3 MPa, and setting the rotating speed of a rotor at 300-400 r/min;
fourthly, after the reaction is finished, taking out the reaction tank when the temperature of the reaction tank is cooled to 55-60 ℃ and the pressure is 0 MPa;
fifthly, transferring the reactant into a glass bottle, then cleaning the wall surface of the reaction tank by using ethyl acetate, and extracting the residual reactant.
Further, in the step 3), a specific method for obtaining the bio-oil by rotary evaporation is adopted: transferring the liquid into a round-bottom flask, performing rotary evaporation at 40 ℃ to remove ethyl acetate, heating to 60 ℃ to remove ethanol, and performing rotary evaporation to obtain the bio-oil product.
Further, the preparation method of the alkali modified HZSM-5 comprises the following steps:
1) ZSM-5 zeolite with 5wt% NH 4 NO 3 Ion exchange is carried out on the solution for 4-5 hours at the temperature of 80-90 ℃; washing the solid product to neutrality by using distilled water; repeating the steps for 2 times, drying the obtained sample in an oven at 100 ℃ for 24 hours, and calcining the dried sample at 500-550 ℃ for 5 hours to prepare HZSM-5;
2) adding HZSM-5 into an alkaline solution, stirring for 1 hour at 40 ℃, then cooling a sample to room temperature, adjusting the pH of the obtained solution to 8-8.5, filtering, washing and drying the solution after the pH is adjusted, and then calcining a solid sample for 5 hours in an air environment at 500-550 ℃ to prepare the organic modified HZSM-5 catalyst.
Further, the alkaline solution is tetrapropylammonium hydroxide solution, and the concentration is 0.5 mol/L.
In the present invention, the "high-quality bio-oil" means a bio-oil having a relatively high hydrocarbon content and a relatively high calorific value.
The invention has the following technical effects:
1) the invention discloses two technical means of coupling catalytic hydrolysis and microwave heating, and aims to convert algae biomass into high-quality bio-oil rich in hydrocarbons through catalysis, so that the high-quality bio-oil becomes a low-cost and high-benefit fossil fuel substitute, and the problems of energy crisis and carbon emission reduction are solved. Compared with the traditional heating mode, the microwave heating mode is more uniform, and the heating rate is higher. And the algae is hydrolyzed, and treatment such as drying and the like is not needed, so that the complicated treatment is simplified, and the energy consumption is reduced.
2) The patent combines the advantages of metal element Ni and organic alkali modified molecular sieve catalyst to construct a novel heterogeneous composite molecular sieve catalyst with metal elements.
Drawings
FIG. 1 is a graph showing the calculation results of the ratios of the respective substances in the bio-oil product of example 1. Wherein the abscissa represents various substances contained in the bio-oil.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and it is apparent that the described examples are only a part of the examples of the present invention, and not all of the examples.
Example 1
Firstly, ZSM-5 zeolite and 5wt% of NH 4 NO 3 Ion exchange of the solution at 80 deg.c for 4 hr; washing the solid product to neutrality by using distilled water; repeating the steps for 2 times, drying the obtained sample in an oven at 100 ℃ for 24 hours, and calcining the dried sample at 550 ℃ for 5 hours to prepare HZSM-5;
adding HZSM-5 into an alkaline solution tetrapropylammonium hydroxide (TPAOH) solution with the concentration of 0.5mol/L, stirring for 1 hour at 40 ℃, then cooling a sample to room temperature, adjusting the pH of the obtained solution to 8.5, filtering, washing and drying the solution after the pH is adjusted, and then calcining a solid sample for 5 hours in an air environment with the temperature of 550 ℃ to prepare an organic modified HZSM-5 catalyst;
dissolving 0.082g of nickel nitrate into 200mL of deionized water, then adding 0.5g of the HZSM-5 molecular sieve modified by the alkali prepared in the step two into the solution, stirring for 4 hours on a water bath at 80 ℃, filtering the reaction mixture after finishing the exchange, drying the filtered solid substance for 10 hours at 80 ℃, then calcining for 4 hours at 550 ℃, and grinding, tabletting, crushing and sieving the sample into particles of 40 meshes after the sample is cooled;
fourthly, weighing 4g of the catalyst Ni/HZSM-5 obtained in the third step and 4g of algae, pouring the catalyst Ni/HZSM-5 and the algae into a reaction tank, and stirring to uniformly mix the catalyst Ni/HZSM-5 and the algae;
fifthly, preparing a sulfuric acid solution: measuring 50mL of deionized water by using a measuring cylinder, pouring the deionized water into a beaker, adding 3mL of concentrated sulfuric acid, measuring 47mL of deionized water by using the measuring cylinder, and pouring the deionized water into the beaker;
and sixthly, pouring the prepared acid solution into a reaction tank, and adding a rotor. Placing the reaction tank into a microwave device, heating to 80 deg.C for 3min, and maintaining the temperature for 25 min; adding weighed catalyst; raising the temperature to 200 ℃ for 7min, and keeping the temperature for 25 min; the pressure is 1.9MPa, and the rotating speed of the magnetic stirring rotor is set to be 300 r/min.
And seventhly, after the reaction is finished, taking out the reaction tank after the temperature of the reaction tank is cooled to 60 ℃ and the pressure is 0 MPa. The reaction was transferred to a glass bottle, and then the wall of the reaction tank was washed with ethyl acetate to extract the remaining reaction.
Eighthly, after the reaction is finished, cooling to room temperature at the same temperature, cleaning the reaction kettle with sufficient ethyl acetate and ethanol, transferring all reactants, cleaning liquid and solids into a beaker, performing suction filtration by using a solvent filtering device, washing the solids for multiple times by using the ethyl acetate until the cleaning liquid becomes colorless and transparent, transferring the first cleaning liquid and cleaning liquid into a round-bottom flask, performing rotary evaporation at 40 ℃ to remove the ethyl acetate, then heating to 60 ℃ to remove the ethanol, and obtaining a bio-oil product after the rotary evaporation is finished.
The method for calculating the ratio of each substance in the bio-oil product (refer to the literature of 'research on mechanism for preparing high-grade liquid fuel by biomass two-stage catalytic reforming' and 'research on pyrolysis characteristics of combustible solid waste and numerical simulation of process of the combustible solid waste'), comprises the following specific steps: the liquid product was collected in a collection flask and analyzed using GC/MS (7890A/5975C, Agilent). GC/MS used high purity helium (99.999%) at a constant flow rate of 1.0 mL/min. Gas chromatography was carried out by means of a capillary chromatography column (HP-5MS, 0.25 mm. times.0.25 um. times.30 m) with a split ratio of 1: 80. The temperature rise of the GC column oven consists of two stages, the first stage is from 40 ℃ to 180 ℃ with a heating rate of 5 ℃/min, and the second stage is from 180 ℃ to 280 ℃ with a heating rate of 10 ℃/min. Electron impact ionization source (EI) ionization energy is 70eV, mass spectrometry scan range: and m/z is 28-350. The chromatographic peak is determined by referring to NIST MS database of national institute of standards and technology to obtain the material composition of the pyrolysis gas.
The relative content of each component is determined by using a semi-quantitative method, which is characterized in that the relative content of each substance in the liquid product is determined by calculating the area percentage of chromatographic peaks, and the formula is as follows:
wherein, P i Is a certainPeak area of the Compound, P total Is the total peak area of all compounds.
The results of the experiment are shown in FIG. 1. As can be seen from fig. 1: the content of ketone is obviously improved, and the content of other compounds is relatively reduced.
And (4) conclusion: the method for preparing high-quality bio-oil by catalyzing algae microwave hydrolysis by using the heterogeneous composite molecular sieve provided by the invention has the advantages that the content of carbon and hydrogen in the bio-oil is increased, and the calorific value is increased.
The above description is only an example of the present invention and is not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention as described in the specification of the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (8)
1. A method for preparing high-quality bio-oil by catalyzing algae microwave hydrolysis by using heterogeneous composite molecular sieve, which is characterized by comprising the following steps:
1) loading Ni ions on an alkali modified HZSM-5 catalyst;
2) adding algae and the Ni/HZSM-5 catalyst prepared in the previous step into a polytetrafluoroethylene reaction tank, adding a rotor, stirring and preheating for 80 ℃, wherein the preheating time is 20-30 minutes, then raising the temperature to 160-210 ℃, the reaction time is 20-30 minutes, and the pressure is 2-3 MPa, and hydrolyzing the algae under the conditions;
3) after the reaction is finished, cooling to room temperature, washing with sufficient ethyl acetate and ethanol, transferring all the reactants, the washing liquid and the solid into a beaker, then carrying out suction filtration by using a solvent filtering device, washing the solid for multiple times by using ethyl acetate until the washing liquid becomes colorless and transparent, and obtaining the bio-oil by using rotary evaporation.
2. The method as claimed in claim 1, wherein in the step 1), the specific method for loading Ni ions on the alkali-modified HZSM-5 catalyst is as follows: dissolving a proper amount of nickel nitrate in deionized water, adding an alkali modified HZSM-5 catalyst into the solution, stirring for 4-5 hours in a water bath at 80-90 ℃, filtering the reaction mixture after finishing the exchange, drying the filtered solid matter for 10-12 hours at 80-90 ℃, calcining for 4 hours at 500-550 ℃, and grinding, tabletting, crushing and screening the sample into particles of 20-40 meshes after the sample is cooled; wherein the weight ratio of the nickel nitrate to the alkali modified HZSM-5 catalyst is 1: 6.
3. the method as claimed in claim 1, wherein in the step 2), magnetic stirring is adopted, and the specific method of magnetic stirring is as follows: and adding a rotor with a proper size into the reaction kettle, and adjusting the rotating speed of a motor in the microwave reaction furnace to be 300-400 r/min.
4. The method according to claim 1, wherein in the step 2), the catalyst is added by the following method: firstly, adding algae, an acidic solution and a magnetic stirring rotor into a reaction kettle, heating to a preheating temperature, keeping the temperature for a period of time, then adding a catalyst, and continuing to heat for reaction.
5. The method as claimed in claim 1, wherein in the step 2), the specific method for microwave hydrolysis of algae is as follows:
weighing algae and a catalyst Ni/HZSM-5 respectively, pouring the algae and the catalyst Ni/HZSM-5 into a reaction tank, and stirring to uniformly mix the algae and the catalyst Ni/HZSM-5; wherein the weight ratio of the algae organisms to the catalyst Ni/HZSM-5 is 1-2: 1-2;
pouring 6-10% v/v acid solution into a reaction tank, and adding a rotor;
thirdly, placing the reaction tank into a microwave device, raising the temperature to 80 ℃ at a temperature rise rate of 25-30 ℃/min, and preserving the temperature for 20-30 minutes; then raising the temperature to 160-210 ℃ at a temperature raising rate of 15-30 ℃/min, preserving the temperature for 20-30 minutes, keeping the pressure at 1.8-3 MPa, and setting the rotating speed of a rotor at 300-400 r/min;
fourthly, after the reaction is finished, taking out the reaction tank when the temperature of the reaction tank is cooled to 55-60 ℃ and the pressure is 0 MPa;
fifthly, transferring the reactant into a glass bottle, then cleaning the wall surface of the reaction tank by using ethyl acetate, and extracting the residual reactant.
6. The method as claimed in claim 1, wherein in the step 3), the specific method for obtaining the bio-oil by rotary evaporation is adopted: transferring the liquid into a round-bottom flask, performing rotary evaporation at 40 ℃ to remove ethyl acetate, heating to 60 ℃ to remove ethanol, and performing rotary evaporation to obtain the bio-oil product.
7. The method of claim 2, wherein the alkali-modified HZSM-5 is prepared as follows:
1) ZSM-5 zeolite with 5wt% NH 4 NO 3 Ion exchange is carried out on the solution for 4-5 hours at the temperature of 80-90 ℃; washing the solid product to neutrality by using distilled water; repeating the steps for 2 times, drying the obtained sample in an oven at 100 ℃ for 24 hours, and calcining the dried sample at 500-550 ℃ for 5 hours to prepare HZSM-5;
2) adding HZSM-5 into an alkaline solution, stirring for 1 hour at 40 ℃, then cooling a sample to room temperature, adjusting the pH of the obtained solution to 8-8.5, filtering, washing and drying the solution after the pH is adjusted, and then calcining a solid sample for 5 hours in an air environment at 500-550 ℃ to prepare the organic modified HZSM-5 catalyst.
8. The method of claim 7, wherein the alkaline solution is tetrapropylammonium hydroxide solution with a concentration of 0.5 mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210420087.2A CN114891529A (en) | 2022-04-21 | 2022-04-21 | Method for preparing high-quality bio-oil by catalyzing algae microwave hydrolysis through heterogeneous composite molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210420087.2A CN114891529A (en) | 2022-04-21 | 2022-04-21 | Method for preparing high-quality bio-oil by catalyzing algae microwave hydrolysis through heterogeneous composite molecular sieve |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114891529A true CN114891529A (en) | 2022-08-12 |
Family
ID=82716942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210420087.2A Pending CN114891529A (en) | 2022-04-21 | 2022-04-21 | Method for preparing high-quality bio-oil by catalyzing algae microwave hydrolysis through heterogeneous composite molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114891529A (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101514295A (en) * | 2009-03-26 | 2009-08-26 | 四川大学 | Method for preparing bio-oil by catalytic pyrolysis of microalgae with high fat content by molecular sieve |
| CN102002381A (en) * | 2010-11-05 | 2011-04-06 | 合肥工业大学 | Method for preparing biological oil from algae biomass through direct catalytic liquefaction method |
| CN102888254A (en) * | 2012-10-16 | 2013-01-23 | 上海馨合环保科技有限公司 | Method for producing liquid fuel by cellulose biomass |
| CN102994137A (en) * | 2012-12-13 | 2013-03-27 | 青岛大学 | Method for preparing algae material fuel by catalytic liquefying method |
| CN103724189A (en) * | 2013-10-10 | 2014-04-16 | 华南理工大学 | Method for preparing monophenol compound by liquefying and degrading lignin through microwave concerted catalysis |
| CN104560225A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing high-quality fuel oil from biomass |
| CN105419848A (en) * | 2015-11-18 | 2016-03-23 | 江苏大学 | Method for preparing bio-oil through co-pyrolysis catalytic hydrogenation by means of algae and waste rubber |
| CN105713715A (en) * | 2016-03-21 | 2016-06-29 | 江苏大学 | Method for preparing bio-oil online in layering and catalyzing mode through microalgae vacuum pyrolysis |
| CN107118793A (en) * | 2017-06-26 | 2017-09-01 | 浙江大学 | A kind of application of metal carrying catalyst in grease and biomass copyrolysis prepare aromatic hydrocarbons |
| CN108499598A (en) * | 2018-02-26 | 2018-09-07 | 中山大学惠州研究院 | It is a kind of multistage porous molecular sieve N-Meso-ZSM-5 catalyst and its catalysis pyrolysis lignin prepare bio oil method |
| CN109160521A (en) * | 2018-09-10 | 2019-01-08 | 太原理工大学 | Molecular sieve and preparation method thereof, catalyst and the preparation method and application thereof |
-
2022
- 2022-04-21 CN CN202210420087.2A patent/CN114891529A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101514295A (en) * | 2009-03-26 | 2009-08-26 | 四川大学 | Method for preparing bio-oil by catalytic pyrolysis of microalgae with high fat content by molecular sieve |
| CN102002381A (en) * | 2010-11-05 | 2011-04-06 | 合肥工业大学 | Method for preparing biological oil from algae biomass through direct catalytic liquefaction method |
| CN102888254A (en) * | 2012-10-16 | 2013-01-23 | 上海馨合环保科技有限公司 | Method for producing liquid fuel by cellulose biomass |
| CN102994137A (en) * | 2012-12-13 | 2013-03-27 | 青岛大学 | Method for preparing algae material fuel by catalytic liquefying method |
| CN103724189A (en) * | 2013-10-10 | 2014-04-16 | 华南理工大学 | Method for preparing monophenol compound by liquefying and degrading lignin through microwave concerted catalysis |
| CN104560225A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing high-quality fuel oil from biomass |
| CN105419848A (en) * | 2015-11-18 | 2016-03-23 | 江苏大学 | Method for preparing bio-oil through co-pyrolysis catalytic hydrogenation by means of algae and waste rubber |
| CN105713715A (en) * | 2016-03-21 | 2016-06-29 | 江苏大学 | Method for preparing bio-oil online in layering and catalyzing mode through microalgae vacuum pyrolysis |
| CN107118793A (en) * | 2017-06-26 | 2017-09-01 | 浙江大学 | A kind of application of metal carrying catalyst in grease and biomass copyrolysis prepare aromatic hydrocarbons |
| CN108499598A (en) * | 2018-02-26 | 2018-09-07 | 中山大学惠州研究院 | It is a kind of multistage porous molecular sieve N-Meso-ZSM-5 catalyst and its catalysis pyrolysis lignin prepare bio oil method |
| CN109160521A (en) * | 2018-09-10 | 2019-01-08 | 太原理工大学 | Molecular sieve and preparation method thereof, catalyst and the preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| YINGBIN ZHUANG ET AL.: ""Microwave-assisted direct liquefaction of Ulva prolifera for bio-oil production by acid catalysis"", 《BIORESOURCE TECHNOLOGY》 * |
| 李昭莹: ""基于脱氧加氢的介微孔复合分子筛催化稻壳热解制备高品质生物油特性研究"", 《中国博士学位论文全文数据库（工程科技I辑）》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ye et al. | A review about GVL production from lignocellulose: Focusing on the full components utilization | |
| CN104711007A (en) | Preparation method of aviation kerosene or diesel oil scope liquid alkane | |
| CN101514295B (en) | Method for preparing bio-oil by catalytic pyrolysis of microalgae with high fat content by molecular sieve | |
| CN102807483B (en) | Method for preparing cyclopentanone and/or cyclopentanol by furfural or furfuryl alcohol | |
| Rao et al. | Light-driven transformation of biomass into chemicals using photocatalysts–Vistas and challenges | |
| CN105237371A (en) | Method for preparing vanillin through catalytic oxidation degradation of lignin | |
| CN110117499B (en) | Method for preparing alkane by hydrodeoxygenation of oxygen-containing organic compound | |
| CN101407727A (en) | Method for preparing biomass liquefied oil by biomass catalytic liquefaction | |
| CN108671960A (en) | A kind of high hydrothermal stability MOFs catalyst, the method for preparing and preparing chemicals for cellulose conversion | |
| Wu et al. | Research progress on the preparation and application of biomass derived methyl levulinate | |
| CN113402485A (en) | Method for preparing 5-hydroxymethylfurfural by converting cellulose in composite molten salt hydrate | |
| CN102389829A (en) | Solid base catalyst for synthetizing aviation fuel intermediates by using furfural and acetone aldol as well as preparation method and purpose | |
| Luo et al. | Preparation of bio-jet fuels by a controllable integration process: Coupling of biomass fermentation and olefin polymerization | |
| CN106902877B (en) | A kind of polyacid catalyst and preparation method thereof and application method | |
| Rodríguez-Padrón et al. | Biomass valorization: Catalytic approaches using benign-by-design nanomaterials | |
| CN114891529A (en) | Method for preparing high-quality bio-oil by catalyzing algae microwave hydrolysis through heterogeneous composite molecular sieve | |
| CN111545202A (en) | Cheap metal catalyst for lignin oligomer hydrogenation depolymerization synchronous quality improvement and preparation method and application thereof | |
| CN107286006A (en) | A kind of method that catalyzed alcoholysis lignin prepares Acetovanillone and acetosyringone | |
| CN104788408B (en) | A kind of method that γ valerolactones are produced by hemicellulose | |
| CN102757310A (en) | Method of preparing isopropanol by catalytic conversion of cellulose | |
| Quereshi et al. | Catalytic conversion of lignocellulosic biomass into fuels and value-added chemicals | |
| CN112979406B (en) | Method for catalyzing alpha-pinene dimerization-hydrogenation reaction by bifunctional microporous molecular sieve | |
| CN110128236B (en) | Method for preparing linear α -olefin by low-temperature decarbonylation/dehydration of fatty acid | |
| CN111434657B (en) | Preparation method of gamma-valerolactone and levulinate ester compound | |
| CN105772076A (en) | Mesoporous catalyst with hydrothermal stability and preparation method thereof and method for preparing bio-oil by catalyzing hydrothermally-liquidized microalgae through mesporous catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |