CN105602612B - A method for hydrofining bio-crude oil using a high-temperature gas-cooled reactor - Google Patents

Abstract

The invention discloses a waterproof and heatproof hydrogenation catalyst. The catalyst is a meso-porous molecular sieve SBA-15 doped with active metal and grafted with an organic functional group, wherein the doped active metal is one or more of Pt, Pd, Zr, Ru, Ni, Co and Mo, and the grafted organic functional group is one or more of an amino group, a carboxyl group and a sulfonyl group. The invention also discloses a method for hydrofinishing biological crude oil by using a high temperature gas cooled reactor. The method comprises the following steps: heating second helium flow with high temperature helium from the core of the high temperature gas cooled reactor, driving a thermochemical circulating hydrogen production process by the second helium flow, preheating and gasifying total components of the oil phase and the water phase of biological crude oil by the second helium flow to form biological crude oil steam, and hydrofinishing the biological crude oil steam and prepared hydrogen under the action of the catalyst to obtain biofuel oil and a non-condensable fuel gas.

Description

A method for hydrofining bio-crude oil using a high-temperature gas-cooled reactor

technical field

The invention relates to a method for hydrofining all components of biological crude oil (including organic components in oil phase and water phase) by using a high-temperature air-cooled nuclear reactor, and belongs to the field of utilizing nuclear energy and the field of renewable biomass energy.

Background technique

Energy and the environment are the two major themes of human development. Currently, fossil energy reserves are limited and gradually exhausted, and the use of fossil energy has brought serious environmental pollution. Therefore, the development of renewable energy can help reduce dependence on fossil resources, which is of great significance. The energy consumption of my country's transportation industry is huge, and it is increasing year by year. It currently accounts for more than 20% of the total energy consumption of the society, and it is expected to reach 1/3 of the same level as developed countries in recent years. Compared with fuel engines, electric vehicles cannot provide the powerful power required for driving in various road conditions, so the vast majority (more than 95%) of transportation energy consumption depends on liquid fuels, making the demand for liquid fuels very large. It is estimated that by 2050 , my country's liquid fuel demand is about 400-500 million tons. Domestic oil production is difficult to meet the requirements, and more than half of the gap needs to be supplemented by other means. Therefore, it is urgent to develop renewable liquid fuels. Biomass is the only renewable energy that can produce liquid fuels, so it is necessary to develop technologies for producing liquid fuels from biomass.

The conversion of biomass into bio-crude oil by thermal cracking and other thermochemical methods is one of the most important and effective utilization methods of biomass. Bio-crude oil needs further hydrotreating to be converted into high-quality transportation power fuel. The refining process consumes a lot of heat energy and hydrogen, which is one of the main bottlenecks restricting the promotion and utilization of bio-crude oil.

Nuclear energy is a clean primary energy source. At present, nuclear energy is mainly used for power generation. It cannot directly obtain liquid fuel, and it is difficult to enter the field of transportation energy consumption.

Using the heat generated by the high-temperature gas-cooled reactor, cheap hydrogen can be produced on a large scale through thermochemical cycles such as the iodine-sulfur cycle, and the process heat and hydrogen produced by the high-temperature reactor can be used for the hydrofining of bio-crude oil, from the form of energy conversion From the point of view, nuclear energy is injected into the production process of liquid fuel in the form of nuclear hydrogen and nuclear heat, and the utilization of nuclear energy in the field of transportation is realized indirectly.

Compared with other existing technologies, the beneficial effects of the integrated process of nuclear energy hydrogen production and bio-crude oil are:

(1) Utilizing the nuclear heat of the high temperature gas-cooled reactor and the nuclear hydrogen produced to carry out gasification and hydrofining of bio-crude oil, while significantly reducing the economic cost of bio-fuels, it also greatly reduces the carbon dioxide emissions during the refining process of bio-crude oil quantity.

(2) The co-supply of heat, electricity and hydrogen of the high-temperature reactor improves the utilization efficiency of the high-temperature reactor and expands the field of non-electric utilization of nuclear energy. In addition, the injection of nuclear energy into the production process of liquid fuel in the form of nuclear heat and nuclear hydrogen makes nuclear energy indirectly enter the large market in the field of transportation.

Simple calculation of relevant data is as follows: my country's annual available all kinds of biomass raw material total amount is about 1,000,000,000 tons, and the utilization rate is 20%, and it is expected to replace 1/4 wherein with the new method of the present invention, then the biological crude oil obtained is 25 million tons, if the hydrogen consumption in refining is calculated as 8%, the total hydrogen consumption is 2 million tons; the high-temperature reactor module is calculated as 250MWt, the heat supply load factor is 85%, and the heat required for 25 million tons of bio-oil hydrorefining The value is 1.4418 million tons of standard coal, 6.3 high-temperature reactor modules are required, and carbon dioxide emissions are reduced by 3.84 million tons; nuclear energy accounts for 26% of the refined bio-oil.

Here is a brief introduction to nuclear energy hydrogen production and bio-crude oil hydrotreating technology as follows:

1. Biological cracking crude oil hydrofining technology

Biomass is the only renewable energy that can be directly converted into liquid fuels. It has attracted widespread attention around the world due to its advantages of huge output, renewable and carbon neutrality.

Converting low-density solid biomass raw materials into liquid fuels with high energy density is one of the most important contents of biomass utilization. Biomass thermochemical conversion method is one of the main methods for producing liquid fuels from biomass raw materials. Economical, profitable without government subsidies, and suitable for mass production. Under the optimal reaction conditions, the yield of biomass pyrolysis bio-oil is generally 50-70%, and the calorific value of bio-oil is 16-20MJ/kg, which is about 2/5 of the calorific value of diesel oil.

The total amount of biomass raw materials available in my country is not less than 1 billion tons per year. If 20% of them are used for pyrolysis to produce bio-oil, more than 100 million tons of bio-oil can be obtained a year. It can reduce 40 million tons of crude oil imports for the country. In addition, compared with the use of fossil fuels, the use of 1 ton of bio-oil can reduce CO ₂ emissions by 800kg, and the environmental protection benefits are also very significant.

The liquid product obtained from the thermochemical conversion of biomass is called bio-oil or bio-crude oil (bio-oil or bio-crude) or biomass cracking crude oil, which has the disadvantages of high oxygen content, low calorific value, poor stability and corrosiveness. It is refined to reduce the oxygen content and adjust the ratio of C and H, so as to increase the combustion calorific value and obtain high-quality power fuel oil.

The refining of biomass cracked crude oil is currently a research hotspot in the world. Among them, the catalytic hydrotreating of biomass cracked crude oil can refer to the corresponding process and technology in the petrochemical field, and it can also realize the mixing and co-refining of bio crude oil and petrochemical crude oil, so it has a good prospects for industrialization. Catalytic hydrogenation of biomass cracked crude oil is to hydrogenate biomass cracked crude oil under the pressure of 7-20MPa and temperature of 250-400°C under the condition of hydrogen or hydrogen-donating solvent. The oxygen element in biomass is replaced by water form removed.

There are also obvious deficiencies in the catalytic hydrofining of bio-oil, the most important being that the hydrogenation process consumes a large amount of hydrogen and the cost is high. Complete deoxygenation of every kilogram of bio-oil needs to consume 600-1000L of hydrogen (equivalent to 6-9% of the mass of bio-oil, similar to coal liquefaction), of which about 50% of the hydrogen consumed is used for deoxygenation, and the rest of the hydrogen is in the oil Play the role of increasing H/C. However, because H ₂ itself is a high-priced energy-containing fuel, it is difficult to widely develop the catalytic hydrogenation process of biomass cracking crude oil.

2. Nuclear energy hydrogen production technology

From the perspective of nuclear energy utilization efficiency, the current form of nuclear energy utilization is mainly power generation, but in the world's final energy consumption structure, the proportion of electricity is not high. In 2009, my country accounted for 18.5%. non-electric consumption. Due to the characteristics of high temperature, good safety, and modular and flexible configuration, high-temperature reactors have become one of the most suitable reactor types for application in non-electrical fields such as process heat. Among them, power generation, process heat application, and hydrogen production will be high-temperature gas The three most important application areas of cold stacks.

Although the thermochemical conversion of biomass and subsequent hydrofining of crude oil from biomass cracking have very obvious advantages, the product yield is high, and the quality of fuel oil obtained is good, but the disadvantage is that it needs to consume a lot of energy and hydrogen, and the cost is high. . Hydrogen is chemically active. There is no pure hydrogen in nature, and it needs to be obtained through other primary energy production. Nuclear energy is a clean primary energy source. Nuclear energy hydrogen production uses the heat generated by nuclear reactors as the energy source for hydrogen production. By selecting an appropriate process, efficient and large-scale production of hydrogen can be achieved; at the same time, greenhouse gas emissions can be reduced or even eliminated.

Hydrogen production by thermochemical cycle splitting of water is one of the most promising methods. Compared with direct water splitting for hydrogen production, thermochemical cycle hydrogen production can not only reduce the reaction temperature, but also avoid the hydrogen-oxygen separation problem. There are many ways to produce hydrogen by thermochemical cycle, among which iodine-sulfur thermochemical cycle is considered to be one of the most promising processes. The first step of the process is to decompose H ₂ SO ₄ into H ₂ O, SO ₂ and O ₂ at high temperature (800-950°C) and low pressure, and to separate O ₂ ; the second step is the iodine-sulfur process, That is, I ₂ reacts with SO ₂ and H ₂ O (steam) at lower temperatures to generate HI and H ₂ SO ₄ (exothermic reaction), and at moderate temperatures (200-500°C), HI decomposes into H ₂ and I ₂ .

Among the various reactor types currently being studied, the high-temperature gas-cooled reactor with helium as the coolant can reach a maximum outlet temperature of 950-1000°C, which can well meet the maximum temperature required by the iodine-sulfur thermochemical cycle process. Temperature, thus driving the hydrogen production system, the overall hydrogen production efficiency can reach more than 50%. Therefore, the high-temperature gas-cooled reactor has been considered to be the most suitable reactor type for hydrogen production.

3. Nuclear-hydrogen-biomass

Biomass raw materials are dispersed, while nuclear reactors are highly concentrated, and the geographical distribution of the two is highly mismatched. In addition, the nuclear hydrogen produced by nuclear reactors is also difficult and inconvenient to store and transport. In order to adapt to this situation, the biomass thermochemical conversion method can adopt the production mode of dispersed liquefaction and concentrated refining. According to the highly dispersed characteristics of biomass raw materials, a thermochemical conversion point should be established nearby, and a refinery should be established next to the high-temperature pile. The liquefaction plant converts nearby biomass raw materials into high-density liquid bio-crude oil, and then transports these bio-crude oils to the concentrated refinery near the reactor for hydrofining.

The refining of bio-crude oil is a hydrogen-consuming and heat-consuming process, and the high-temperature gas-cooled reactor can provide energy and the energy required for hydrogen production. Using the high-temperature reactor for the hydro-refining process of bio-crude oil can well realize its The advantages of hydrogen production and process heat utilization form the concept of "nuclear-hydrogen-biomass".

Compared with existing nuclear reactors, high-temperature reactors have better inherent safety, which provides a strong guarantee for the establishment of bio-crude oil refineries nearby. In this way, the contradiction between the highly dispersed biomass raw materials and the highly concentrated geographical distribution of nuclear reactors is resolved. Except for biomass thermochemical conversion, it is difficult for other biomass utilization methods to solve this mismatch of geographical distribution. Therefore, biomass thermochemical conversion and high-temperature gas-cooled reactors are an excellent combination of the concept of "nuclear-hydrogen-biomass".

The "nuclear-hydrogen-biomass process" has a great promotion effect on both nuclear energy and biomass energy: (1) Promotion of nuclear energy: combined supply of hydrogen, heat and electricity, increased overall utilization efficiency of nuclear reactors, and greatly expanded high-temperature reactors Application in non-electric fields; injecting nuclear energy into the transportation energy system in the form of nuclear heat and nuclear hydrogen; (2) Promotion of biomass energy: significantly improved the conversion efficiency of biomass energy, and the economical market of liquid biofuels Competitiveness has been significantly enhanced.

4. Bio-crude oil phase and water phase hydrogenation technology

The biomass cracked crude oil obtained after biomass cracking is mainly composed of oil phase and water phase, of which the volume of the water phase accounts for 10-30%, and the rest is the oil phase. The oil and water phases often coexist in the form of emulsion mixing. Only water can separate the two phases of oil and water.

About 10-20% of the organic carbon and hydrogen contained in the biomass raw material (equivalent to 15-25% of the energy of the initial raw material) are converted into the water phase, so the efficient resource utilization of the water phase cannot be ignored. The organic components of the water phase are mainly small molecule carboxylic acids such as acetic acid and propionic acid (including levulinic acid, etc., of which acetic acid is the main one), these carboxylic acids account for more than 50% of the total organic matter in the water phase; in addition, there are furfural , 5-hydroxymethylfurfural and other furfural substances.

After the hydrogenation reaction, these small molecules in the water phase can be converted into corresponding small molecule hydrocarbons, which finally exist in the form of gas. These small molecular carboxylic acids may also undergo ketonylation reactions to generate ketones. Under the catalysis of basic groups, these ketones undergo further aldol condensation reactions with furfurals to obtain macromolecular hydrophobic organic compounds, which can be naturally separated from water. , and become a liquid fuel after further hydrogenation. In short, after hydrogenation, the small molecules in the water phase of bio-oil can become combustible gases, and can also be further condensed into macromolecules in the oil phase, which improves the yield of liquid fuels.

If all components of oil phase and water phase are co-vaporized and hydrogenated after biomass cracking, high requirements are placed on the hydrothermal stability of the catalyst. Molecular sieves are commonly used catalysts or catalyst carriers for hydrogenation. Considering that there are many long-chain macromolecules in bio-oil, microporous molecular sieves commonly used in petrochemical processes are too small to be used, while mesoporous molecular sieves such as SBA-15 can be used as macromolecules. The hydrogenation reaction provides a suitable reaction space. However, the thermal stability of these mesoporous molecular sieves is very poor, usually not exceeding 200 ° C, and the stability is even worse when there is water, and the catalytic hydrotreating of crude oil from biomass cracking is usually performed at 300-400 ° C. Therefore, the preparation can simultaneously withstand Mesoporous molecular sieve materials that are resistant to high temperature and high moisture content are very important.

Contents of the invention

The purpose of the present invention is to provide a method for simultaneously hydrofining the oil-water two-phase full components of biomass cracked crude oil by using a high-temperature air-cooled nuclear reactor. The required hydrogen and heat are used to simultaneously hydrotreat all components of the bio-crude water phase and oil phase.

One aspect of the present invention provides a hydrogenation catalyst with water resistance and high temperature resistance, the catalyst is a mesoporous molecular sieve SBA-15 doped with an active metal and grafted with an organic functional group (it can be represented by M-SBA-15-X, where M represents active metal, X represents an organic functional group); wherein the doped active metal is one or more of Pt, Pd, Zr, Ru, Ni, Co, Mo, and the grafted organic functional group is one of the amino, carboxyl and sulfonic acid groups one or several.

The method for catalyst doping active metal comprises the following steps: respectively weigh a certain amount of metal salt and dissolve it in anhydrous ethanol: anhydrous acetic acid: concentrated hydrochloric acid in a mixed solution prepared with a volume ratio of 60:5:2, and add a certain amount of The prepared SBA-15 was ultrasonically vibrated and stirred alternately for 0.5h, and the mixture was evenly transferred to a watch glass, and the solvent was evaporated at 30°C to gel, aged at 65°C for 24h, and the obtained product was heated in a muffle furnace for 2 The temperature was raised to 550°C/min, and the solid powder obtained after calcination at 550°C for 5 hours was mesoporous molecular sieve SBA-15 doped with active metals.

The metal salt is one or a mixture of platinum nitrate, palladium nitrate, zirconium nitrate, ruthenium trichloride, nickel nitrate, cobalt nitrate and molybdenum nitrate, and the amount of the metal salt is ethanol: the molar ratio of metal = 1600: 1-320:1; the amount of SBA-15 is the molar ratio of ethanol:Si in SBA-15=32:1-320:1.

The method for grafting organic functional groups includes the following steps: take a certain amount of SBA-15 doped with active metals, add it to absolute ethanol or hydrochloric acid solution, ultrasonically disperse until it is completely suspended, and then add a certain amount of modifying reagents. Reflux for 24 hours, filter after cooling, and wash with absolute ethanol for 3 to 5 times. After oxidation or acidification, filter to obtain a white solid. After drying at room temperature, it is a mesoporous molecular sieve SBA-15 doped with active metal and grafted with organic functional Indicated by M-SBA-15-X).

The added modifying agent is one or more of aminopropyltrimethoxysilane, mercaptophenylpropyltrimethoxysilane, and nitrilepropyltrimethoxysilane. The molar ratio of atomic N or S to Si in the mesoporous molecular sieve SBA-15 is 0.02-0.10.

The invention designs and prepares a novel multifunctional mesoporous molecular sieve catalyst with high temperature and hydrothermal resistance, improves the water resistance and heat resistance of the catalyst, and makes it suitable for hydrogenation of all components of the oil phase and water phase after biomass cracking . The introduction of organic functional groups, on the one hand, seals the hydroxyl groups on the surface of mesoporous molecular sieves through silanization, thereby further improving the hydrothermal stability of the obtained molecular sieves, so as to adapt to the harsh conditions required for catalytic modification of bio-oil. On the other hand, the introduction of organic functional groups can Introduce acidic or basic functional groups on the catalyst and endow other catalytic activities, for example: acidic functional groups have higher catalytic activity for reactions such as dehydration and decarboxylation, while basic functional groups have higher catalytic activity for reactions such as condensation.

Another aspect of the present invention provides a method for simultaneously hydrofining the oil-water dual-phase full components of biomass cracked crude oil by using a high-temperature air-cooled nuclear reactor. The method includes three relatively independent processes:

(1) High-temperature heating process: the first stream of helium is heated to 800-1000°C through the core of a high-temperature gas-cooled nuclear reactor, and then passes through the first heat exchanger to exchange heat with the second stream of helium. After cooling down, the gas is recycled back to the core of the high-temperature gas-cooled nuclear reactor for heating;

(2) Hydrogen production process, the second helium gas at 800-950°C from the first heat exchange heat exchanger passes through the hydrogen production reactor to drive the thermochemical cycle hydrogen production process, and decomposes water to obtain hydrogen and oxygen. The two strands of helium are reduced to a medium temperature of 400-500°C, which is called medium temperature helium; the thermochemical cycle hydrogen production process in the hydrogen production process is an iodine-sulfur cycle process.

(3) Biomass pyrolysis crude oil hydrofining process, biomass pyrolysis crude oil oil-water dual-phase full components first enter the second heat exchanger, conduct heat exchange with medium-temperature helium, and convert into biomass pyrolysis crude oil vapor at 300-400 °C , and then mixed with the hydrogen obtained from the hydrogen production process, it enters the hydrogenation fixed-bed reactor, and is converted into a refined biological substance mainly composed of hydrocarbons under the action of the mesoporous molecular sieve SBA-15 catalyst doped with active metals and grafted with organic functional groups. Oil vapor, after condensation and gas-liquid separation, liquid fuel oil and flammable non-condensable gas are obtained.

In the high-temperature heating process, the second stream of helium from the first heat exchanger is high-temperature helium at a temperature of 800-950°C. This high-temperature helium first enters the hydrogen production process, and becomes Medium-temperature helium, which is cooled to 200-300°C to become low-temperature helium after heat exchange through the second heat exchanger, and the low-temperature helium enters the first heat exchanger and is then combined with the high-temperature air-cooled nuclear reactor core The first stream of helium at 800-1000°C is used for heat exchange; in the whole process, the heat of the second stream of helium is used in a cascade manner.

The oil phase and the water phase contained in the oil-water dual-phase of biomass cracked crude oil are not separated, and the entire components of the oil-water dual-phase are directly vaporized and then hydrogenated.

The hydrogenation temperature range is 200-400°C, preferably 250-350°C; the pressure is 2-20Mpa, preferably 5-15MPa; the total components of bio-crude oil: hydrogen (mass ratio) is 100:5-100:10, preferably It is 100:7～100:9.

The advantages of the present invention are as follows:

1) The catalyst of the present invention is both water-resistant and heat-resistant, and is suitable for simultaneous hydrofining of the oil-water two-phase full components of biomass-cracked crude oil without oil-water separation of biomass-cracked crude oil. This is equivalent to saving at least one oil-water separation step in the entire hydrogenation process. According to the biomass cracking crude oil hydrogenation process before the present invention, because the catalyst is neither resistant to water nor high temperature, it is necessary to first separate the oil from the biomass cracking crude oil, and then only hydrogenate the oil phase, and the hydrogenation process is due to A large amount of water must also be produced through deoxygenation, so a second oil-water separation process is required after hydrogenation to obtain biomass fuel oil. However, the present invention does not need the oil-water separation step before hydrogenation, and can directly carry out hydrogenation refining on the oil-water two-phase full components of biomass cracked crude oil at the same time, which simplifies the process flow and saves equipment investment.

2) Because the oil-water two-phase full components of biomass cracking crude oil can be hydrogenated and refined at the same time, the organic matter in the water phase can be hydrogenated, which improves the utilization rate of organic matter and increases the yield of biomass fuel. It also reduces the cost of subsequent treatment of the aqueous phase.

3) The unique method of the present invention utilizes a high-temperature air-cooled nuclear reactor to simultaneously carry out hydrofining of the oil-water dual-phase full components of biomass pyrolysis crude oil, and utilizes the heat from the high-temperature air-cooled nuclear reactor in stages to improve the overall energy utilization efficiency .

Description of drawings

Figure 1 is a schematic diagram of the catalyst composition and structure of the present invention.

Fig. 2 is a schematic process flow diagram of the method for simultaneous hydrofining of bio-crude oil-water two-phase full components by using a high-temperature air-cooled reactor according to the present invention.

The reference signs have the following meanings:

1. High temperature air-cooled nuclear reactor core; 2. Hot gas mixing chamber; 3. Helium blower; 4. First heat exchanger; 5. I-S cycle hydrogen production reactor; 6. Gas mixer; 7. Second heat exchanger ; 8. Catalytic hydrogenation reactor; 9. Catalyst bed; 10. Gas-liquid separator;

detailed description

A method for simultaneous hydrofining of oil-water dual-phase full components of biological crude oil by using a high-temperature air-cooled nuclear reactor proposed by the present invention is described in detail in conjunction with the accompanying drawings and examples as follows.

The process is briefly described as follows:

After the first stream of helium is pressurized by the helium blower 3, it enters the core 1 of the high-temperature gas-cooled reactor, and after being heated by the core of the high-temperature reactor, the high-temperature helium is mixed evenly in the hot gas mixing chamber 2, and the temperature is 800-1000°C , through the high-temperature helium-helium heat exchanger (first heat exchanger) 4, after cooling down, enter the high-temperature gas-cooled reactor core for heating and recycling after being pressurized by the helium blower 3;

Another stream of helium comes out of the heat exchanger 4, and the temperature is 800-950°C. The high-temperature helium passes through the hydrogen production reactor 5, drives the thermochemical cycle reaction, decomposes water to obtain hydrogen and oxygen, and reduces the helium to 400-500°C. Medium temperature in °C; the medium temperature helium gas enters the heat exchanger (second heat exchanger) 7, and after heat exchange with the incoming bio-crude oil, it becomes low temperature helium gas with a temperature of 200-300 °C. The bio-crude oil vapor and the hydrogen obtained from the hydrogen production process are fully mixed in the gas mixer 6. Due to the heat preservation of the gas mixer and the catalytic hydrogenation fixed-bed reactor, the bio-crude oil vapor and hydrogen can maintain a higher temperature to ensure energy efficiency. A hydrogenation reaction occurs. The mixed gas includes the organic components in the oil phase and the gas phase, and the hydrogenation reaction occurs under the action of the mesoporous molecular sieve SBA-15 catalyst doped with active metals and grafted with organic functional groups in the catalytic bed 9 in the hydrogenation reactor 8, and the conversion It is a refined bio-oil vapor mainly composed of hydrocarbon components. After condensation and gas-liquid separation, liquid fuel oil and flammable non-condensable gas are obtained. The reacted bio-oil vapor and unreacted hydrogen enter the gas-liquid separator 10 . In the gas-liquid separator 10, the mixed gas is condensed and divided into several phases: the gas is mainly small molecule hydrocarbons and unreacted hydrogen, which can be used as gas fuel, and the oil phase is hydrocarbon liquid fuel, which is the main phase of the present invention. target product, and an aqueous phase. Compared with the water phase in bio-crude oil, the organic content in the condensed water phase is very small.

Embodiment 1. In crude oil by biomass cracking, the oil phase is 75%, the water phase is 25%, the oxygen content of the oil phase is 30%, and the calorific value is 22MJ/kg. Bio-oil vapor and hydrogen (the mass ratio of the two is 100:7) are mixed and then enter the catalytic hydrogenation fixed-bed reactor 8. The hydrogenation reaction temperature is 350°C and the hydrogen pressure is 15MPa. The catalyst is mesoporous molecular sieve SBA-15 doped with Pt and added amino organic functional groups. The oil phase obtained after the hydrogenation reaction is completed and condensed and separated accounts for 80%, the oxygen content of the oil phase is 2.5%, the calorific value is 39MJ/kg, the gas phase accounts for 3%, and the rest is the water phase.

Embodiment 2, in bio-crude oil, the oil phase is 75% by mass, the water phase is 25%, the oxygen content of the oil phase is 30%, and the heat value is 22MJ/kg. Bio-oil vapor and hydrogen (the mass ratio of the two is 100:6) are mixed and then enter the catalytic hydrogenation fixed-bed reactor 8, the hydrogenation reaction temperature is 280°C, and the hydrogen pressure is 4MPa. The catalyst is mesoporous molecular sieve SBA-15 doped with Pd-Co and grafted with amino and carboxyl organic functional groups. The oil phase obtained after the hydrogenation reaction is completed and condensed and separated accounts for 80%, the oxygen content of the oil phase is 0.5%, the calorific value is 41.2MJ/kg, the gas phase accounts for 4%, and the rest is the water phase.

Embodiment 3, the mass ratio of bio-crude oil is 75%, the water phase is 25%, the oxygen content of the oil phase is 30%, and the calorific value is 22MJ/kg. Bio-oil vapor and hydrogen (the mass ratio of the two is 100:9) are mixed and then enter the catalytic hydrogenation fixed-bed reactor 8. The hydrogenation reaction temperature is 320°C and the hydrogen pressure is 10MPa. The catalyst is mesoporous molecular sieve SBA-15 doped with Pt-Ni and grafted amino and sulfonic acid organic functional groups at the same time. The oil phase obtained after the hydrogenation reaction is completed and condensed and separated accounts for 80%, the oxygen content of the oil phase is 1.5%, the calorific value is 40MJ/kg, the gas phase accounts for 5%, and the rest is the water phase.

Embodiment 4, in bio-crude oil, the oil phase is 75%, the water phase is 25%, the oxygen content of the oil phase is 30%, and the calorific value is 22MJ/kg. Bio-oil vapor and hydrogen (the mass ratio of the two is 100:6) are mixed and then enter the catalytic hydrogenation fixed-bed reactor 8. The hydrogenation reaction temperature is 300°C and the hydrogen pressure is 12MPa. The catalyst is mesoporous molecular sieve SBA-15 doped with Mo and grafted with sulfonic acid organic functional groups. The oil phase obtained after the hydrogenation reaction is completed and condensed and separated accounts for 79%, the oxygen content of the oil phase is 3.5%, the calorific value is 37.5MJ/kg, the gas phase accounts for 2%, and the rest is the water phase.

Claims (9)

1. A water-resistant and heat-resistant hydrogenation catalyst, the catalyst is a mesoporous molecular sieve SBA-15 doped with an active metal and grafted with an organic functional group; wherein the doped active metal is Pt, Pd, Zr, Ru, Ni One or more of Co, Mo, and the grafted organic functional group is one or more of amino, carboxyl and sulfonic acid groups; it is characterized in that the method for catalyst doping active metal comprises the following steps: weighing The metal salt is dissolved in the mixed solution of absolute ethanol: anhydrous acetic acid: concentrated hydrochloric acid with a volume ratio of 60:5:2 by ultrasonic vibration, and then SBA-15 is added. After alternating ultrasonic vibration and stirring for 0.5h, the mixture is evenly transferred to the surface Evaporate the solvent at 30°C to gel, and then age at 65°C for 24 hours. The product obtained is heated to 550°C at 2°C/min in a muffle furnace, and the solid powder obtained after calcination at 550°C for 5 hours is doped SBA-15 for active metals. 2. The catalyst according to claim 1, characterized in that said metal salt is one or more of platinum nitrate, palladium nitrate, zirconium nitrate, ruthenium trichloride, nickel nitrate, cobalt nitrate and molybdenum nitrate mixture, the amount of the metal salt is ethanol: the molar ratio of metal = 1600:1 ~ 320:1; the amount of SBA-15 is the molar ratio of ethanol to Si in SBA-15 = 32:1 ~ 320: 1. 3. The catalyst according to claim 1, characterized in that the method for grafting organic functional groups comprises the following steps: taking SBA-15 doped with active metals, adding it to absolute ethanol or hydrochloric acid solution, ultrasonically dispersing to complete suspension, and then Add modification reagents, reflux at 120°C for 24 hours, filter after cooling, and wash with absolute ethanol for 3-5 times. After oxidation or acidification, filter to obtain a white solid. After drying at room temperature, it is doped with active metals and grafted with organic functional groups. The mesoporous molecular sieve SBA-15. 4. Catalyst according to claim 3, it is characterized in that described modifying agent is the one in aminopropyltrimethoxysilane, mercaptophenylpropyltrimethoxysilane, nitrile propyltrimethoxysilane or Several types, the amount of the modifying agent added is such that the molar ratio of the heteroatom N or S in the modifying agent to the Si in the mesoporous molecular sieve SBA-15 is 0.02-0.10. 5. A method for hydrorefining bio-crude oil utilizing a high-temperature gas-cooled reactor, characterized in that the method comprises three relatively independent processes: (1) High-temperature heating process: the first stream of helium is heated to 800-1000°C through the core of a high-temperature gas-cooled nuclear reactor, and then passes through the first heat exchanger to exchange heat with the second stream of helium. After cooling down, the gas is recycled back to the core of the high-temperature gas-cooled nuclear reactor for heating; (2) Hydrogen production process, the second helium gas at 800-950°C from the first heat exchange heat exchanger passes through the hydrogen production reactor to drive the thermochemical cycle hydrogen production process, and decomposes water to obtain hydrogen and oxygen. The second strand of helium is lowered to a medium temperature of 400-500°C, which is called medium temperature helium; (3) Bio-crude oil hydrofining process, the bio-crude oil-water dual-phase full components first enter the second heat exchanger, conduct heat exchange with the medium-temperature helium gas, and convert it into bio-crude oil vapor at 300-400 °C, and then mix with the production The hydrogen obtained in the hydrogen process enters the hydrogenation fixed-bed reactor after being mixed, and is converted into refined bio-oil vapor mainly composed of hydrocarbons under the action of the catalyst according to claim 1, and liquid fuel oil and combustible oil are obtained after condensation and gas-liquid separation. Not condensed. 6 . The method for hydrofining bio-crude oil by using a high-temperature gas-cooled reactor according to claim 5, characterized in that, the thermochemical cycle hydrogen production process in the hydrogen production process is an iodine-sulfur cycle process. 7. the method for utilizing high temperature gas-cooled reactors to carry out hydrofining of bio-crude oil according to claim 5, characterized in that the oil phase and the water phase contained in the bio-crude oil are not separated, and the oil-water dual-phase full components of the bio-crude oil are directly treated Hydrogenation is carried out after vaporization. 8. The method for hydrofining bio-crude oil using a high-temperature gas-cooled reactor according to claim 7, characterized in that the hydrogenation temperature range is 200-400°C, the pressure is 2-20Mpa, and the bio-crude oil-water two-phase complete group The mass ratio of hydrogen to hydrogen is 100:5-100:10. 9. The method for hydrofining bio-crude oil using a high-temperature gas-cooled reactor according to claim 7, characterized in that the hydrogenation temperature range is 250-350°C, the pressure is 5-15MPa, and the bio-crude oil-water two-phase complete group The mass ratio of hydrogen to hydrogen is 100:7-100:9.