CN108264918B - Hydrolysis hydrogenation process of biomass - Google Patents

Hydrolysis hydrogenation process of biomass Download PDF

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Publication number
CN108264918B
CN108264918B CN201711420301.XA CN201711420301A CN108264918B CN 108264918 B CN108264918 B CN 108264918B CN 201711420301 A CN201711420301 A CN 201711420301A CN 108264918 B CN108264918 B CN 108264918B
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slurry
biomass
pressure
hydrogen
straws
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CN108264918A (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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Priority to PCT/CN2018/122667 priority patent/WO2019128867A1/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
    • C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
    • 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
    • C10G1/008—Controlling or regulating of liquefaction processes
    • 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
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
    • 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
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/086—Characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • C10G2300/1007—Used oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • 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
    • C10G2300/70—Catalyst aspects
    • C10G2300/703—Activation

Abstract

The invention relates to the field of biological energy, in particular to a biomass hydrolysis hydrogenation process, which comprises the steps of preparing slurry, sequentially drying, primarily crushing, compressing and secondarily crushing straws, mixing the straws with a catalyst to obtain a mixture, and adding the mixture into an oil product to grind and pulp the mixture to obtain the slurry with the straw concentration of 30-60 wt%. The invention initiatively carries out the treatment process of firstly compressing and then secondarily crushing the straws, and the biomass is compressed, so that the loose straws are subjected to the stages of rearrangement, mechanical denaturation, moulding rheology and the like, the volume of the straws is greatly reduced, the porosity of the straws can be reduced, 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 improved, the concentration of reaction materials is increased, the conveying capacity of the pump for the biomass in unit time is improved, the stable operation and the conveying of the pump are ensured, and the conversion rate of the biomass is improved.

Description

Hydrolysis hydrogenation process of biomass
Technical Field
The invention relates to the field of biological energy, in particular to a hydrolysis hydrogenation process of biomass.
Background
Fossil non-renewable energy sources such as coal, crude oil, natural gas, and oil shale are gradually depleted with the rapid development of socioeconomic performance, and CO generated by their combustion2、SO2、NOxThe increasing environmental pollution caused by the pollutants causes that people have to seriously consider ways to obtain energy and methods for improving the environment. The biomass refers to all organic substances formed by directly or indirectly utilizing photosynthesis of green plants, including plants, animals, microorganisms and excretions and metabolites thereof, and has renewability, low pollution and wide distribution, so that the development and utilization of biomass has become the strategic focus of the current development of renewable energy sources from the viewpoints of energy safety and environmental protection.
The biomass liquefaction technology is an important component in biomass resource utilization, and the liquefaction mechanism 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, the technology of direct liquefaction of biomass mainly includes two major categories, namely indirect liquefaction and direct liquefaction, wherein the technology of direct liquefaction of biomass is to directly liquefy biomass from solid to liquid at a 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. The biomass direct liquefaction technology mainly comprises pyrolysis liquefaction, catalytic liquefaction, pressurized hydrogenation liquefaction and the like, particularly the pressurized hydrogenation liquefaction product has high yield and good quality, and generally comprises complex processes of solid material drying, crushing, pulping, heating, pressurizing, reacting, separating and the like. For example, chinese patent document CN103242871A discloses a heavy oil-biomass hydrogenation co-liquefaction process, in which dried biomass is pre-pulverized to 40-100 mesh, and then mixed with heavy oil to form slurry, a catalyst and a vulcanizing agent are added to the slurry, and then the slurry is placed in a slurry bed hydrogenation reactor, the reaction temperature is controlled to 370-430 ℃, the hydrogen partial pressure is 4-8MPa, a hydrogenation thermal cracking reaction is performed, and the reaction product is fractionated to obtain bio-oil and coke.
The process realizes the conversion from biomass to bio-oil, but in the above technology, on one hand, slurry formed by biomass and heavy oil needs to be conveyed to a slurry bed hydrogenation reactor by a pump, and most of biomass (such as straw) has low specific gravity due to rich porosity, so that the biomass is difficult to dissolve in a biomass liquefaction solvent, and the concentration of the biomass in the slurry is low (the biomass in the above technology only accounts for 5-20 wt% of the mass of the heavy oil), so that the conveying amount of the biomass in unit time by the pump is limited, and the 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 liquefied solvent, and the viscosity of the heavy oil used as the slurry solvent is high, so that the slurry is difficult to flow, the conveying pipeline is easy to block, and the stable transportation of the pump is difficult to realize. 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. In addition, the conversion rate of biomass is low (the conversion rate is only about 90%) in the above technology.
Therefore, how to improve the existing biomass liquefaction process to increase the concentration of biomass in the slurry, improve the delivery amount of the pump to the biomass in unit time, realize smooth transportation of the pump, reduce energy consumption and improve the biomass conversion rate still remains a technical problem to be solved.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of small conveying amount of the pump to the biomass, unstable transportation, low biomass conversion rate and high energy consumption in the existing biomass liquefaction process, and further provide a biomass hydrolysis hydrogenation process.
Therefore, the technical scheme adopted by the invention for solving the problems is as follows:
a process for the hydrolytic hydrogenation of biomass, comprising the steps of:
preparing slurry containing a catalyst and biomass, introducing hydrogen into the slurry to react, and controlling the reaction pressure to be 15-20MPa and the reaction temperature to be 380-420 ℃ to finally prepare bio-oil;
the biomass is straws, and the slurry is prepared by the steps of drying, primarily crushing, compressing and secondarily crushing the straws in sequence, mixing the straws with the catalyst to obtain a mixture, adding the mixture into an oil product, and grinding and pulping to obtain the slurry with the straw concentration of 30-60 wt%.
The straw raw material in the invention can be cereal crop straws of wheat, rice, corn, reed, sorghum, millet and the like, can also be leguminous plant straws of soybean, small bean, mung bean, broad bean, pea and the like, can also be fiber crop straws of cotton, flax, ramie, hemp and the like, and can also be a biomass raw material formed by a plurality of straws.
In the slurry preparation step, 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。
In the slurry, the viscosity of the slurry was 500-1400mPa ∙ s (50 ℃).
In the slurry, the content of the biomass is 55-60 wt%.
In the preparation step of the slurry, the oil product 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 grinding pulping is stirring pulping, dispersing pulping, emulsifying pulping, shearing pulping or homogenizing pulping.
In the slurry, the content of the catalyst is 0.1-10 wt%, preferably 2 wt%; the particle size of the catalyst is 5-500 μm;
the specific method for introducing hydrogen into the slurry comprises the following steps:
injecting high-pressure hydrogen into the slurry, and controlling the volume ratio of the high-pressure hydrogen to the slurry to be (600-1000): 1, thereby forming a reaction feedstock;
feeding the reaction raw materials into a slurry bed reactor to carry out hydrolysis, cracking and hydrogenation reactions, and injecting high-pressure cold hydrogen into the slurry bed reactor at the same time, wherein the total gas velocity in the slurry bed reactor is controlled to be 0.02-0.2 m/s, and preferably 0.05-0.08 m/s;
the pressure of the high-pressure hydrogen and the pressure of the high-pressure cold hydrogen are both 15-22MPa, and the temperature of the high-pressure cold hydrogen is 50-135 ℃.
Injecting the high-pressure hydrogen into the slurry twice, specifically:
after injecting high-pressure medium-temperature hydrogen into the slurry for the first time, carrying out heat exchange on the slurry and heating the slurry to 380-420 ℃, and then injecting high-pressure high-temperature hydrogen into the slurry for the second time;
wherein the temperature of the high-pressure medium-temperature hydrogen is 360-420 ℃, and the temperature of the high-pressure high-temperature hydrogen is 430-510 ℃.
And injecting the cold hydrogen through 3-5 injection ports on the side wall of the slurry bed reactor.
The inventory of the catalyst in the slurry bed reactor is controlled to be 5-30 wt% of the mass of the liquid phase in the slurry bed reactor.
The reaction time is 30-120 min.
The catalyst is biomass charcoal which is subjected to vulcanization treatment and loaded with active components, the active components are one or more of ferric oxide, iron oxyhydroxide or ferric hydroxide, and the content of the active components is 10-50 wt% based on the total mass of the active components and the biomass charcoal;
the preparation method of the biomass charcoal loaded with the active components comprises the following steps:
(1) taking biomass charcoal as a biomass charcoal carrier;
(2) and loading an active component on the biomass charcoal carrier to prepare the catalyst.
The specific method for loading the active component on the biomass charcoal carrier comprises the following steps:
mixing the biomass charcoal carrier and the active component aqueous solution to prepare a suspension, adding a precipitator to precipitate the active component on the biomass charcoal carrier, and washing and drying to prepare the catalyst; wherein the precipitant is ammonia water or at least one aqueous solution of carbonate, bicarbonate and hydroxide of alkali metal, the temperature in the precipitation process is controlled to be 30-90 ℃, and the pH value is 7-9.
Or the catalyst is amorphous iron oxyhydroxide after vulcanization treatment.
The technical scheme of the invention has the following advantages:
1. the invention provides a biomass hydrolysis hydrogenation process, which comprises the steps of preparing slurry, drying, primarily crushing, compressing and secondarily crushing straws in sequence, mixing the mixture with a catalyst to obtain a mixture, adding the mixture into an oil product, grinding and pulping to obtain the slurry with the straw concentration of 30-60 wt%, initiatively carrying out 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, rearrangement 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, facilitating the straws to be dispersed in the oil product, improving the content of the straws in the oil product and increasing the concentration of reaction materials, wherein the content of the straws in the slurry can be as high as 30-60 wt% and is far higher than 5-16 wt% in the prior art, 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.
The invention prepares the slurry containing catalyst and biomass, then introduces hydrogen into the slurry to react, and controls the reaction pressure to be 15-20MPa and the reaction temperature to be 380-.
2. According to the hydrolysis hydrogenation process of the substance, the compression temperature is controlled to be 30-60 ℃, the straw is compressed at the temperature, the rheological property of the straw can be obviously enhanced, and the viscosity of the biomass slurry is reduced.
3. The invention provides a process for hydrolyzing and hydrogenating biomass, which comprises the steps of adopting a slurry bed reactor, firstly sending reaction raw materials into the slurry bed reactor from the bottom of the reactor to react, and simultaneously injecting cold hydrogen into the reactor, thus realizing the difference control of flow velocity of each phase state in the reactor by depending on different specific gravities of gas, liquid and solid materials and matching with the change of specific gravity difference caused by the yield of light oil products after reaction, leading the biomass raw materials to be hydrolyzed, cracked and hydrogenated from bottom to top in the reactor, returning the biomass and catalyst solid particles with large specific gravity to the bottom to participate in the reaction again under the action of cold hydrogen on the upper part even if the biomass and the catalyst solid particles with large specific gravity rise along with the gas and the light oil products in the process, properly adjusting the hydrogen content and the cold hydrogen injection quantity in slurry entering the reactor according to the material densities of the upper part, the middle part and the lower part of the reactor, thereby realizing the circulation of the unconverted biomass in the reactor and the balanced discharge of the catalyst, ensuring the full progress of reactions such as hydrolysis hydrogenation and the like, and being beneficial to improving the biomass conversion rate and the bio-oil yield.
4. According to the biomass hydrolysis hydrogenation process provided by the invention, high-pressure hydrogen is injected into the slurry twice, namely, the high-pressure hydrogen is injected once before and after the temperature of the slurry is raised, and the disturbance of the slurry in the heat exchanger can be increased by the previous high-pressure hydrogen injection, so that the deposition of solid biomass and a catalyst is avoided.
5. According to the biomass hydrolysis hydrogenation process provided by the invention, the catalyst added into the slurry is subjected to vulcanization treatment, and the vulcanized catalyst has good hydrogenation performance, so that coke formation can be further avoided, and the hydrolysis hydrogenation reaction is more sufficient.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. 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
A process for the hydrolytic hydrogenation of biomass, comprising the steps of:
pretreatment of biomass
Feeding rice straws and reed straws into a dryer, drying for 5h at 50 ℃ until the water content is lower than 2 wt%, then feeding the rice straws and the reed straws into a superfine pulverizer to be primarily pulverized, wherein the median particle size after primary pulverization is 100 mu m, then feeding the rice straws and the reed straws after primary pulverization into a briquetting machine to be compressed and extruded and molded at the temperature of 30 ℃ and under the pressure of 3MPa, then carrying out secondary pulverization, wherein the median particle size after secondary pulverization is 30 mu m, and the bulk density after secondary pulverization is 500kg/m3And then standby.
Preparation of the catalyst
(1) Taking biomass charcoal as a biomass charcoal carrier;
(2) and loading iron oxide on the biomass charcoal carrier, and carrying out vulcanization treatment to obtain the catalyst.
The specific method for loading ferric oxide on the biomass charcoal carrier comprises the following steps:
mixing the biomass charcoal carrier and the aqueous solution of the iron oxide to prepare a suspension, adding the aqueous solution of sodium carbonate and ammonia water as a precipitator, precipitating the iron oxide on the biomass charcoal carrier, and washing, drying and vulcanizing to prepare the catalyst, wherein the temperature in the precipitation process is 90 ℃, the pH value is 7, and the content of the iron oxide is 50 wt% based on the total mass of the iron oxide and the biomass charcoal carrier.
Preparation of biomass slurry
Mixing the pretreated biomass and a catalyst to obtain a mixture, adding the mixture into mixed oil of hogwash oil and residual oil, stirring and pulping to form slurry, wherein the total content of rice straws and reed straws in the slurry is 60 wt%, the viscosity of the slurry is 500mPa ∙ s (50 ℃), the content of the catalyst in the slurry is 10 wt%, and the particle size of the added catalyst is 5 mu m.
Hydrolysis and hydrogenation reaction:
introducing hydrogen into the biomass slurry to react, and controlling the reaction pressure to be 20MPa and the reaction temperature to be 380 ℃ to prepare bio-oil;
the specific method for introducing the hydrogen comprises the following steps: injecting high-pressure hydrogen into the slurry, and controlling the volume ratio of the high-pressure hydrogen to the slurry to be 600: 1, thereby forming a reaction feedstock; feeding the reaction raw materials into a slurry bed reactor to carry out hydrolysis, cracking and hydrogenation reactions, and injecting high-pressure cold hydrogen into the slurry bed reactor at the same time, wherein the total gas velocity in the slurry bed reactor is controlled to be 0.2 m/s; wherein the pressure of the high-pressure hydrogen and the pressure of the high-pressure cold hydrogen are both 22MPa, and the temperature of the high-pressure cold hydrogen is 135 ℃;
the high pressure cold hydrogen was injected through 3 injection ports on the side wall of the slurry bed reactor. The inventory of the catalyst in the slurry bed reactor accounts for 30 wt% of the mass of the liquid phase in the slurry bed reactor, and the reaction time is 30 min.
Example 2
A process for the hydrolytic hydrogenation of biomass, comprising the steps of:
pretreatment of biomass
Feeding wheat straws and corn straws into a dryer, drying for 3h at 70 ℃ until the water content is lower than 2 wt%, then feeding into a superfine pulverizer to perform primary grinding, wherein the median particle size after primary grinding is 300 mu m, then feeding the wheat straws and the corn straws after primary grinding into a briquetting machine, performing compression extrusion forming at the temperature of 60 ℃ and under the pressure of 0.5MPa, then performing secondary grinding, wherein the median particle size after secondary grinding is 50 mu m, and the bulk density after secondary grinding is 400kg/m3And then standby.
Preparation of the catalyst
(1) Taking biomass charcoal as a biomass charcoal carrier;
(2) and loading iron oxyhydroxide on the biomass charcoal carrier, and carrying out vulcanization treatment to obtain the catalyst.
The specific method for loading the hydroxyl ferric oxide on the biomass charcoal carrier comprises the following steps:
mixing the biomass carbon carrier and the aqueous solution of the iron oxyhydroxide to prepare suspension, adding the aqueous solution of sodium bicarbonate and potassium hydroxide as a precipitator, precipitating the iron oxyhydroxide on the biomass carbon carrier, and washing, drying and vulcanizing to prepare the catalyst, wherein the temperature in the precipitation process is 30 ℃, the pH value is 9, and the content of the iron oxyhydroxide is 10 wt% based on the total mass of the iron oxyhydroxide and the biomass carbon carrier.
Preparation of biomass slurry
Mixing the pretreated biomass and a catalyst to obtain a mixture, adding the mixture into mixed oil of waste lubricating oil and waste engine oil to be dispersed and pulped to form slurry, detecting that the total content of wheat straws and corn straws in the slurry is 50 wt%, the viscosity of the slurry is 1400mPa ∙ s (50 ℃), the content of the catalyst in the slurry is 0.1 wt%, and the particle size of the added catalyst is 500 mu m.
Hydrolysis and hydrogenation reaction:
introducing hydrogen into the biomass slurry to react, and controlling the reaction pressure to be 15MPa and the reaction temperature to be 420 ℃ to prepare bio-oil;
the specific method for introducing the hydrogen comprises the following steps: injecting high-pressure hydrogen into the slurry, and controlling the volume ratio of the high-pressure hydrogen to the slurry to be 1000: 1, thereby forming a reaction feedstock; feeding the reaction raw materials into a slurry bed reactor to carry out hydrolysis, cracking and hydrogenation reactions, and injecting high-pressure cold hydrogen into the slurry bed reactor at the same time, wherein the total gas velocity in the slurry bed reactor is controlled to be 0.02 m/s; wherein the pressure of the high-pressure hydrogen and the pressure of the high-pressure cold hydrogen are both 15MPa, and the temperature of the high-pressure cold hydrogen is 50 ℃;
the high pressure cold hydrogen was injected through 5 injection ports on the side wall of the slurry bed reactor. The inventory of the catalyst in the slurry bed reactor accounts for 5 wt% of the mass of the liquid phase in the slurry bed reactor, and the reaction time is 120 min.
Example 3
A process for the hydrolytic hydrogenation of biomass, comprising the steps of:
pretreatment of biomass
Drying cotton stalk, and drying at 60 deg.C in a drier4 hours till the water content is lower than 2 wt%, then sending into an ultrafine grinder for primary grinding, wherein the median particle size after primary grinding is 200 μm, then sending the cotton straw after primary grinding into a plodder for compression and extrusion forming at the temperature of 40 ℃ and under the pressure of 2MPa, then carrying out secondary grinding, wherein the median particle size after secondary grinding is 40 μm, and the bulk density after secondary grinding is 450kg/m3And then standby.
Preparation of the catalyst
(1) Taking biomass charcoal as a biomass charcoal carrier;
(2) and loading ferric hydroxide and iron oxyhydroxide on the biomass charcoal carrier, and carrying out vulcanization treatment to obtain the catalyst.
The specific method for loading ferric hydroxide and iron oxyhydroxide on the biomass charcoal carrier comprises the following steps:
mixing the biomass charcoal carrier, the aqueous solution of ferric hydroxide and the aqueous solution of ferric oxyhydroxide to prepare a suspension, adding aqueous solution of ammonia water and sodium hydroxide as a precipitator, precipitating the ferric hydroxide and the ferric oxyhydroxide on the biomass charcoal carrier, washing, drying and vulcanizing to prepare the catalyst, wherein the temperature in the precipitation process is 40 ℃, the pH value is 7.5, and the total content of the ferric hydroxide and the ferric oxyhydroxide is 40 wt% based on the total mass of the ferric hydroxide, the ferric oxyhydroxide and the biomass charcoal carrier.
Preparation of biomass slurry
Mixing the pretreated biomass and a catalyst to obtain a mixture, adding the mixture into mixed oil of heavy oil and wash oil to emulsify and pulp to form slurry, and detecting that the content of cotton straws in the slurry is 55 wt%, the viscosity of the slurry is 650mPa ∙ s (50 ℃), the content of the catalyst in the slurry is 2 wt%, and the particle size of the added catalyst is 300 mu m.
Hydrolysis and hydrogenation reaction:
introducing hydrogen into the biomass slurry to react, and controlling the reaction pressure to be 16MPa and the reaction temperature to be 400 ℃ to prepare bio-oil;
the specific method for introducing the hydrogen comprises the following steps: injecting high-pressure hydrogen into the slurry, and controlling the volume ratio of the high-pressure hydrogen to the slurry to be 900: 1, thereby forming a reaction feedstock; feeding the reaction raw materials into a slurry bed reactor to carry out hydrolysis, cracking and hydrogenation reactions, and injecting high-pressure cold hydrogen into the slurry bed reactor at the same time, wherein the total gas velocity in the slurry bed reactor is controlled to be 0.1 m/s; wherein the pressure of the high-pressure hydrogen and the pressure of the high-pressure cold hydrogen are both 19MPa, and the temperature of the high-pressure cold hydrogen is 105 ℃;
the high pressure cold hydrogen was injected through 4 injection ports on the side wall of the slurry bed reactor. The inventory of the catalyst in the slurry bed reactor accounts for 15 wt% of the mass of the liquid phase in the slurry bed reactor, and the reaction time is 40 min.
Example 4
A process for the hydrolytic hydrogenation of biomass, comprising the steps of:
pretreatment of biomass
Feeding cotton straws and soybean straws into a dryer, drying at 65 ℃ for 3h until the water content is lower than 2 wt%, then feeding into a superfine pulverizer to perform primary grinding, wherein the median particle size after primary grinding is 150 mu m, then feeding the cotton straws and the soybean straws after primary grinding into a briquetting machine, performing compression extrusion forming at the temperature of 50 ℃ and under the pressure of 1MPa, then performing secondary grinding, wherein the median particle size after secondary grinding is 40 mu m, and the bulk density after secondary grinding is 420kg/m3And then standby.
Preparation of biomass slurry
Mixing the pretreated biomass and vulcanized amorphous iron oxyhydroxide serving as a catalyst to obtain a mixture, adding the mixture into rancid oil, shearing and pulping to form slurry, wherein the total content of cotton straws and soybean straws in the slurry is 30 wt%, the viscosity of the slurry is 1000mPa ∙ s (50 ℃), the content of the amorphous iron oxyhydroxide is 2 wt%, and the particle size of the added amorphous iron oxyhydroxide is 400 mu m.
Hydrolysis and hydrogenation reaction:
introducing hydrogen into the biomass slurry to react, and controlling the reaction pressure to be 18MPa and the reaction temperature to be 380 ℃ to prepare bio-oil;
the specific method for introducing the hydrogen comprises the following steps: injecting high-pressure hydrogen into the biomass slurry twice, specifically: after injecting high-pressure medium-temperature hydrogen into the slurry for the first time, carrying out heat exchange on the slurry and heating the slurry to 380 ℃, and then injecting high-pressure high-temperature hydrogen into the slurry for the second time; wherein the temperature of the high-pressure medium-temperature hydrogen is 360 ℃, and the temperature of the high-pressure high-temperature hydrogen is 510 ℃; the ratio of the total volume of the high-pressure medium-temperature hydrogen and the high-pressure high-temperature hydrogen to the volume of the slurry is 950: 1, thereby forming a reaction feedstock; feeding the reaction raw materials into a slurry bed reactor to carry out hydrolysis hydrogenation reaction, and injecting high-pressure cold hydrogen into the slurry bed reactor at the same time, wherein the total gas velocity in the slurry bed reactor is controlled to be 0.05 m/s; wherein the pressure of the high-pressure hydrogen and the pressure of the high-pressure cold hydrogen are both 21MPa, and the temperature of the high-pressure cold hydrogen is 75 ℃;
the high pressure cold hydrogen was injected through 4 injection ports on the side wall of the slurry bed reactor. The inventory of the catalyst in the slurry bed reactor accounts for 15 wt% of the mass of the liquid phase in the slurry bed reactor, and the reaction time is 40 min.
Example 5
A process for the hydrolytic hydrogenation of biomass, comprising the steps of:
pretreatment of biomass
Sending pea straws, sorghum straws and rice straws into a dryer to be dried for 3 hours at 50 ℃ until the water content is lower than 2 wt%, then sending the pea straws, the sorghum straws and the rice straws into a superfine pulverizer to be primarily pulverized, wherein the median particle size after primary pulverization is 250 mu m, then sending the pea straws, the sorghum straws and the rice straws after primary pulverization into a plodder to be compressed and extruded and molded at the temperature of 55 ℃ and under the pressure of 1.5MPa, then carrying out secondary pulverization, wherein the median particle size after secondary pulverization is 45 mu m, and the bulk density after secondary pulverization is 440kg/m3And then standby.
Preparation of biomass slurry
Mixing the pretreated biomass with vulcanized amorphous iron oxyhydroxide serving as a catalyst to obtain a mixture, adding the mixture into mixed oil of hogwash oil and residual oil for homogenizing and pulping to form slurry, wherein the total content of pea straws, sorghum straws and rice straws in the slurry is 40 wt%, the viscosity of the slurry is 820mPa ∙ s (50 ℃), the content of the amorphous iron oxyhydroxide is 8 wt%, and the particle size of the added amorphous iron oxyhydroxide is 300 mu m.
Hydrolysis and hydrogenation reaction:
introducing hydrogen into the biomass slurry to react, and controlling the reaction pressure to be 17MPa and the reaction temperature to be 420 ℃ to prepare bio-oil;
the specific method for introducing the hydrogen comprises the following steps: injecting high-pressure hydrogen into the slurry twice, specifically: after injecting high-pressure medium-temperature hydrogen into the slurry for the first time, carrying out heat exchange on the slurry and heating the slurry to 420 ℃, and then injecting high-pressure high-temperature hydrogen into the slurry for the second time; wherein the temperature of the high-pressure medium-temperature hydrogen is 420 ℃, and the temperature of the high-pressure high-temperature hydrogen is 430 ℃; the volume ratio of the total volume of the introduced high-pressure medium-temperature hydrogen and high-pressure high-temperature hydrogen to the volume of the slurry is 900: 1, thereby forming a reaction feedstock; feeding the above-mentioned reaction raw material into slurry bed reactor to make hydrolysis hydrogenationReaction ofSimultaneously injecting high-pressure cold hydrogen into the slurry bed reactor, and controlling the total gas velocity in the slurry bed reactor to be 0.08 m/s; wherein the pressure of the high-pressure hydrogen and the pressure of the high-pressure cold hydrogen are both 20MPa, and the temperature of the high-pressure cold hydrogen is 95 ℃;
the high pressure cold hydrogen was injected through 5 injection ports on the side wall of the slurry bed reactor. The inventory of the catalyst in the slurry bed reactor accounts for 25 wt% of the mass of the liquid phase in the slurry bed reactor, and the reaction time is 50 min.
Example 6
A process for the hydrolytic hydrogenation of biomass, comprising the steps of:
pretreatment of biomass
Feeding wheat straws and flax straws into a dryer, drying at 70 ℃ for 5h until the water content is lower than 2 wt%, then feeding into a superfine pulverizer to perform primary grinding, wherein the median particle size after primary grinding is 300 mu m, then feeding the wheat straws and the flax straws after primary grinding into a plodder, performing compression extrusion forming at the temperature of 60 ℃ and under the pressure of 3MPa, then performing secondary grinding, wherein the median particle size after secondary grinding is 48 mu m, and the bulk density after secondary grinding is 490kg/m3And then standby.
Preparation of biomass slurry
Mixing the biomass obtained by pretreatment with vulcanized amorphous iron oxyhydroxide serving as a catalyst to obtain a mixture, adding the mixture into mixed oil of anthracene oil and cycle distillate oil, and stirring and pulping to form slurry; through detection, the total content of wheat straws and flax straws in the slurry is 45 wt%, the viscosity of the slurry is 530mPa ∙ s (50 ℃), the content of the amorphous ferric hydroxide is 0.3 wt%, and the particle size of the added amorphous ferric hydroxide is 20 mu m.
Hydrolysis and hydrogenation reaction:
introducing hydrogen into the biomass slurry to react, and controlling the reaction pressure to be 19MPa and the reaction temperature to be 390 ℃ to prepare bio-oil;
the specific method for introducing the hydrogen comprises the following steps: injecting high-pressure hydrogen into the slurry twice, specifically: after injecting high-pressure medium-temperature hydrogen into the slurry for the first time, carrying out heat exchange on the slurry and heating the slurry to 390 ℃, and then injecting high-pressure high-temperature hydrogen into the slurry for the second time; wherein the temperature of the high-pressure medium-temperature hydrogen is 400 ℃, and the temperature of the high-pressure high-temperature hydrogen is 490 ℃; the volume ratio of the total volume of the introduced high-pressure medium-temperature hydrogen and high-pressure high-temperature hydrogen to the volume of the slurry is 800: 1, thereby forming a reaction feedstock; feeding the above-mentioned reaction raw material into slurry bed reactor to make hydrolysis hydrogenationReaction ofSimultaneously injecting high-pressure cold hydrogen into the slurry bed reactor, and controlling the total gas velocity in the slurry bed reactor to be 0.07 m/s; wherein the pressure of the high-pressure hydrogen and the pressure of the high-pressure cold hydrogen are both 22MPa, and the temperature of the high-pressure cold hydrogen is 105 ℃;
the high pressure cold hydrogen was injected through 5 injection ports on the side wall of the slurry bed reactor. The inventory of the catalyst in the slurry bed reactor accounts for 23 wt% of the mass of the liquid phase in the slurry bed reactor, and the reaction time is 100 min.
Example 7
A process for the hydrolytic hydrogenation of biomass, comprising the steps of:
pretreatment of biomass
Mixing hemp stalk and broad bean stalkFeeding stalks into a dryer, drying at 55 deg.C for 3.5 hr until the water content is less than 2 wt%, primarily pulverizing in a superfine pulverizer to obtain primary pulverized hemp stalk and broad bean stalk with median particle size of 100 μm, feeding the primarily pulverized hemp stalk and broad bean stalk into a briquetting machine, compressing and extruding at 30 deg.C under 0.5MPa, and secondarily pulverizing to obtain secondary pulverized hemp stalk and broad bean stalk with median particle size of 33 μm and bulk density of 500kg/m3And then standby.
Preparation of the catalyst
(1) Taking biomass charcoal as a biomass charcoal carrier;
(2) and loading iron oxide on the biomass charcoal carrier, and carrying out vulcanization treatment to obtain the catalyst.
The specific method for loading ferric oxide on the biomass charcoal carrier comprises the following steps:
mixing the biomass charcoal carrier and the aqueous solution of the iron oxide to prepare a suspension, adding the aqueous solution of sodium hydroxide and ammonia water as a precipitator, precipitating the iron oxide on the biomass charcoal carrier, and washing, drying and vulcanizing to prepare the catalyst, wherein the temperature in the precipitation process is 80 ℃, the pH value is 7.5, and the content of the iron oxide is 50 wt% based on the total mass of the iron oxide and the biomass charcoal carrier.
Preparation of biomass slurry
Mixing the pretreated biomass with the catalyst to obtain a mixture, adding the mixture into illegal cooking oil to disperse and pulp to form slurry, and detecting that the total content of hemp straws and broad bean straws in the slurry is 55 wt%, the viscosity of the slurry is 510mPa ∙ s (50 ℃), the content of the catalyst is 0.2 wt%, and the particle size of the added catalyst is 12 microns.
Hydrolysis and hydrogenation reaction:
introducing hydrogen into the biomass slurry to react, and controlling the reaction pressure to be 20MPa and the reaction temperature to be 410 ℃ to prepare bio-oil;
the specific method for introducing the hydrogen comprises the following steps: injecting high-pressure hydrogen into the slurry twice, specifically: after high-pressure medium-temperature hydrogen is injected into the slurry for the first time, the slurry is heated to the temperature of high temperature through heat exchangeInjecting high-pressure and high-temperature hydrogen into the slurry for the second time at the temperature of 410 ℃; wherein the temperature of the high-pressure medium-temperature hydrogen is 410 ℃, and the temperature of the high-pressure high-temperature hydrogen is 480 ℃; the ratio of the total volume of the introduced high-pressure medium-temperature hydrogen and high-pressure high-temperature hydrogen to the volume of the slurry is 650: 1, thereby forming a reaction feedstock; feeding the above-mentioned reaction raw material into slurry bed reactor to make hydrolysis, cracking and hydrogenationReaction ofSimultaneously injecting high-pressure cold hydrogen into the slurry bed reactor, and controlling the total gas velocity in the slurry bed reactor to be 0.07 m/s; wherein the pressure of the high-pressure hydrogen and the pressure of the high-pressure cold hydrogen are both 22MPa, and the temperature of the high-pressure cold hydrogen is 130 ℃;
the high pressure cold hydrogen was injected through 3 injection ports on the side wall of the slurry bed reactor. The inventory of the catalyst in the slurry bed reactor accounts for 7 wt% of the mass of the liquid phase in the slurry bed reactor; the reaction time was 110 min.
Example 8
A process for the hydrolytic hydrogenation of biomass, comprising the steps of:
pretreatment of biomass
Sending corn straws and ramie straws into a dryer to be dried for 4.5h at 65 ℃ until the water content is lower than 2 wt%, then sending the corn straws and the ramie straws into a superfine pulverizer to be primarily pulverized, wherein the median particle size after primary pulverization is 300 mu m, then sending the corn straws and the ramie straws after primary pulverization into a briquetting machine to be compressed and extruded and molded at the temperature of 50 ℃ and under the pressure of 2.5MPa, then carrying out secondary pulverization, wherein the median particle size after secondary pulverization is 44 mu m, and the bulk density after secondary pulverization is 410kg/m3And then standby.
Preparation of biomass slurry
Mixing the pretreated biomass and vulcanized amorphous iron oxyhydroxide serving as a catalyst to obtain a mixture, adding the mixture into illegal cooking oil for emulsification pulping to form slurry, wherein the total content of corn straws and ramie straws in the slurry is 57 wt%, the viscosity of the slurry is 1130mPa ∙ s (50 ℃), the content of the vulcanized amorphous iron oxyhydroxide is 4 wt%, and the particle size of the added vulcanized amorphous iron oxyhydroxide is 120 mu m.
Hydrolysis and hydrogenation reaction:
introducing hydrogen into the biomass slurry to react, and controlling the reaction pressure to be 17MPa and the reaction temperature to be 400 ℃ to prepare bio-oil;
the specific method for introducing the hydrogen comprises the following steps: injecting high-pressure hydrogen into the slurry twice, specifically: after injecting high-pressure medium-temperature hydrogen into the slurry for the first time, carrying out heat exchange on the slurry and heating the slurry to 400 ℃, and then injecting high-pressure high-temperature hydrogen into the slurry for the second time; wherein the temperature of the high-pressure medium-temperature hydrogen is 410 ℃, and the temperature of the high-pressure high-temperature hydrogen is 500 ℃; the ratio of the total volume of the high-pressure medium-temperature hydrogen and the high-pressure high-temperature hydrogen to the volume of the slurry is 950: 1, thereby forming a reaction feedstock; feeding the above-mentioned reaction raw material into slurry bed reactor to make hydrolysis hydrogenationReaction ofSimultaneously injecting high-pressure cold hydrogen into the slurry bed reactor, and controlling the total gas velocity in the slurry bed reactor to be 0.05 m/s; wherein the pressure of the high-pressure hydrogen and the pressure of the high-pressure cold hydrogen are both 21MPa, and the temperature of the high-pressure cold hydrogen is 75 ℃;
the high pressure cold hydrogen was injected through 4 injection ports on the side wall of the slurry bed reactor. The inventory of the catalyst in the slurry bed reactor accounts for 15 wt% of the mass of the liquid phase in the slurry bed reactor, and the reaction time is 40 min.
Test example 1
The distributions of the products prepared by the processes of examples 1-8 of the present invention are compared as shown in table 1 below.
Table 1 comparison of product distributions for examples 1-8
Figure BDA0001522835140000201
As can be seen from Table 1, the biomass conversion obtained by the process of the present invention is 95-99%, the yield of the oil phase is 70-80%, the amount of residue is less than 0.1 wt%, and the obtained oil phase has a carbon content of 73-90 wt%, a hydrogen content of 5-17 wt%, and an oxygen content of 5-10 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 (9)

1. The biomass hydrolysis hydrogenation process is characterized by comprising the following steps:
preparing slurry containing a catalyst and biomass, introducing hydrogen into the slurry to react, and controlling the reaction pressure to be 15-20MPa and the reaction temperature to be 380-420 ℃ to finally prepare bio-oil;
the biomass is straws, and the preparation of the slurry comprises the steps of drying, primary crushing, compression and secondary crushing of the straws in sequence, mixing with the catalyst to obtain a mixture, adding the mixture into an oil product, and grinding and pulping to obtain the slurry with the straw concentration of 30-60 wt%;
in the slurry preparation step, the compression pressure of the straws is 0.5-3 MPa, and the temperature is 30-60 ℃;
in the step of preparing the slurry, the slurry is prepared,
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；
The specific method for introducing hydrogen into the slurry comprises the following steps:
injecting high-pressure hydrogen into the slurry, and controlling the volume ratio of the high-pressure hydrogen to the slurry to be (600-1000): 1, thereby forming a reaction feedstock;
feeding the reaction raw materials into a slurry bed reactor to perform hydrolysis, cracking and hydrogenation reactions, and injecting high-pressure cold hydrogen into the slurry bed reactor at the same time, wherein the total gas velocity in the slurry bed reactor is controlled to be 0.02-0.2 m/s;
the pressure of the high-pressure hydrogen and the pressure of the high-pressure cold hydrogen are both 15-22MPa, and the temperature of the high-pressure cold hydrogen is 50-135 ℃.
2. The process of hydrolytic hydrogenation of biomass according to claim 1, wherein the biomass content in the slurry is 55 to 60 wt.%.
3. The process of claim 1, wherein the oil product is one or more of waste animal and vegetable oil, waste mineral oil, mineral oil or distillate oil.
4. The process for the hydrolytic hydrogenation of biomass according to claim 1, wherein the catalyst is contained in the slurry in an amount of 0.1 to 10 wt%; the particle size of the catalyst is 5-500 μm.
5. The process for the hydrolytic hydrogenation of biomass according to any one of claims 1 to 4,
the specific method for introducing hydrogen into the slurry comprises the following steps:
and controlling the total gas velocity in the slurry bed reactor to be 0.05-0.08 m/s.
6. The process for the hydrolytic hydrogenation of biomass according to claim 5, wherein the high pressure hydrogen is injected into the slurry in two portions, in particular:
after injecting high-pressure medium-temperature hydrogen into the slurry for the first time, carrying out heat exchange on the slurry and heating the slurry to 380-420 ℃, and then injecting high-pressure high-temperature hydrogen into the slurry for the second time;
wherein the temperature of the high-pressure medium-temperature hydrogen is 360-420 ℃, and the temperature of the high-pressure high-temperature hydrogen is 430-510 ℃.
7. The process of hydrolytic hydrogenation of biomass according to claim 6, wherein the inventory of the catalyst in the slurry bed reactor is controlled to be 5 to 30 wt% of the mass of the liquid phase in the slurry bed reactor.
8. The process for the hydrolytic hydrogenation of biomass according to claim 7, wherein the reaction time is 30-120 min.
9. The process for the hydrolytic hydrogenation of biomass according to claim 8, wherein the catalyst is sulfided biomass char loaded with active components, and the active components are one or more of iron oxide, iron oxyhydroxide or iron hydroxide;
or the catalyst is amorphous iron oxyhydroxide after vulcanization treatment.
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CN102127462A (en) * 2010-01-12 2011-07-20 Ifp新能源公司 Direct biomass hydroliquefaction process comprising two ebullated bed hydroconversion steps
CN106111187A (en) * 2016-06-29 2016-11-16 中国矿业大学 A kind of supported nickel catalyst preparation method for biomass catalyzing hydrocracking

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102127462A (en) * 2010-01-12 2011-07-20 Ifp新能源公司 Direct biomass hydroliquefaction process comprising two ebullated bed hydroconversion steps
CN106111187A (en) * 2016-06-29 2016-11-16 中国矿业大学 A kind of supported nickel catalyst preparation method for biomass catalyzing hydrocracking

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
生物质固化成型技术研究进展与展望;景元琢等;《中国工程科学》;20111231;第72页 *

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