CN113308265A - Method for preparing biological crude oil by catalytic conversion method - Google Patents
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1014—Biomass of vegetal origin
Abstract
The invention discloses a method for catalytically converting biological raw bio-oil by a two-step method, which relates to the technical field of preparation of biological raw oil by hydrothermal liquefaction of biomass and catalytic pyrolysis, and provides a method for preparing biological raw oil by a catalytic conversion method, which comprises the following steps: step 1), carrying out hydrothermal liquefaction on a biomass raw material to obtain biological crude oil; and 2) carrying out catalytic pyrolysis conversion on the bio-crude oil by using a molecular sieve catalyst loaded with group VIII metal to obtain the upgraded bio-crude oil. The method utilizes the green and environment-friendly technology, not only prepares the biological crude oil with high yield and high quality, but also realizes the resource treatment of the biomass.
Description
Technical Field
The invention relates to a method for preparing biological crude oil, and belongs to the technical field of preparation of biofuels.
Background
The eutrophication problem of water bodies is more and more serious due to the over-standard discharge of industrial wastewater and domestic sewage and the abuse of chemical fertilizers and pesticides, so that the mass propagation of algae plants is realized. The excessive propagation algae consume a large amount of oxygen in water, so that other organisms in the water are difficult to survive due to oxygen deficiency, and organic substances and plankton accumulated under the water are decomposed in the oxygen-deficient environment to generate harmful gas and toxin, so that other organisms are harmed.
Hydrothermal liquefaction is a technology for effectively treating algae biomass, and is a thermochemical conversion process for converting biomass into biological crude oil under the condition of taking water as a solvent, wherein the reaction temperature is 180-. Hydrothermal liquefaction is a refining technology suitable for aquatic biomass, and compared with a pyrolysis technology, the technology can directly convert wet biomass, so that the pretreatment cost is effectively saved. The high calorific value of the hydrothermal liquefied crude oil is as high as 30-38MJ/kg, which is 60-95% of the calorific value of petroleum, so the biological crude oil is a potential fossil energy substitute. However, some problems still remain to be solved in the storage and utilization processes of the bio-crude oil produced by the traditional hydrothermal liquefaction technology, such as: the biological crude oil has high oxygen content, so that the quality of the crude oil in the storage process is unstable, and in addition, the biological crude oil has strong acidity and high viscosity, thereby bringing difficulties in storage and pipeline transportation. Thus, more and more research is currently focused on hydrothermal liquefaction-catalytic conversion processes.
Chinese patent CN 103059895A discloses a method for preparing bio-oil by hydrothermal liquefaction of Enteromorpha prolifera, which utilizes K2CO3As a catalyst, the algae is catalyzed by a hydrothermal liquefaction process.
Chinese patent CN1102002381A discloses a method for preparing bio-oil by direct catalytic liquefaction of algae biomass, which comprises soaking algae in acid solution or alkali solution, and catalyzing hydrothermal liquefaction process with modified natural mordenite catalyst.
Chinese patent CN 106170534A discloses a method for hydrothermally converting biomass into bio-crude oil by using a catalyst, wherein ionic liquid is used as the catalyst to prepare hydrothermally liquefied bio-crude oil, the yield of the obtained bio-crude oil is between 40 and 78 percent, and the carbon content of the bio-crude oil is between 60 and 80 percent.
From the prior art and process, the research of catalytic hydrothermal liquefaction mainly focuses on adding a catalyst in the hydrothermal liquefaction process and regulating and controlling the hydrothermal reaction path, so that high-quality biological crude oil is obtained. Common catalysts are homogeneous catalysts, such as metal salts (Na)2CO3、Rb2CO3) Strong alkali, alkali(Ca(OH)2KOH), strong acids (HCl, H)2SO4) Etc., also heterogeneous catalysts, such as Pd/CoMo, Pt/Ni, Ru/Ni/SiO2Or Ni/HZSM-5, etc. The most commonly used catalyst is a homogeneous catalyst, but liquid-phase wastewater after hydrothermal liquefaction reaction is seriously polluted, is not beneficial to discharge, and has higher subsequent treatment cost. The supported heterogeneous catalyst shows better catalytic effect than that of a supported substance or a supported substance used for the catalyst alone, and plays a certain positive role in improving the yield of crude oil and the quality of the crude oil. However, the commonly used load is noble metal, so that the cost is high, and the method is not beneficial to industrial production. In addition, in the research on the subsequent treatment of the hydrothermal liquefied bio-crude, a catalyst such as Ni — Mo is generally added in a hydrogen atmosphere to realize the hydrodenitrogenation reaction of the crude. However, there is currently little research on the subsequent catalytic treatment of bio-crude produced by hydrothermal liquefaction in a non-hydrogen atmosphere.
Disclosure of Invention
The invention aims to provide a method for preparing biological crude oil by a catalytic conversion method, which is used for obtaining high-yield and high-quality biological crude oil by utilizing a catalyst with simple preparation method, high recovery rate and good hydrothermal stability.
The purpose of the invention is realized by the following technical scheme:
a method for producing bio-crude by catalytic conversion, comprising: step 1), carrying out hydrothermal liquefaction on a biomass raw material to obtain biological crude oil; and 2) carrying out catalytic pyrolysis conversion on the bio-crude oil by using a molecular sieve catalyst loaded with group VIII metal to obtain the upgraded bio-crude oil.
The biomass hydrothermal liquefaction in the step 1) can be performed according to a conventional method, generally, a biomass raw material is added with a proper amount of water and then added into a reaction kettle for hydrothermal liquefaction, four products of biological crude oil, solid residues, gas and liquid phase are obtained after the reaction is completed, and the biological crude oil is obtained through operations of filtering, extracting, distilling, drying and the like.
The initial pressure of the hydrothermal liquefaction in the step 1) is usually 0MPa-8 MPa, the reaction temperature is usually 200-. The reaction temperature is preferably 250-350 ℃, and the heat preservation time is 60-120 min.
The biomass raw material can be algae, cellulose, municipal sludge, household garbage, kitchen waste, livestock and poultry manure, crop straws, forestry waste and the like, and preferably the algae is one or more than one of microalgae biomass such as nannochloropsis oculata, scenedesmus, spirulina, blue algae, nostoc, diatom, red algae and the like.
Wherein, the step 2) of catalytic pyrolysis conversion of the biological crude oil further comprises the following steps: drying and pretreating the biological crude oil to remove water, putting the biological crude oil and the molecular sieve catalyst loaded with the VIII family metal into a reaction kettle together for high-temperature catalytic pyrolysis, wherein the reaction conditions are that the reaction temperature is 200-700 ℃, the reaction residence time is 10-200 min, the preferred reaction temperature is 280-350 ℃, and the reaction residence time is 60-120min, after the reaction is finished, extracting and recovering the biological crude oil by using an organic solvent, calcining the solid residue at high temperature, and regenerating the catalyst.
In the step 2), the molecular sieve is selected from one or more of microporous zeolite molecular sieves such as HZSM-22, HZSM-5, H-beta, MCM-22, SAPO-11 and the like.
In the step 2), the group VIII metal is preferably iron, and the loading of the metal is 1-20 wt%, preferably 5-15 wt%, based on the total mass of the catalyst. The amount of catalyst added is 1-30 wt%, preferably 5-10 wt% of the mass of the bio-crude.
In step 2), the preparation method of the group VIII metal-loaded molecular sieve catalyst comprises the following steps: firstly, mixing an acidic molecular sieve with a salt solution of a metal in the VIII group, heating the mixed solution for 5-20min under the microwave with the power of 500-900W, preferably 600-700W, then washing solid residues, drying and roasting. Wherein the drying condition is that the temperature is 100-150 ℃ and the time is 5-15h, and finally the mixture is placed in a muffle furnace for roasting, the roasting temperature is 400-700 ℃, the roasting time is 1-6 h, the preferred roasting temperature is 450-550 ℃, and the roasting time is 2-4 h.
In the step 2), the salt solution of the VIII family metal is one of ferric nitrate, ferric sulfate and ferric chloride.
In the step 1) and the step 2), the obtained biological crude oil is extracted and separated, and the extraction solvent is one of organic solvents such as acetone, ethanol, methanol, dichloromethane, diethyl ether, ethyl acetate, n-hexane, pentane, xylene and trichloromethane.
In the step 1) and the step 2), inert gas is also introduced to be used as carrier gas to ensure oxygen insulation in the reaction kettle, and the carrier gas is N2Or He, the gas flow is 150mL/min-300 mL/min.
In the step 1) and the step 2), the reactor is an intermittent or continuous high-temperature high-pressure reaction kettle.
The invention utilizes a microwave-impregnation method to load the VIII family metal on the molecular sieve. Compared with the conventional heating method for preparing the Fe-loaded molecular sieve catalyst, the microwave method has the following advantages: (1) uniform heating, high efficiency, high speed, controllable temperature and power and reduced side reaction. (2) The metal dispersibility is good. The inventor finds that the pore diameter and the pore volume of the catalyst obtained by the microwave method are larger than those of the catalyst obtained by the heating method, so that the microwave method is favorable for metal to enter the inside of the pore channel of the catalyst, and the loading capacity and the active sites of the catalyst are increased, thereby being favorable for reactants and intermediate products to enter and exit the inside of the pore channel, leading the reactants and the intermediate products to fully react with the active sites on the inner surface and the outer surface of the molecular sieve, inhibiting the generation of carbon deposition, and improving the service life and the reuse rate of the catalyst.
Therefore, the catalyst prepared by the microwave method can promote the exchange and the loading of metal ions, increase the loading capacity of the metal ions, promote the uniform dispersion of the metal ions in the pore channel structure of the molecular sieve, ensure the full contact of reactants with the acid sites and the metal active sites of the molecular sieve, be beneficial to the catalytic reaction and have obvious effects on the catalytic reaction and the quality improvement of products.
Drawings
FIG. 1 is a process flow diagram of an embodiment of the present invention.
Detailed Description
The present invention is further described below with reference to the flow chart. The present embodiment is for illustration and is not limited to the scope of the invention of the present application.
In the embodiment, the content of carbon, hydrogen and nitrogen in the biological crude oil is measured by using an element analyzer, and the content of oxygen is calculated by using a difference method; calculating the heat value of the biological crude oil by a Dulong formula; and (3) determining the content of hydrocarbon substances in the biological crude oil by using a gas chromatography-mass spectrometer.
Example 1
(1) Mixing an HZSM-5 molecular sieve with a ferric nitrate solution, preparing a metal loading ratio of 10 wt%, heating for 10min under the low-power condition of a 500W 10% microwave oven, washing the catalyst with deionized water, drying at 120 ℃, and roasting in a 500 ℃ muffle furnace for 3h to finish the preparation of the catalyst.
(2) Adding 250g of dry spirulina powder into a reaction kettle, sealing the reaction kettle, introducing nitrogen to enable the pressure in the reaction kettle to reach the initial pressure, enabling the rotating speed of a stirrer to be 800rmp, and enabling the pressure to be stable and unchanged within 10min, so that the airtightness of the reaction kettle is considered to be good.
(3) The temperature of the reaction kettle is heated to 280 ℃, the heating rate is 5 ℃/min, and the reaction residence time is 120 min.
(4) And after the reaction kettle is cooled to room temperature, collecting a gas product after reaction, collecting a water phase product by using a glass cup, extracting the remainder by using acetone, and then filtering, wherein the part insoluble in the acetone is solid residue, and the part soluble in the acetone is biological crude oil.
(5) Pouring the biological crude oil into a separating funnel, standing and layering, wherein the lowest layer is water, pouring the upper layer liquid phase into an extraction bottle for distillation, recovering acetone, and then putting the biological crude oil into a drying oven for drying for 12 hours to obtain dried biological crude oil.
(6) Mixing the bio-crude oil obtained in the step (5) with 5 wt% of catalyst, putting the mixture into a reaction kettle, introducing nitrogen for 10min to ensure the oxygen insulation in the kettle, and then heating the reaction kettle to 280 ℃ for reaction for 180 min.
(7) After the reaction is finished, extracting the reaction residue by using acetone, wherein the solid residue insoluble in acetone is coke and a catalyst, and the part soluble in acetone is high-quality biological crude oil.
(8) Calcining the solid residue at 575 deg.c for 8 hr to regenerate and recover the catalyst.
(9) Calculating the bio-crude yield using the ratio of the mass of upgraded bio-crude to the mass of non-upgraded bio-crude; the composition, calorific value and other indexes of the high-quality bio-crude are shown in Table 1.
(10) Compared with the biological crude oil before catalytic pyrolysis, the oxygen content of the prepared high-quality biological crude oil is reduced by 24.5 percent, the heat value is increased by 16.0 percent, and the content of hydrocarbon substances is increased by 1.29 times.
(11) Compared with the catalyst prepared by the traditional heating method, the yield of the biological crude oil catalyzed by the catalyst prepared by the microwave preparation method is improved by 3.95%, the carbon content is improved by 6.87%, the oxygen content is reduced by 9.21%, the calorific value is improved by 10.33%, and the content of hydrocarbon substances is improved by 1.42 times, which shows that the yield and the calorific value of the biological crude oil are effectively improved by the catalyst prepared by the microwave method, and the occurrence of carbon deposition is inhibited.
(12) The catalyst prepared by the microwave method is recycled and regenerated for 5 times, the heat value reduction rate is 4.18 percent, and the catalyst has stable structure and low loss rate of active sites.
Example 2
(1) Mixing an HZSM-5 molecular sieve with a ferric nitrate solution, preparing a metal loading ratio of 10 wt%, heating for 10min under the low-power condition of a 700W 10% microwave oven, washing the catalyst with deionized water, drying, and roasting in a muffle furnace at 500 ℃ for 3h to finish the preparation of the catalyst.
(2) Adding 250g of dry spirulina powder into a reaction kettle, sealing the reaction kettle, introducing nitrogen to enable the pressure in the reaction kettle to reach the initial pressure, enabling the rotating speed of a stirrer to be 800rmp, and enabling the pressure to be stable and unchanged within 10min, so that the airtightness of the reaction kettle is considered to be good.
(3) The temperature of the reaction kettle is heated to 280 ℃, the heating rate is 5 ℃/min, and the reaction residence time is 120 min.
(4) And after the reaction kettle is cooled to room temperature, collecting a gas product after reaction, collecting a water phase product by using a glass cup, extracting the remainder by using acetone, and then filtering, wherein the part insoluble in the acetone is solid residue, and the part soluble in the acetone is biological crude oil.
(5) Pouring the biological crude oil into a separating funnel, standing and layering, wherein the lowest layer is water, pouring the upper layer liquid phase into an extraction bottle for distillation, recovering acetone, and then putting the biological crude oil into a drying oven for drying for 12 hours to obtain dried biological crude oil.
(6) Mixing the bio-crude oil obtained in the step (5) with 8 wt% of catalyst, putting the mixture into a reaction kettle, introducing nitrogen for 10min to ensure the oxygen insulation in the kettle, and then heating the reaction kettle to 320 ℃ for reaction for 180 min.
(7) After the reaction is finished, extracting the reaction residue by using acetone, wherein the solid residue insoluble in acetone is coke and a catalyst, and the part soluble in acetone is high-quality biological crude oil.
(8) Calcining the solid residue at 575 deg.c for 8 hr to regenerate and recover the catalyst.
(9) Calculating the bio-crude yield using the ratio of the mass of upgraded bio-crude to the mass of non-upgraded bio-crude; the composition, calorific value and other indexes of the high-quality bio-crude are shown in Table 1.
(10) Compared with the biological crude oil before catalytic pyrolysis, the oxygen content of the prepared high-quality biological crude oil is reduced by 75.2 percent, the heat value is increased by 30 percent, and the content of hydrocarbon substances is increased by 3.5 times.
(11) Compared with the catalyst prepared by the traditional heating method, the yield of the biological crude oil catalyzed by the catalyst prepared by the microwave preparation method is improved by 9.71%, the carbon content is improved by 12.83%, the oxygen content is reduced by 11.05%, the calorific value is improved by 15.97%, and the content of hydrocarbon substances is improved by 1.75 times, which shows that the yield and the calorific value of the biological crude oil are effectively improved by the catalyst prepared by the microwave method, and the occurrence of carbon deposition is inhibited.
(12) After the catalyst prepared by the microwave method is recycled and regenerated and is repeatedly used for 5 times, the heat value reduction rate is 3.66 percent, which shows that the catalyst has stable structure and low loss rate of active sites.
Example 3
(1) Mixing an HZSM-5 molecular sieve with a ferric nitrate solution, preparing a metal loading ratio of 10 wt%, heating for 10min under the low-power condition of a 900W 10% microwave oven, washing the catalyst with deionized water, drying, and roasting in a muffle furnace at 500 ℃ for 3h to finish the preparation of the catalyst.
(2) Adding 250g of dry spirulina powder into a reaction kettle, sealing the reaction kettle, introducing nitrogen to enable the pressure in the reaction kettle to reach the initial pressure, enabling the rotating speed of a stirrer to be 800rmp, and enabling the pressure to be stable and unchanged within 10min, so that the airtightness of the reaction kettle is considered to be good.
(3) The temperature of the reaction kettle is heated to 280 ℃, the heating rate is 5 ℃/min, and the reaction residence time is 120 min.
(4) And after the reaction kettle is cooled to room temperature, collecting a gas product after reaction, collecting a water phase product by using a glass cup, extracting the remainder by using acetone, and then filtering, wherein the part insoluble in the acetone is solid residue, and the part soluble in the acetone is biological crude oil.
(5) Pouring the biological crude oil into a separating funnel, standing and layering, wherein the lowest layer is water, pouring the upper layer liquid phase into an extraction bottle for distillation, recovering acetone, and then putting the biological crude oil into a drying oven for drying for 12 hours to obtain dried biological crude oil.
(6) Mixing the bio-crude oil obtained in the step (5) with 10 wt% of catalyst, putting the mixture into a reaction kettle, introducing nitrogen for 10min to ensure the oxygen insulation in the kettle, and then heating the reaction kettle to 280 ℃ for reaction for 120 min.
(7) After the reaction is finished, extracting the reaction residue by using acetone, wherein the solid residue insoluble in acetone is coke and a catalyst, and the part soluble in acetone is high-quality biological crude oil.
(8) Calcining the solid residue at 575 deg.c for 8 hr to regenerate and recover the catalyst.
(9) Calculating the bio-crude yield using the ratio of the mass of upgraded bio-crude to the mass of non-upgraded bio-crude; the composition, calorific value and other indexes of the high-quality bio-crude are shown in Table 1.
(10) Compared with the biological crude oil before catalytic pyrolysis, the oxygen content of the prepared high-quality biological crude oil is reduced by 41.2 percent, the heat value is increased by 24.3 percent, and the content of hydrocarbon substances is increased by 1.52 times.
(11) Compared with the catalyst prepared by the traditional heating method, the yield of the biological crude oil catalyzed by the catalyst prepared by the microwave preparation method is improved by 5.55%, the carbon content is improved by 9.23%, the oxygen content is reduced by 8.90%, the calorific value is improved by 13.09%, and the content of hydrocarbon substances is improved by 1.46 times, which shows that the yield and the calorific value of the biological crude oil are effectively improved by the catalyst prepared by the microwave method, and the occurrence of carbon deposition is inhibited.
(12) The catalyst prepared by the microwave method is recycled and regenerated, and is reused for 5 times, the heat value reduction rate is 5.37 percent, which shows that the catalyst has stable structure and low loss rate of active sites.
Example 4
(1) Mixing the HZSM-5 molecular sieve with the solution, preparing a metal loading ratio of 10 wt%, heating for 10min under the low-power condition of a 900W 10% microwave oven, washing the catalyst with deionized water, drying, and roasting in a muffle furnace at 500 ℃ for 3h to finish the preparation of the catalyst.
(2) Adding 250g of dry spirulina powder into a reaction kettle, sealing the reaction kettle, introducing nitrogen to enable the pressure in the reaction kettle to reach the initial pressure, enabling the rotating speed of a stirrer to be 800rmp, and enabling the pressure to be stable and unchanged within 10min, so that the airtightness of the reaction kettle is considered to be good.
(3) The temperature of the reaction kettle is heated to 280 ℃, the heating rate is 5 ℃/min, and the reaction residence time is 120 min.
(4) And after the reaction kettle is cooled to room temperature, collecting a gas product after reaction, collecting a water phase product by using a glass cup, extracting the remainder by using acetone, and then filtering, wherein the part insoluble in the acetone is solid residue, and the part soluble in the acetone is biological crude oil.
(5) Pouring the biological crude oil into a separating funnel, standing and layering, wherein the lowest layer is water, pouring the upper layer liquid phase into an extraction bottle for distillation, recovering acetone, and then putting the biological crude oil into a drying oven for drying for 12 hours to obtain dried biological crude oil.
(6) Mixing the bio-crude oil obtained in the step (5) with 8 wt% of catalyst, putting the mixture into a reaction kettle, introducing nitrogen for 10min to ensure the oxygen insulation in the kettle, and then heating the reaction kettle to 320 ℃ for reaction for 120 min.
(7) After the reaction is finished, extracting the reaction residue by using acetone, wherein the solid residue insoluble in acetone is coke and a catalyst, and the part soluble in acetone is high-quality biological crude oil.
(8) Calcining the solid residue at 575 deg.c for 8 hr to regenerate and recover the catalyst.
(9) Calculating the bio-crude yield using the ratio of the mass of upgraded bio-crude to the mass of non-upgraded bio-crude; the composition, calorific value and other indexes of the high-quality bio-crude are shown in Table 1.
(10) Compared with the biological crude oil before the catalytic pyrolysis, the oxygen content of the prepared high-quality biological crude oil is reduced by 28.5 percent, the heat value is increased by about 22.0 percent, and the content of hydrocarbon substances is increased by 2.5 times.
(11) Compared with the catalyst prepared by the traditional heating method, the yield of the biological crude oil catalyzed by the catalyst prepared by the microwave preparation method is improved by 16.23%, the carbon content is improved by 21.90%, the oxygen content is reduced by 17.67%, the calorific value is improved by 22.78%, and the content of hydrocarbon substances is improved by 2.45 times, which shows that the yield and the calorific value of the biological crude oil are effectively improved by the catalyst prepared by the microwave method, and the occurrence of carbon deposition is inhibited.
(12) The catalyst prepared by the microwave method is recycled and regenerated for 5 times, the heat value reduction rate is 2.54 percent, and the catalyst has stable structure and low loss rate of active sites.
TABLE 1 physicochemical Properties of high quality biocrude
The above examples are merely illustrative of the operational procedures of the present invention, but the scope of the present application is not limited thereto. Any modification and variation made in the technology of the present invention should be covered within the protection scope of the present invention.
Claims (13)
1. A method for producing bio-crude by catalytic conversion, comprising: step 1), carrying out hydrothermal liquefaction on a biomass raw material to obtain biological crude oil; and 2) carrying out catalytic pyrolysis conversion on the bio-crude oil by using a molecular sieve catalyst loaded with group VIII metal to obtain the upgraded bio-crude oil.
2. The method according to claim 1, wherein the hydrothermal liquefaction initial pressure in step 1) is 0MPa to 8 MPa, the reaction temperature is 200 ℃ to 500 ℃, and the reaction holding time is 10min to 200 min.
3. The method of claim 1, wherein step 2) comprises: and after the biological crude oil is dried and pretreated to remove moisture, the biological crude oil and the molecular sieve catalyst loaded with the VIII family metal are placed in a reaction kettle for high-temperature catalytic pyrolysis, the reaction temperature is 200-700 ℃, and the reaction residence time is 10-250 min.
4. The process of claim 3, wherein the reaction temperature of step 2) is 280 ℃ to 320 ℃ and the reaction residence time is 60min to 180 min.
5. The method as claimed in claim 1, wherein in step 2), the molecular sieve is selected from one or more of HZSM-22, HZSM-5, H-beta, MCM-22, SAPO-11 microporous zeolite molecular sieves.
6. The process of claim 1 wherein in step 2) the group VIII metal comprises iron.
7. The process according to claim 1, wherein in step 2), the loading of the group VIII metal is 1-20 wt% based on the total mass of the catalyst, and the catalyst is added in an amount of 1-30 wt% based on the mass of the bio-crude.
8. The process according to claim 1, wherein in step 2), the loading of the group VIII metal is from 5 to 15% by weight, based on the total mass of the catalyst.
9. The method according to claim 1, wherein the catalyst is added in an amount of 5 to 10 wt% based on the mass of the bio-crude in the step 2).
10. The process of claim 1 wherein in step 2) the group VIII metal-loaded molecular sieve catalyst is prepared by a process comprising: firstly, mixing an acidic molecular sieve with a salt solution of a metal in the VIII group, heating the mixed solution for 5-20min under the microwave with the power of 500-900W, then washing solid residues, drying and roasting.
11. The method according to claim 10, wherein the drying temperature is 100 ℃ to 150 ℃ and the drying time is 5 to 15 hours; the roasting temperature is 400-700 ℃, and the roasting time is 1-5 h.
12. The method according to claim 10 wherein the salt solution of a group VIII metal is selected from one of ferric nitrate, ferric sulphate, ferric chloride.
13. A biocrude prepared by the method of any one of claims 1-12.
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