CN108315039B - Method for producing light oil by biomass liquefaction - Google Patents

Method for producing light oil by biomass liquefaction Download PDF

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CN108315039B
CN108315039B CN201711420279.9A CN201711420279A CN108315039B CN 108315039 B CN108315039 B CN 108315039B CN 201711420279 A CN201711420279 A CN 201711420279A CN 108315039 B CN108315039 B CN 108315039B
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reaction
biomass
oil
straws
light
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CN108315039A (en
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林科
李林
郭立新
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Beijing Haixin Energy Technology Co ltd
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Beijing SJ Environmental Protection and New Material Co Ltd
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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
    • 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
    • C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/208—Sediments, e.g. bottom sediment and water or BSW
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/06—Gasoil

Abstract

The invention relates to the field of biological energy, in particular to a method for producing light oil by liquefying biomass, which comprises the specific preparation steps of drying, primarily crushing, compressing and secondarily crushing straws in sequence, mixing the straws with a hydrogenation catalyst and a vulcanizing agent to obtain a mixture, adding the mixture into solvent oil, grinding and pulping to prepare biomass slurry with the straw concentration of 30-60 wt%, initiatively carrying out the treatment process of firstly compressing and then secondarily crushing the straws, and compressing biomass to ensure that loose straws are subjected to the stages of rearrangement, mechanical denaturation, plastic rheology and the like in sequence, so that the density and the specific gravity of the straws are increased, the straws are favorably dispersed in oil products, the content of the straws in the oil products can be increased, the concentration of reaction materials is increased, and the conveying capacity of the biomass in unit time by a pump is increased, ensures the stable operation and transportation of the pump and improves the yield of the light oil.

Description

Method for producing light oil by biomass liquefaction
Technical Field
The invention belongs to the technical field of biomass liquefaction, and particularly relates to a method for producing light oil by biomass liquefaction.
Background
All organic matters capable of growing are collectively called as biomass, and in a broad sense, the biomass refers to all plants and microorganisms, animals taking the plants and the microorganisms as food and waste produced by the animals; in a narrow sense, biomass mainly refers to lignocellulose (lignin for short) such as straws and trees except grains and fruits in the production process of agriculture and forestry, leftovers in the processing industry of agricultural products, wastes in agriculture and forestry, and livestock and poultry manure and wastes in the production process of animal husbandry. Typical biomass materials are crop plants, crop wastes, wood wastes, animal wastes, and the like. Various biomasses have interdependence and interaction relationship, the biomasses can be used as food and industrial raw materials, can improve the environment and adjust the climate, and in addition, the biomasses have the characteristics of renewability, low pollution and wide distribution, so that the biomasses become important components of renewable energy sources, and how to efficiently develop and utilizeThe biomass energy plays a very positive role in solving the problems of energy and ecological environment. The liquefied oil obtained by directly liquefying biomass is an important component in biomass resource utilization. The mechanism of liquefaction of biomass is as follows: biomass is first cracked into oligomers, which are then dehydrated, dehydroxylated, dehydrogenated, deoxygenated and decarboxylated to form small molecule compounds, which are then reacted via condensation, cyclization, polymerization, etc. to produce new compounds. At present, biomass liquefaction technologies can be mainly divided into two major categories, namely indirect liquefaction and direct liquefaction, wherein the biomass direct liquefaction technology is to directly liquefy biomass from solid to liquid at proper temperature and pressure by adopting hydrolysis and supercritical liquefaction or introducing hydrogen, inert gas and the like under the action of a solvent or a catalyst. For example, chinese patent document CN 102127462 a discloses a process for the direct hydro-liquefaction of biomass comprising two ebullated bed hydroconversion steps. The method comprises the following steps: a) preparing a suspension of biomass particles in a solvent; b) the suspension is subjected to at least one fluidized bed catalyst at a temperature of 300-440 ℃ and a total pressure of 15-25MPa for a period of 0.1-5h-1Hourly mass flow rate and at a rate of 0.1-2Nm3A first hydroconversion stage in the presence of hydrogen in a reactor operating with a hydrogen/feed ratio/kg; c) at least a portion of the effluent obtained in step b) is subjected to at least one catalyst comprising an ebullated bed form and at a temperature of 350-470 ℃ and a total pressure of 15-25MPa for a period of 0.1-5h-1Hourly mass flow rate and at a rate of 0.1-2Nm3A second hydroconversion stage in the presence of hydrogen in a reactor operating with a hydrogen/feed ratio/kg. The above technology directly liquefies the biomass feedstock into a liquid substance through the first hydroconversion step and the second hydroconversion step.
However, in the above-mentioned technologies, on one hand, a suspension (i.e. biomass slurry) formed by biomass particles in a solvent needs to be delivered to a fluidized bed hydrogenation reactor by a pump, and most of the biomass (e.g. straw) has a low specific gravity due to its abundant porosity, so that it is difficult to dissolve in the solvent, and the concentration of the biomass in the suspension is low, so that the delivery amount of the biomass in a unit time by the pump is limited, and the above-mentioned hydrogenation co-liquefaction process has low production efficiency, high industrial cost and large energy consumption; on the other hand, the biomass with porosity is easy to float on the surface of the solvent, and the viscosity of the biomass solvent is higher, so that the suspension is difficult to flow, and the conveying pipeline is easy to block, and the stable transportation of the pump is difficult to realize. Although the above-mentioned technology tries to reduce the particle size of the biomass as much as possible to increase the dispersibility of the biomass in the solvent and thus increase the proportion of the biomass in the solvent, since the biomass has a large number of pore structures, the reduction of the particle size of the biomass exposes the micro pores further, which only allows the micro pores to absorb more solvent oil, so that the viscosity of the biomass slurry prepared from the biomass with smaller particle size is rather high, and since the biomass slurry needs to be transferred to the reactor by a pump, the smooth operation and transfer of the pump are inevitably seriously affected. In the prior art, although the dispersing agent is added into the slurry to improve the concentration and the dispersibility of the biomass in the slurry, the addition of the dispersing agent often influences the quality of the prepared bio-oil. Furthermore, the above-mentioned technique provides, by separating the liquid substances, a gas phase, a water phase, and a light fraction of at least one naphtha, kerosene and/or diesel type liquid hydrocarbon, a vacuum gas oil heavy hydrocarbon fraction, a vacuum residue fraction and a solid fraction capable in the vacuum residue. The vacuum gas oil heavy hydrocarbon fraction and the vacuum residue fraction may have light fractions entrained therein during the separation process, resulting in a decrease in the yield of the light fractions, and the light fractions may also have heavy fractions entrained therein during the separation process, also affecting the yield of the light fractions.
Therefore, how to improve the existing biomass liquefaction process to increase the concentration of biomass in the slurry, improve the delivery amount of the biomass by the pump in unit time, realize smooth transportation of the pump, reduce energy consumption and improve the yield of light oil still remains a technical problem to be solved urgently for the technical staff in the field.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of small conveying capacity of the pump to the biomass, unstable transportation, high energy consumption and low yield of the light oil in the existing biomass liquefaction process, and further provide a method for producing the light oil by biomass liquefaction.
The technical scheme adopted by the invention for solving the problems is as follows:
a method for producing light oil by biomass liquefaction comprises the following steps:
(1) mixing biomass, a hydrogenation catalyst, a vulcanizing agent and solvent oil to prepare biomass slurry;
(2) carrying out a first liquefaction reaction on the biomass slurry and hydrogen, and collecting a first reaction product;
(3) carrying out a second liquefaction reaction on the first reaction product and hydrogen, and collecting a second reaction product;
(4) carrying out first separation on the second reaction product, and collecting a light component and a heavy component;
(5) carrying out reduced pressure distillation on the heavy components, and collecting light fractions;
(6) mixing the light component and the light fraction to carry out hydrogenation reaction, and collecting a hydrogenation product;
(7) fractionating the hydrogenation product to obtain light oil;
in the step (1), the biomass is straws, and the preparation of the biomass slurry comprises the steps of drying, primary crushing, compression and secondary crushing of the straws in sequence, mixing with the hydrogenation catalyst and the vulcanizing agent to obtain a mixture, adding the mixture into the solvent oil, and grinding and pulping to obtain the slurry with the straw concentration of 30-60 wt%.
The straw in the invention can be cereal crop straw such as wheat, rice, corn, reed, sorghum, millet and the like, can also be leguminous plant straw such as soybean, small bean, mung bean, broad bean, pea and the like, can also be fiber crop straw such as cotton, flax, ramie, hemp and the like, and can be a straw or a biomass raw material formed by a plurality of straws.
In the step of preparing the biomass slurry, the compression pressure of the straws is 0.5-3 MPa, and the temperature is 30-60 ℃.
In the preparation step of the slurry, the drying temperature of the straws is 50-70 ℃, the drying time is 3-5h, and the water content of the dried straws is less than 2 wt%; the median particle size after primary crushing is 100-; the median particle size after the secondary crushing is 30-50 mu m, and the bulk density after the secondary crushing is 400-3。
The viscosity of the slurry was 500-1400mPa ∙ s (50 ℃).
In the slurry, the content of the straw is 55-60 wt%.
The grinding pulping is stirring pulping, dispersing pulping, emulsifying pulping, shearing pulping or homogenizing pulping.
The solvent oil is one or more of waste animal and vegetable oil, waste mineral oil, mineral oil or distillate oil.
Further, the waste animal and vegetable oil is one or more of waste oil, hogwash oil or rancid oil;
the waste mineral oil is one or two of waste lubricating oil or waste engine oil;
the mineral oil is one or more of heavy oil, residual oil, anthracene oil or wash oil.
The mass ratio of the biomass to the hydrogenation catalyst to the vulcanizing agent is 100: (0.5-5): (0.1-0.4).
In the step (2), the reaction conditions of the first liquefaction reaction are as follows:
the reaction temperature is 350-450 ℃;
the reaction pressure is 15-25 MPa;
the gas-liquid ratio is 1000-;
the space velocity of the biomass slurry is 0.5-2h-1。
In the step (3), the reaction conditions of the second liquefaction reaction are as follows:
the reaction temperature is 380-490 ℃;
the reaction pressure is 15-25 MPa;
the gas-liquid ratio is 700-;
the space velocity of the biomass slurry is 0.3-2h-1。
In the step (5), the temperature of the reduced pressure distillation is 320-400 ℃, and the pressure is 5-20 kPa.
In the step (6), the reaction conditions of the hydrogenation reaction are as follows:
the reaction temperature is 380-420 ℃;
the reaction pressure is 15-20 MPa;
the volume ratio of hydrogen to oil is 1000-1700;
the space velocity is 0.4-2h-1。
In the step (8), the temperature of the fractionation is 340-390 ℃.
And collecting distillate oil obtained after the vacuum distillation step and heavy fraction obtained in the fractionation step, and taking the distillate oil and the heavy fraction as the solvent oil.
Before fractionation, the hydrogenation product also comprises a step of carrying out secondary separation on the hydrogenation product to respectively obtain hydrogen, gas-phase light hydrocarbon and a liquid phase, wherein the hydrogen is circularly used in the first liquefaction reaction, the second liquefaction reaction and the hydrogenation reaction.
In the step (1), the temperature of the mixing step is 25-180 ℃.
The hydrogenation catalyst is at least one of the following catalysts:
1) amorphous iron oxide and/or amorphous iron oxyhydroxide;
2) the amorphous alumina is loaded with active ingredients, the active ingredients are at least one of VIB metal, VIIB metal or VIII metal oxides, and the content of the active ingredients is 10-25 wt%.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a method for producing light oil by biomass liquefaction, which comprises the steps of preparing biomass slurry, drying, primarily crushing, compressing and secondarily crushing straws in sequence, mixing the mixture with a hydrogenation catalyst and a vulcanizing agent to obtain a mixture, adding the mixture into solvent oil, grinding and pulping to obtain slurry with the straw concentration of 30-60 wt%, initiatively performing a treatment process of firstly compressing and then secondarily crushing the straws, and compressing the biomass to ensure that loose straws are subjected to the stages of collapse, closure and the like, re-positioning and mechanical deformation to greatly reduce the volume of the straws, thereby reducing the porosity of the straws, increasing the density and the specific gravity of the straws, being beneficial to dispersing in oil products, improving the content of the straws in the oil products, increasing the concentration of reaction materials, and ensuring that the content of the straws in the slurry can be as high as 30-60 wt%, meanwhile, the increase of the biomass concentration in the slurry also inevitably improves the delivery amount of the pump to the biomass in unit time, thereby improving the efficiency of the whole biomass liquefaction process and reducing the industrial cost and energy consumption; in addition, the increase of the specific gravity of the straw is also beneficial to the suspension and dispersion of the biomass in the slurry, so that the viscosity of the biomass slurry can be reduced, the smooth flowing of the slurry after the biomass is slurried in a pipeline is realized, the blockage of the pipeline is avoided, the stable operation and the conveying of a pump are realized, and meanwhile, high-viscosity waste oil which cannot be used as a biomass liquefaction solvent in the prior art, such as waste engine oil, illegal cooking oil, rancid oil and the like, can also be utilized.
Mixing biomass, a hydrogenation catalyst, a vulcanizing agent and solvent oil to prepare biomass slurry; then, sequentially carrying out a first liquefaction reaction and a second liquefaction reaction on the biomass slurry and the hydrogen, collecting a second reaction product, and ensuring that the biomass is fully liquefied into a liquid phase through two liquefaction reactions so as to improve the yield of liquid oil; then separating the second reaction product, and collecting light components and heavy components; then carrying out reduced pressure distillation on the heavy components, and collecting light fractions; then mixing the light component and the light fraction for hydrogenation reaction; the separation of light components and heavy components is realized through three continuous steps of separation, reduced pressure distillation and hydrogenation reaction, light fractions mixed in the heavy components are separated from the heavy components through reduced pressure distillation, meanwhile, heavy fractions difficult to be hydrogenated and liquefied are separated out, so that the subsequent conversion of light oil is not influenced, then the light fractions and the light components are mixed for hydrogenation reaction, a small amount of heavy components which are easy to be changed into light components in the light components can be converted into the light components through hydrogenation reaction, the yield of the light oil is improved, particularly the yield of low-boiling-point oil in the light oil, such as naphtha and the like, the residue in the light oil is enriched and agglomerated as much as possible by separating and distilling the biomass oil in advance, and then the residue is removed from the bottom of a reduced pressure distillation device, so that the residue content in the subsequent light oil is reduced; and finally, fractionating the hydrogenation product to obtain light oil, heavy oil and oil residue. Through test, the biomass conversion rate of the method is more than or equal to 99 percent, the yield of the light bio-oil with the distillation range below 520 ℃ is 70-80 percent, and the residue content in the light bio-oil is less than 0.1 percent by weight.
(2) The method for producing the light oil by liquefying the biomass, provided by the invention, has the advantages that the compression temperature is controlled at 30-60 ℃, the straw is compressed at the temperature, the rheological property of the straw can be obviously enhanced, and the viscosity of biomass slurry is reduced.
(3) The method for producing the light oil by biomass liquefaction further comprises the step of collecting distillate oil obtained after the vacuum distillation step and heavy fraction obtained in the fractionation step, and taking the distillate oil and the heavy fraction as the solvent oil.
(4) According to the method for producing the light oil by liquefying the biomass, provided by the embodiment of the invention, before fractionation, the hydrogenated product further comprises a step of carrying out secondary separation on the hydrogenated product to respectively obtain hydrogen, gas-phase light hydrocarbon and a liquid phase, wherein the hydrogen can be circularly used in the first liquefaction reaction, the second liquefaction reaction and the hydrogenation reaction.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic process flow diagram of the method for producing light oil by biomass liquefaction according to the invention.
Reference numerals:
1-a vulcanizing agent; 2-biomass; 3-a hydrogenation catalyst; 4-a biomass slurry tank; 5-a suspended bed reactor; 6-internal circulation suspension bed reactor; 7-suspension bed hydrogenation products; 8-a hot high pressure separator; 9-light component; 10-heavy ends; 11-a high differential pressure relief valve; 12-a vacuum column; 13-overhead oil; 14-measuring line distillate oil; 15-fixed bed hydrogenation reactor; 16-fixed bed hydrogenation product; 17-a separator; 18-hydrogen; 19-gas phase light hydrocarbons; 20-distillate oil; 21-a fractionation column; 22-biomass naphtha; 23-biodiesel; 24-biomass tower bottoms oil; 25-residue; 26-hydrogen.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific embodiments. This invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the concept of the invention to those skilled in the art, and the present invention will only be defined by the appended claims.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
The embodiment provides a method for producing light oil by biomass liquefaction, which comprises the following steps as shown in figure 1:
(1) feeding wheat straw into a dryer, drying at 50 deg.C for 5 hr until the water content is less than 2 wt%, primarily pulverizing with a superfine pulverizer to obtain a median particle size of 100 μm, and feeding into a plodderCompression extrusion molding is carried out at the temperature of 30 ℃ and under the pressure of 3MPa, then secondary crushing treatment is carried out, wheat straw particles 2 with the median particle size of 30 mu m are obtained after secondary crushing, and the bulk density of the wheat straw particles 2 is 500kg/m3；
Mixing the wheat straw particles 2, amorphous alumina 3 loaded with Mo oxide and Ni oxide (the particle size is 5-50 μm, the loading amount is 10 wt%) and sulfur 1 according to the mass ratio of 100: 0.5: 0.4, uniformly mixing the mixture in a biomass slurry tank 4 to obtain a mixture, adding the mixture into illegal cooking oil, uniformly mixing the mixture at the temperature of 100 ℃, and stirring and pulping the mixture to form biomass slurry with the biomass content of 60 wt%, wherein the viscosity of the slurry is 500mPa ∙ s (50 ℃) for later use;
(2) carrying out a first liquefaction reaction on the biomass slurry and the added hydrogen 26 in the suspension bed reactor 5, and collecting a first reaction product, wherein the parameters of the first liquefaction reaction are as follows: the reaction temperature is 350 ℃, the reaction pressure is 25MPa, the gas-liquid ratio is 1000L/kg, and the space velocity of the biomass slurry is 2h-1；
(3) And (3) carrying out a second liquefaction reaction on the first reaction product and hydrogen in an internal circulation suspension bed reactor 6, and collecting a second reaction product, namely a suspension bed hydrogenation product 7, wherein the parameters of the second liquefaction reaction are as follows: the reaction temperature is 380 ℃, the reaction pressure is 25MPa, the gas-liquid ratio is 700L/kg, and the space velocity of the biomass slurry is 2h-1；
(4) Carrying out first separation on the second reaction product in a hot high-pressure separator 8 under the pressure of 19MPa, and collecting a light component 9 and a heavy component 10;
(5) the heavy component 10 is depressurized by a high-pressure-difference depressurization valve 11 and then enters a depressurization tower 12, reduced-pressure distillation is carried out at the temperature of 320 ℃ and the pressure of 20kPa, light fractions, namely, tower top oil 13 and measurement line distillate oil 14 in the depressurization tower 12 are collected, the measurement line distillate oil 14 is returned to the step (1) to be used as solvent oil 1, and residue 25 is recovered from the bottom of the depressurization tower 12;
(6) mixing the light component 9 with the tower top oil 13, feeding the mixture into a fixed bed hydrogenation reactor 16 for hydrogenation reaction, and collecting a fixed bed hydrogenation product 16, wherein the hydrogenation reaction condition isThe following were used: the reaction temperature is 380 ℃, the reaction pressure is 20MPa, the volume ratio of hydrogen to oil is 1000, and the space velocity is 2h-1；
(7) The fixed bed hydrogenation product 16 enters a separator 17 for second separation to obtain hydrogen 18, gas-phase light hydrocarbon 19 and liquid phase, namely distillate oil 20, wherein the hydrogen 18 can be used in the first liquefaction reaction, the second liquefaction reaction and the hydrogenation reaction, and the gas-phase light hydrocarbon 19 is recycled;
(8) the distillate oil 20 enters a fractionating tower 21 and is fractionated at 360 ℃, naphtha is separated from the top of the tower, diesel oil is separated from the middle upper part of the tower, and bottom oil 24, namely heavy fraction, is discharged from the bottom of the tower and is returned to the step (1) as the solvent oil 1.
Through test, the conversion rate of the biomass is 99 percent, wherein the yield of the light biomass oil with the distillation range below 520 ℃ is 80 percent, and the residue content in the light biomass oil is 0.08 percent by weight;
elemental analysis of the obtained light biomass oil revealed that the light biomass oil had an organic carbon content of 85 wt%, an organic hydrogen content of 14.5 wt%, and an organic oxygen content of 0.5 wt%.
Example 2
The embodiment provides a method for producing light oil by biomass liquefaction, which comprises the following steps:
(1) sending rice straws, ramie straws and pea straws into a dryer to be dried for 3 hours at 70 ℃ until the water content is lower than 2 wt%, then sending the rice straws, the ramie straws and the pea straws into a superfine pulverizer to be primarily pulverized, wherein the median particle size after primary pulverization is 300 mu m, then sending the rice straws, the ramie straws and the pea straws after primary pulverization into a plodder to be compressed and extruded at the temperature of 60 ℃ and under the pressure of 0.5MPa, then carrying out secondary pulverization treatment, obtaining mixed particles 2 of the rice straws, the ramie straws and the pea straws with the median particle size of 50 mu m after secondary pulverization, wherein the bulk density of the mixed particles 2 is 400kg/m3；
Mixing the mixed particles 2, amorphous alumina 3 (with the particle diameter of 100-150 μm and the loading of 25%) loaded with W oxide and Pd oxide and carbon disulfide 1 according to the mass ratio of 100: 5:0.1, uniformly mixing the mixture in a biomass slurry tank 4 to obtain a mixture, adding the mixture into mixed oil of waste lubricating oil and residual oil, uniformly mixing the mixture at 180 ℃, and then performing dispersed pulping to form biomass slurry with the biomass content of 55 wt%, wherein the viscosity of the slurry is 1400mPa ∙ s (50 ℃) for later use;
(2) carrying out a first liquefaction reaction on the biomass slurry and the added hydrogen 26 in the suspension bed reactor 5, and collecting a first reaction product, wherein the parameters of the first liquefaction reaction are as follows: the reaction temperature is 450 ℃, the reaction pressure is 15MPa, the gas-liquid ratio is 1600L/kg, and the space velocity of the biomass slurry is 0.5h-1；
(3) And (3) carrying out a second liquefaction reaction on the first reaction product and hydrogen in an internal circulation suspension bed reactor 6, and collecting a second reaction product, namely a suspension bed hydrogenation product 7, wherein the parameters of the second liquefaction reaction are as follows: the reaction temperature is 490 ℃, the reaction pressure is 15MPa, the gas-liquid ratio is 1600L/kg, and the space velocity of the biomass slurry is 0.3h-1；
(4) Carrying out first separation on the second reaction product in a hot high-pressure separator 8 under the pressure of 15MPa, and collecting a light component 9 and a heavy component 10;
(5) reducing the pressure of the heavy component 10 by a high-pressure-difference pressure reducing valve 11, then feeding the heavy component into a pressure reducing tower 12, carrying out reduced pressure distillation at the temperature of 400 ℃ and the pressure of 5kPa, collecting light fractions, namely tower top oil 13 and line-measuring distillate oil 14 in the pressure reducing tower 12, returning the line-measuring distillate oil 14 to the step (1) to be used as solvent oil 1, and recovering residue 25 from the bottom of the pressure reducing tower 12;
(6) mixing the light component 9 with the tower top oil 13, feeding the mixture into a fixed bed hydrogenation reactor 16 for hydrogenation reaction, and collecting a fixed bed hydrogenation product 16, wherein the hydrogenation reaction conditions are as follows: the reaction temperature is 420 ℃, the reaction pressure is 15MPa, the hydrogen-oil volume ratio is 1750, and the space velocity is 0.4h-1；
(7) The fixed bed hydrogenation product 16 enters a separator 17 for second separation to obtain hydrogen 18, gas-phase light hydrocarbon 19 and liquid phase, namely distillate oil 20, wherein the hydrogen 18 can be used in the first liquefaction reaction, the second liquefaction reaction and the hydrogenation reaction, and the gas-phase light hydrocarbon 19 is recycled;
(8) the distillate oil 20 enters a fractionating tower 21 and is fractionated at 390 ℃, naphtha is separated from the top of the tower, diesel oil is separated from the middle upper part of the tower, and bottom oil 24, namely heavy fraction, is discharged from the bottom of the tower and is returned to the step (1) as the solvent oil 1.
Through test, the conversion rate of the biomass is 99.2 percent, wherein the yield of the light biomass oil with the distillation range below 520 ℃ is 78 percent, and the residue content in the light biomass oil is 0.06 percent by weight;
elemental analysis of the obtained light biomass oil revealed that the light biomass oil had an organic carbon content of 80 wt%, an organic hydrogen content of 19 wt%, and an organic oxygen content of 1 wt%.
Example 3
The embodiment provides a method for producing light oil by biomass liquefaction, which comprises the following steps:
(1) feeding soybean straws and cotton straws into a dryer, drying for 4h at 60 ℃ until the water content is lower than 2 wt%, then feeding the soybean straws and the cotton straws into a superfine pulverizer to be primarily pulverized, wherein the median particle size of the primarily pulverized soybean straws and cotton straws is 200 mu m, then feeding the primarily pulverized soybean straws and cotton straws into a plodder, compressing and extruding the primarily pulverized soybean straws and cotton straws at the temperature of 40 ℃ under the pressure of 2MPa, performing secondary pulverization, and obtaining mixed particles 2 of the soybean straws and the cotton straws with the median particle size of 40 mu m after secondary pulverization, wherein the bulk density of the mixed particles 2 is 450kg/m3；
Mixing the mixed particles 2, amorphous alumina loaded with Mn oxide (the particle size is 100-150 μm, the loading amount is 15%), amorphous iron oxide and sulfur according to the mass ratio of 100:2: 2: 0.3 evenly mixing the mixture in a biomass slurry tank 4 to obtain a mixture, adding the mixture into mixed oil formed by heavy oil and hogwash oil, evenly mixing the mixture at 25 ℃, and then emulsifying and pulping the mixture to form biomass slurry with the biomass content of 55 wt%, wherein the viscosity of the biomass slurry is 700mPa ∙ s (50 ℃) for later use;
(2) carrying out a first liquefaction reaction on the biomass slurry and the added hydrogen 26 in the suspension bed reactor 5, and collecting a first reaction product, wherein the parameters of the first liquefaction reaction are as follows: the reaction temperature is 400 ℃ and the reaction pressure20MPa, gas-liquid ratio of 1400L/kg, and airspeed of the biomass slurry of 1h-1；
(3) And (3) carrying out a second liquefaction reaction on the first reaction product and hydrogen in an internal circulation suspension bed reactor 6, and collecting a second reaction product, namely a suspension bed hydrogenation product 7, wherein the parameters of the second liquefaction reaction are as follows: the reaction temperature is 450 ℃, the reaction pressure is 20MPa, the gas-liquid ratio is 1000L/kg, and the space velocity of the biomass slurry is 1h-1；
(4) Carrying out first separation on the second reaction product in a hot high-pressure separator 8 under the pressure of 15MPa, and collecting a light component 9 and a heavy component 10;
(5) reducing the pressure of the heavy component 10 by a high-pressure-difference pressure reducing valve 11, then feeding the heavy component into a pressure reducing tower 12, carrying out reduced pressure distillation at the temperature of 380 ℃ and the pressure of 10kPa, collecting light fractions, namely tower top oil 13 and line-measuring distillate oil 14 in the pressure reducing tower 12, returning the line-measuring distillate oil 14 to the step (1) to be used as solvent oil 1, and recovering residue 25 from the bottom of the pressure reducing tower 12;
(6) mixing the light component 9 with the tower top oil 13, feeding the mixture into a fixed bed hydrogenation reactor 16 for hydrogenation reaction, and collecting a fixed bed hydrogenation product 16, wherein the hydrogenation reaction conditions are as follows: the reaction temperature is 400 ℃, the reaction pressure is 18MPa, the hydrogen-oil volume ratio is 1500, and the space velocity is 1.5h-1；
(7) The fixed bed hydrogenation product 16 enters a separator 17 for second separation to obtain hydrogen 18, gas-phase light hydrocarbon 19 and liquid phase, namely distillate oil 20, wherein the hydrogen 18 can be used in the first liquefaction reaction, the second liquefaction reaction and the hydrogenation reaction, and the gas-phase light hydrocarbon 19 is recycled;
(8) the distillate oil 20 enters a fractionating tower 21 and is fractionated at 360 ℃, naphtha is separated from the top of the tower, diesel oil is separated from the middle upper part of the tower, and bottom oil 24, namely heavy fraction, is discharged from the bottom of the tower and is returned to the step (1) as the solvent oil 1.
Through test, the conversion rate of the biomass is 99.5 percent, wherein the yield of the light biomass oil with the distillation range below 520 ℃ is 70 percent, and the residue content in the light biomass oil is 0.07 percent by weight;
elemental analysis of the obtained light biomass oil shows that the light biomass oil contains 80 wt% of organic carbon, 18 wt% of organic hydrogen and 2 wt% of organic oxygen.
Example 4
The embodiment provides a method for producing light oil by biomass liquefaction, which comprises the following steps:
(1) sending sorghum straws, mung bean straws and hemp straws into a dryer to be dried for 3.5h at 55 ℃ until the water content is lower than 2 wt%, then sending the sorghum straws, mung bean straws and hemp straws into a superfine pulverizer to be primarily pulverized, wherein the median particle size of the primarily pulverized straws is 150 mu m, then sending the primarily pulverized sorghum straws, mung bean straws and hemp straws into a plodder to be compressed and extruded at the temperature of 40 ℃ and under the pressure of 2.5MPa, then carrying out secondary pulverization, obtaining mixed particles 2 of the sorghum straws, the mung bean straws and the hemp straws with the median particle size of 35 mu m after secondary pulverization, wherein the bulk density of the mixed particles 2 is 420kg/m3And is ready for use;
uniformly mixing the mixed particles 2 with amorphous iron oxyhydroxide 3 and dimethyl disulfide 1 in a biomass slurry tank 4 according to a mass ratio of 100:4:0.2 to obtain a mixture, adding the mixture into mixed oil of washing oil and distillate oil, uniformly mixing at 100 ℃, and then performing shearing pulping to form biomass slurry with the biomass content of 30 wt%, wherein the viscosity of the slurry is 620mPa ∙ s (50 ℃) for later use;
(2) carrying out a first liquefaction reaction on the biomass slurry and the added hydrogen 26 in the suspension bed reactor 5, and collecting a first reaction product, wherein the parameters of the first liquefaction reaction are as follows: the reaction temperature is 380 ℃, the reaction pressure is 18MPa, the gas-liquid ratio is 1300L/kg, and the space velocity of the biomass slurry is 1.5h-1；
(3) And (3) carrying out a second liquefaction reaction on the first reaction product and hydrogen in an internal circulation suspension bed reactor 6, and collecting a second reaction product, namely a suspension bed hydrogenation product 7, wherein the parameters of the second liquefaction reaction are as follows: the reaction temperature is 450 ℃, the reaction pressure is 18MPa, the gas-liquid ratio is 1200L/kg, and the space velocity of the biomass slurry is 1.5h-1；
(4) Carrying out first separation on the second reaction product in a hot high-pressure separator 8 under the pressure of 22MPa, and collecting a light component 9 and a heavy component 10;
(5) the heavy component 10 is depressurized by a high-pressure-difference depressurization valve 11 and then enters a depressurization tower 12, the pressure is reduced and distilled at the temperature of 380 ℃ and the pressure of 8kPa, light fractions, namely tower top oil 13 and line-measuring distillate oil 14 in the depressurization tower 12 are collected, and residue 25 is recovered from the bottom of the depressurization tower 12;
(6) mixing the light component 9 with the tower top oil 13, feeding the mixture into a fixed bed hydrogenation reactor 16 for hydrogenation reaction, and collecting a fixed bed hydrogenation product 16, wherein the hydrogenation reaction conditions are as follows: the reaction temperature is 400 ℃, the reaction pressure is 18MPa, the hydrogen-oil volume ratio is 1100, and the space velocity is 1.3h-1；
(7) The fixed bed hydrogenation product 16 enters a separator 17 for second separation to obtain hydrogen 18, gas-phase light hydrocarbon 19 and liquid phase, namely distillate oil 20, wherein the hydrogen 18 can be used in the first liquefaction reaction, the second liquefaction reaction and the hydrogenation reaction, and the gas-phase light hydrocarbon 19 is recycled;
(8) the distillate oil 20 enters a fractionating tower 21 and is fractionated at 390 ℃, naphtha is separated from the top of the tower, diesel oil is separated from the middle upper part of the tower, and bottom oil 24, namely heavy fraction, is discharged from the bottom of the tower.
Through test, the conversion rate of biomass is 99.5%, wherein the yield of light biomass oil with the distillation range below 520 ℃ is 75%, and the residue content in the light biomass oil is 0.07 wt%;
elemental analysis of the obtained light biomass oil revealed that the light biomass oil had an organic carbon content of 82 wt%, an organic hydrogen content of 16.5 wt%, and an organic oxygen content of 1.5 wt%.
Example 5
The embodiment provides a method for producing light oil by biomass liquefaction, which comprises the following steps:
(1) feeding corn stalks into a dryer, drying at 65 ℃ for 4.5h until the water content is lower than 2 wt%, then feeding into a superfine pulverizer to perform primary pulverization, wherein the median particle size after primary pulverization is 250 mu m, and then feeding the corn stalks after primary pulverization into a briquetting machinePerforming compression extrusion molding at 55 deg.C under 1MPa, performing secondary pulverization to obtain corn stalk granule 2 with median diameter of 45 μm, and bulk density of the corn stalk granule 2 of 480kg/m3And then standby.
Uniformly mixing the wheat straw particles 2, the amorphous iron oxide, the amorphous iron oxyhydroxide and the sulfur 1 in a biomass slurry tank 4 according to the mass ratio of 100:2:1.5:0.1 to obtain a mixture, adding the mixture into mixed oil of residual oil and waste engine oil, uniformly mixing at 100 ℃, and then performing homogeneous pulping to form biomass slurry with the biomass content of 40 wt%, wherein the viscosity of the slurry is 1110mPa ∙ s (50 ℃), and keeping for later use;
(2) carrying out a first liquefaction reaction on the biomass slurry and the added hydrogen 26 in the suspension bed reactor 5, and collecting a first reaction product, wherein the parameters of the first liquefaction reaction are as follows: the reaction temperature is 360 ℃, the reaction pressure is 21MPa, the gas-liquid ratio is 1300L/kg, and the space velocity of the biomass slurry is 1.1h-1；
(3) And (3) carrying out a second liquefaction reaction on the first reaction product and hydrogen in an internal circulation suspension bed reactor 6, and collecting a second reaction product, namely a suspension bed hydrogenation product 7, wherein the parameters of the second liquefaction reaction are as follows: the reaction temperature is 470 ℃, the reaction pressure is 24MPa, the gas-liquid ratio is 1500L/kg, and the space velocity of the biomass slurry is 1.6h-1；
(4) Carrying out first separation on the second reaction product in a hot high-pressure separator 8 under the pressure of 21MPa, and collecting a light component 9 and a heavy component 10;
(5) reducing the pressure of the heavy component 10 by a high-pressure-difference pressure reducing valve 11, then feeding the heavy component into a pressure reducing tower 12, carrying out reduced pressure distillation at the temperature of 330 ℃ and the pressure of 11kPa, collecting light fractions, namely tower top oil 13 and line-measuring distillate oil 14 in the pressure reducing tower 12, returning the line-measuring distillate oil 14 to the step (1) to be used as solvent oil 1, and recovering residue 25 from the bottom of the pressure reducing tower 12;
(6) mixing the light component 9 with the tower top oil 13, feeding the mixture into a fixed bed hydrogenation reactor 16 for hydrogenation reaction, and collecting a fixed bed hydrogenation product 16, wherein the hydrogenation reaction conditions are as follows: the reaction temperature is390 ℃, the reaction pressure is 20MPa, the hydrogen-oil volume ratio is 1300, and the space velocity is 1.8h-1；
(7) The fixed bed hydrogenation product 16 enters a separator 17 for second separation to obtain hydrogen 18, gas-phase light hydrocarbon 19 and liquid phase, namely distillate oil 20, wherein the hydrogen 18 can be used in the first liquefaction reaction, the second liquefaction reaction and the hydrogenation reaction, and the gas-phase light hydrocarbon 19 is recycled;
(8) the distillate oil 20 enters a fractionating tower 21 and is fractionated at 380 ℃, naphtha is separated from the top of the tower, diesel oil is separated from the middle upper part of the tower, and bottom oil 24, namely heavy fraction, is discharged from the bottom of the tower and is returned to the step (1) as the solvent oil 1.
Through test, the conversion rate of the biomass is 99.2 percent, wherein the yield of the light biomass oil with the distillation range below 520 ℃ is 79 percent, and the residue content in the light biomass oil is 0.08 percent by weight;
elemental analysis of the obtained light biomass oil revealed that the light biomass oil had an organic carbon content of 83 wt%, an organic hydrogen content of 16.2 wt%, and an organic oxygen content of 0.8 wt%.
Example 6
The embodiment provides a method for producing light oil by biomass liquefaction, which comprises the following steps:
(1) drying small bean straw in a dryer at 70 ℃ for 5h until the water content is lower than 2 wt%, then primarily crushing in an ultrafine crusher to obtain a primary crushed medium particle size of 300 mu m, then compressing and extruding the primary crushed small bean straw in a plodder at 60 ℃ and under the pressure of 3MPa, and then secondarily crushing to obtain small bean straw particles 2 with the medium particle size of 50 mu m, wherein the bulk density of the small bean straw particles 2 is 460kg/m3；
Mixing the small bean straw particles 2, the amorphous ferric oxide 3 and the sulfur 1 according to the mass ratio of 100: 4.5: 0.1, uniformly mixing the mixture in a biomass slurry tank 4 to obtain a mixture, adding the mixture into anthracene oil, uniformly mixing the mixture at the temperature of 30 ℃, and then performing dispersed pulping to form biomass slurry with the biomass content of 59 wt%, wherein the viscosity of the slurry is 560mPa ∙ s (50 ℃) for later use;
(2) carrying out a first liquefaction reaction on the biomass slurry and the added hydrogen 26 in the suspension bed reactor 5, and collecting a first reaction product, wherein the parameters of the first liquefaction reaction are as follows: the reaction temperature is 450 ℃, the reaction pressure is 21MPa, the gas-liquid ratio is 1100L/kg, and the space velocity of the biomass slurry is 2h-1；
(3) And (3) carrying out a second liquefaction reaction on the first reaction product and hydrogen in an internal circulation suspension bed reactor 6, and collecting a second reaction product, namely a suspension bed hydrogenation product 7, wherein the parameters of the second liquefaction reaction are as follows: the reaction temperature is 480 ℃, the reaction pressure is 16MPa, the gas-liquid ratio is 1600L/kg, and the space velocity of the biomass slurry is 0.3h-1；
(4) Carrying out first separation on the second reaction product in a hot high-pressure separator 8 under the pressure of 15MPa, and collecting a light component 9 and a heavy component 10;
(5) reducing the pressure of the heavy component 10 by a high-pressure-difference pressure reducing valve 11, then feeding the heavy component into a pressure reducing tower 12, carrying out reduced pressure distillation at the temperature of 400 ℃ and the pressure of 5kPa, collecting light fractions, namely tower top oil 13 and line-measuring distillate oil 14 in the pressure reducing tower 12, returning the line-measuring distillate oil 14 to the step (1) to be used as solvent oil 1, and recovering residue 25 from the bottom of the pressure reducing tower 12;
(6) mixing the light component 9 with the tower top oil 13, feeding the mixture into a fixed bed hydrogenation reactor 16 for hydrogenation reaction, and collecting a fixed bed hydrogenation product 16, wherein the hydrogenation reaction conditions are as follows: the reaction temperature is 410 ℃, the reaction pressure is 17MPa, the hydrogen-oil volume ratio is 1500, and the space velocity is 0.5h-1；
(7) The fixed bed hydrogenation product 16 enters a separator 17 for second separation to obtain hydrogen 18, gas-phase light hydrocarbon 19 and liquid phase, namely distillate oil 20, wherein the hydrogen 18 can be used in the first liquefaction reaction, the second liquefaction reaction and the hydrogenation reaction, and the gas-phase light hydrocarbon 19 is recycled;
(8) the distillate oil 20 enters a fractionating tower 21 and is fractionated at 390 ℃, naphtha is separated from the top of the tower, diesel oil is separated from the middle upper part of the tower, and bottom oil 24, namely heavy fraction, is discharged from the bottom of the tower and is returned to the step (1) as the solvent oil 1.
Through test, the conversion rate of the biomass is 99.5 percent, wherein the yield of the light biomass oil with the distillation range below 520 ℃ is 80 percent, and the residue content in the light biomass oil is 0.07 percent by weight;
elemental analysis of the obtained light biomass oil revealed that the light biomass oil had an organic carbon content of 81 wt%, an organic hydrogen content of 17.2 wt%, and an organic oxygen content of 1.8 wt%.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (13)

1. A method for producing light oil by biomass liquefaction comprises the following steps:
(1) mixing biomass, a hydrogenation catalyst, a vulcanizing agent and solvent oil to prepare biomass slurry;
(2) carrying out a first liquefaction reaction on the biomass slurry and hydrogen, and collecting a first reaction product;
(3) carrying out a second liquefaction reaction on the first reaction product and hydrogen, and collecting a second reaction product;
(4) carrying out first separation on the second reaction product, and collecting a light component and a heavy component;
(5) carrying out reduced pressure distillation on the heavy components, and collecting light fractions;
(6) mixing the light component and the light fraction to carry out hydrogenation reaction, and collecting a hydrogenation product;
(7) fractionating the hydrogenation product to obtain light oil;
in the step (1), the biomass is straws, and the preparation of the biomass slurry comprises the steps of drying, primary crushing, compression and secondary crushing of the straws in sequence, mixing with the hydrogenation catalyst and the vulcanizing agent to obtain a mixture, adding the mixture into the solvent oil, and grinding and pulping to obtain the slurry with the straw concentration of 30-60 wt%; in the step of preparing the biomass slurry, the compression pressure of the straws is 0.5-3 MPa, and the temperature is 30-60 ℃; the solvent oil is one or more of waste animal and vegetable oil and waste mineral oil.
2. The method according to claim 1, wherein in the step of preparing the slurry,
the drying temperature of the straws is 50-70 ℃, the drying time is 3-5h, and the water content of the dried straws is lower than 2 wt%; the median particle size after primary crushing is 100-; the median particle size after the secondary crushing is 30-50 mu m, and the bulk density after the secondary crushing is 400-3。
3. The method as claimed in claim 1, wherein the content of the straw in the slurry is 55-60 wt%.
4. The method according to claim 1, wherein in the step (1), the mass ratio of the biomass to the hydrogenation catalyst to the sulfiding agent is 100: (0.5-5): (0.1-0.4).
5. The method according to claim 1, wherein in the step (2), the reaction conditions of the first liquefaction reaction are as follows:
the reaction temperature is 350-450 ℃;
the reaction pressure is 15-25 MPa;
the gas-liquid ratio is 1000-;
the space velocity of the biomass slurry is 0.5-2h-1。
6. The method according to claim 1, wherein in the step (3), the reaction conditions of the second liquefaction reaction are as follows:
the reaction temperature is 380-490 ℃;
the reaction pressure is 15-25 MPa;
the gas-liquid ratio is 700-;
the space velocity of the biomass slurry is 0.3-2h-1。
7. The method as claimed in claim 1, wherein the temperature of the reduced pressure distillation in step (5) is 320 ℃ to 400 ℃ and the pressure is 5 to 20 kPa.
8. The method according to claim 1, wherein in the step (6), the reaction conditions of the hydrogenation reaction are as follows:
the reaction temperature is 380-420 ℃;
the reaction pressure is 15-20 MPa;
the volume ratio of hydrogen to oil is 1000-1700;
the space velocity is 0.4-2h-1。
9. The method as claimed in claim 1, wherein the temperature of the fractionation in step (8) is 340-390 ℃.
10. The method of claim 1, further comprising the step of collecting a distillate obtained after the vacuum distillation step and a heavy fraction obtained in the fractionation step, and using the distillate and the heavy fraction as the solvent oil.
11. The process of any one of claims 1-10, wherein the hydrogenated product further comprises a second separation step prior to fractionation to obtain hydrogen, a light hydrocarbon gas phase, and a liquid phase, wherein hydrogen is recycled for use in the first liquefaction reaction, the second liquefaction reaction, and the hydrogenation reaction.
12. The method according to claim 11, wherein the temperature of the mixing step in step (1) is 25-180 ℃.
13. The process of claim 12, wherein the hydrogenation catalyst is at least one of the following:
1) amorphous iron oxide and/or amorphous iron oxyhydroxide;
2) the amorphous alumina is loaded with active ingredients, the active ingredients are at least one of VIB metal, VIIB metal or VIII metal oxides, and the content of the active ingredients is 10-25 wt%.
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