CN108251150B - One-pot liquefaction process of biomass - Google Patents

One-pot liquefaction process of biomass Download PDF

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CN108251150B
CN108251150B CN201711419221.2A CN201711419221A CN108251150B CN 108251150 B CN108251150 B CN 108251150B CN 201711419221 A CN201711419221 A CN 201711419221A CN 108251150 B CN108251150 B CN 108251150B
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slurry
biomass
straws
hydrogen
bed reactor
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CN108251150A (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/CN2018/122665 priority patent/WO2019128866A1/en
Priority to SG11202000174UA priority patent/SG11202000174UA/en
Priority to MYPI2019007761A priority patent/MY191775A/en
Priority to EP18896217.9A priority patent/EP3608387B1/en
Priority to US16/537,527 priority patent/US10975312B2/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
    • C10G1/08—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
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The preparation steps of the slurry of the biomass one-pot liquefaction process provided by the invention are that straws are dried, primarily crushed, compressed and secondarily crushed in sequence, then the straws are mixed with a catalyst and a vulcanizing agent to obtain a mixture, and the mixture is added into water to obtain the slurry with the straw concentration of 35-50 wt%. The invention initiatively compresses the straws and then crushes the straws for the second time, and compresses the biomass to ensure that the loose straws are subjected to the stages of rearrangement, mechanical deformation and the like, so that the volume of the straws is greatly reduced, the density and the specific gravity of the straws can be increased, the straws are favorable for being dispersed in water, the content of the straws in the water can be increased, the conveying capacity of the pump to the biomass in unit time can be increased, the efficiency of the whole biomass liquefaction process is improved, the industrial cost and the energy consumption are reduced, and the stable operation and the conveying of the pump are realized.

Description

One-pot liquefaction process of biomass
Technical Field
The invention relates to the technical field of biological energy conversion, in particular to a one-pot liquefaction 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. Biomass is a renewable energy source, and has huge potential and advantages in meeting energy requirements, reducing environmental pollution and improving energy structure, and biomass refers to all organic substances formed by photosynthesis of directly or indirectly available green plants, including plants, animals, microorganisms and excretion and metabolites thereof, and has renewability, low pollution and wide distribution. In recent years, the conversion and utilization of biomass energy has been moving towards high efficiency, clean, biomass liquefaction technology being an important component thereof.
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, the biomass liquefaction technology mainly comprises two types of indirect liquefaction and direct liquefaction, wherein the direct liquefaction refers to that the biomass is directly liquefied into liquid from solid under the action of a solvent or a catalyst by adopting hydrolysis and supercritical liquefaction or introducing hydrogen, inert gas and the like under proper temperature and pressure. The biomass direct liquefaction technology mainly comprises pyrolysis liquefaction, catalytic liquefaction, pressurized hydrogenation liquefaction and the like, particularly the product obtained by the hydrogenation pressurization liquefaction has high yield and good quality, and generally comprises complex procedures of solid material drying, crushing, pulping, heating, pressurizing, reacting, separating and the like.
For example, chinese patent document CN107163973A discloses a method for preparing bio-oil by in-situ hydrogen supply and liquefaction of biomass, which comprises adding a catalyst and deionized water into a mixture of biomass powder and aluminum powder, and performing a hydrogen supply and liquefaction reaction at a temperature of 280-.
However, in the above-mentioned technologies, on one hand, the specific gravity of the biomass (such as straw) is low due to the abundant porosity, so that the content of the biomass in water is low, the water-carbon ratio is high, and the slurry formed by the biomass and water needs to be conveyed into the reactor by a pump, so that the conveying amount of the biomass by the pump in unit time is limited, and the production efficiency of the biomass liquefaction process is low, the industrial cost is high, and the energy consumption is large; on the other hand, the biomass with porosity is easy to float on the surface of water, so that slurry formed by the biomass and the water is not easy to flow, and a conveying pipeline is easy to block, so that the stable transportation of a 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 yield of the bio-oil prepared by the technology is low (the oil yield is only 18.20-26.54 wt%), so that the industrial large-scale production application cannot be realized.
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 bio-oil yield is still a technical problem to be solved urgently for the technical staff in the field.
Disclosure of Invention
Therefore, the invention aims to overcome the defects of small conveying amount of the pump to the biomass, unstable transportation, high energy consumption and low bio-oil yield in the existing biomass liquefaction process, and further provides a one-pot biomass liquefaction process.
Therefore, the technical scheme adopted by the invention for solving the problems is as follows:
a one-pot liquefaction process of biomass comprises the following steps:
preparing slurry containing a catalyst, a vulcanizing agent and biomass, introducing hydrogen into the slurry to react, and controlling the reaction pressure to be 15-20MPa and the reaction temperature to be 300-400 ℃ to finally prepare the 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 to obtain pretreated biomass, mixing the pretreated biomass with the catalyst and the vulcanizing agent to obtain a mixture, adding the mixture into water, and grinding and pulping to obtain the slurry with the straw concentration of 35-50 wt%;
in the slurry preparation step, the compression pressure of the straws is 2-5 MPa, and the temperature is 30-60 ℃.
In the preparation step of the slurry, the drying temperature of the straws is 70-110 ℃, 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 400-800mPa ∙ s (50 ℃).
The grinding pulping is stirring pulping, dispersing pulping, emulsifying pulping, shearing pulping or homogenizing pulping.
The catalyst comprises one or more of amorphous iron oxyhydroxide, amorphous alumina loaded with an active component or biomass charcoal loaded with the active component, wherein the active component is selected from one or more oxides of metals in VIB, VIIB or VIII groups of the periodic table of elements.
The active component is selected from one or more of oxides of Mo, W, Fe, Co, Ni, Mn or Pd.
The amount of the catalyst is 1-10 wt% of the mass of the pretreated biomass; the particle size of the catalyst is 5-500 mu m; the dosage of the vulcanizing agent is 0.1-0.4 wt% of the mass of the pretreated biomass.
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 (600-1500): 1, thereby forming a reaction feedstock;
heating the reaction raw materials to 300-400 ℃, then sending the reaction raw materials into a slurry bed reactor to carry out hydrolysis, cracking and hydrogenation reactions, simultaneously injecting cold hydrogen into the slurry bed reactor, and controlling the total gas velocity in the slurry bed reactor to be 0.02-0.2 m/s, preferably 0.05-0.08 m/s;
the pressure of the high-pressure hydrogen is 15-22 MPa, and the temperature of the cold hydrogen is 60-135 ℃.
Injecting the high-pressure hydrogen into the slurry twice, specifically:
injecting the high-pressure hydrogen into the slurry for the first time until the volume ratio of the high-pressure hydrogen to the slurry is 50-200:1, then heating the slurry to 200-280 ℃, and then injecting the high-pressure hydrogen into the slurry for the second time.
And injecting the cold hydrogen through 3-5 injection ports which are sequentially arranged on the side wall of the slurry bed reactor along the height direction.
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 30-60 min.
The preparation method of the biomass charcoal loaded with the active components comprises the following steps:
s1, acidifying or alkalizing the biomass charcoal to prepare a biomass charcoal carrier;
and S2, mixing and grinding the active component and the biomass charcoal carrier to obtain the biomass charcoal loaded with the active component.
The active component is one or more selected from oxides of Mo, W, Fe, Co, Ni, Mn or Pd, and accounts for 1-5% of the mass of the biomass charcoal carrier by mass of metal elements.
The mixing and grinding steps of the active component and the biomass charcoal carrier are as follows: and carrying out vibration grinding and/or plane grinding and/or ball milling on the active component and the biomass carbon carrier to obtain the biomass carbon loaded with the active component and having the particle size of 5-500 mu m.
H in the acidified acidic medium+The mass concentration of the substance(s) is 0.5mol/L to 5 mol/L; the volume ratio of the biomass carbon to the acidic medium is 1: 5-1: 15, the acidification temperature is 30-80 ℃, and the acidification time is 1-10 h; OH in the alkalinized alkaline medium-The mass concentration of the substance(s) is 0.5mol/L to 5 mol/L; the volume ratio of the biomass charcoal to the alkaline medium is 1: 5-1: 15, the alkalization temperature is 30-80 ℃, and the alkalization time is 1-10 h.
The vulcanizing agent in the invention can be sulfur, carbon disulfide or dimethyl disulfide.
The technical scheme of the invention has the following advantages:
1. the invention provides a biomass one-pot liquefaction process, which comprises the preparation steps of drying, primarily crushing, compressing and secondarily crushing straws in sequence, mixing the mixture with a catalyst and a vulcanizing agent to obtain a mixture, adding the mixture into water, grinding and pulping to obtain the pulp with the straw concentration of 35-50 wt%, and the invention initiatively compresses and secondarily crushes the straws, compresses biomass, so that loose straws are subjected to the stages of collapse, closure and the like, rearrangement and mechanical deformation, 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 water, the content of the straws in the water can be increased, the concentration of reaction materials is increased, and the biomass concentration in the pulp is increased inevitably, 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, and the stable operation and the conveying of a pump are realized.
According to the invention, slurry containing a catalyst, a vulcanizing agent and biomass is prepared, hydrogen is introduced into the slurry to react, the reaction pressure is controlled to be 15-20MPa, the reaction temperature is controlled to be 300-400 ℃, and the biomass is subjected to cracking and hydrogenation reaction under the action of hydrogen and the catalyst, so that the conversion from the biomass to the bio-oil is realized, the yield of the bio-oil is improved, in the process, the conversion rate of the biomass can reach 95-99%, the yield of the bio-oil is 60-80%, and the residue in the bio-oil is below 0.1 wt%.
2. The one-pot liquefaction process of 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. According to the biomass one-pot liquefaction process provided by the invention, the preferable catalyst is a single catalyst or a combined catalyst of amorphous iron oxyhydroxide, amorphous alumina loaded with an active component or biomass charcoal loaded with an active component, the active component is selected from one or more oxides of metals in VIB, VIIB or VIII groups of the periodic table of elements, and the amorphous iron oxyhydroxide has alkalinity and can promote biomass hydrolysis; the biomass carbon and the amorphous alumina have acidity and a cracking function, and after being loaded by the active component, the cracking function of the catalyst is enhanced, so that the purpose of improving the yield of the bio-oil is achieved.
4. The biomass one-pot liquefaction process provided by the invention adopts a slurry bed reactor, firstly, reaction raw materials are fed into the slurry bed reactor from the bottom of the reactor to react, and simultaneously, cold hydrogen is injected into the reactor, so that the difference control of the flow velocity of each phase state can be realized in the reactor by depending on the 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 the reaction, the biomass raw materials are subjected to hydrolysis, cracking and hydrogenation reaction from bottom to top in the reactor, even if biomass and catalyst solid particles with large specific gravity rise along with the gas and the light oil products in the process, the biomass and the catalyst solid particles return to the bottom to participate in the reaction again under the action of the cold hydrogen on the upper part, the hydrogen content and the cold hydrogen injection amount in slurry entering the reactor are properly adjusted according to the material densities on 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 the reactions such as hydrolysis, cracking, hydrogenation and the like, and being beneficial to improving the biomass conversion rate and the bio-oil yield.
5. According to the one-pot method liquefaction process of biomass, 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.
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 one-pot liquefaction process of biomass comprises the following steps:
pretreatment of biomass
Feeding rice straws and reed straws into a dryer, drying for 5h at 70 ℃ 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 plodder, compressing and extruding and molding at the temperature of 60 ℃ and under the pressure of 2MPa, then carrying out secondary pulverization treatment, wherein the median particle size after secondary pulverization is 30 mu m, and the bulk density of the rice straws and the reed straws after secondary pulverization is 400kg/m3And then standby.
Preparation of the catalyst
S1, acidifying the biomass charcoal to obtain a biomass charcoal carrier;
s2, carrying out vibration grinding on the Mo oxide and the biomass charcoal carrier to obtain the Mo oxide-loaded biomass charcoal with the grain size of 400-500 mu m, namely the catalyst;
in the catalyst, Mo accounts for 1% of the mass of the biomass charcoal carrier in terms of the mass of Mo. H in the acidic medium of the above acidification treatment+The mass concentration of the biomass carbon is 5mol/L, the volume ratio of the biomass carbon to the acidic medium is 1:5, the acidification temperature is 80 ℃, and the acidification time is 1 h.
Preparation of biomass slurry
Mixing the pretreated biomass, the prepared catalyst and sulfur to obtain a mixture, adding the mixture into water, stirring and pulping to form slurry, detecting that the total content of rice straws and reed straws in the slurry is 50 wt%, the viscosity of the slurry is 800mPa ∙ s (50 ℃), wherein the added catalyst is 1 wt% of the mass of the pretreated biomass in the slurry, and the added sulfur is 0.4 wt% of the mass of the pretreated biomass.
And (3) liquefaction reaction:
introducing hydrogen into the biomass slurry to react, and controlling the reaction pressure to be 20MPa and the reaction temperature to be 300 ℃ 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 1500: 1, thereby forming a reaction feedstock; heating the reaction raw materials to 320 ℃, then sending the reaction raw materials into a slurry bed reactor to perform hydrolysis, cracking and hydrogenation reactions, simultaneously injecting cold hydrogen into the slurry bed reactor, and controlling the total gas velocity in the slurry bed reactor to be 0.2 m/s; wherein the pressure of the high-pressure hydrogen is 22MPa, and the temperature of the high-pressure cold hydrogen is 135 ℃;
the cold hydrogen is injected through 3 injection ports which are arranged on the side wall of the slurry bed reactor in sequence along the height direction. The stock of the biomass charcoal loaded with Mo oxide as 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 liquefaction reaction time is 30 min.
Example 2
A one-pot liquefaction process of biomass comprises the following steps:
pretreatment of biomass
Feeding wheat straws and corn straws into a dryer, drying for 3h at 110 ℃ until the water content is lower than 2 wt%, then feeding into an ultrafine grinder for 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 plodder, compressing and extruding at the temperature of 30 ℃ and under the pressure of 5MPa, carrying out secondary grinding, wherein the median particle size after secondary grinding is 50 mu m, and the bulk density of the wheat straws and the corn straws after secondary grinding is 800kg/m3And then standby.
Preparation of the catalyst
S1, acidifying the biomass charcoal to obtain a biomass charcoal carrier;
s2, sequentially carrying out plane grinding and ball milling on the W oxide, the Fe oxide and the biomass charcoal carrier to obtain biomass charcoal loaded with the W oxide and the Fe oxide and having a particle size of 5-150 mu m, namely the catalyst;
in the catalyst, the total mass of W and Fe accounts for 5% of the mass of the biomass charcoal carrier based on the total mass of W and Fe. H in the acidic medium of the above acidification treatment+The amount concentration of the substance(s) is 0.5mol/L, described aboveThe volume ratio of the biomass charcoal to the acidic medium is 1:15, the acidification temperature is 30 ℃, and the acidification time is 10 hours.
Preparation of biomass slurry
And mixing the pretreated biomass, the prepared catalyst and dimethyl disulfide to obtain a mixture, adding the mixture into water for dispersed pulping to form slurry, detecting that the total content of wheat straws and corn straws in the slurry is 45 wt%, the viscosity of the slurry is 400Pa ∙ s (50 ℃), wherein the added catalyst is 10 wt% of the mass of the pretreated biomass in the slurry, and the added dimethyl disulfide is 0.1 wt% of the mass of the pretreated biomass.
And (3) liquefaction reaction:
introducing hydrogen into the biomass slurry to react, and controlling the reaction pressure to be 15MPa 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 600: 1, thereby forming a reaction feedstock; heating the reaction raw materials to 400 ℃, then sending the reaction raw materials into a slurry bed reactor to perform hydrolysis, cracking and hydrogenation reactions, simultaneously injecting cold hydrogen into the slurry bed reactor, and controlling the total gas velocity in the slurry bed reactor to be 0.02 m/s; wherein the pressure of the high-pressure hydrogen is 15MPa, and the temperature of the high-pressure cold hydrogen is 60 ℃;
the cold hydrogen is injected through 5 injection ports which are arranged on the side wall of the slurry bed reactor in sequence along the height direction. The stock amount of the biomass charcoal loaded with W oxide and Fe oxide as 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 liquefaction reaction time is 60 min.
Example 3
A one-pot liquefaction process of biomass comprises the following steps:
pretreatment of biomass
Feeding cotton stalk into a drier, drying at 90 deg.C for 4 hr until the water content is less than 2 wt%, primarily pulverizing with a superfine pulverizer to obtain a median particle diameter of 230 μm, and pulverizingDelivering the crushed cotton stalks into a briquetting machine, performing compression extrusion forming at the temperature of 50 ℃ and under the pressure of 3.5MPa, performing secondary crushing, wherein the median particle size after secondary crushing is 40 mu m, and the bulk density of the cotton stalks after secondary crushing is 620kg/m3And then standby.
Preparation of biomass charcoal loaded with Mo oxide and Pd oxide
S1, acidifying the biomass charcoal to obtain a biomass charcoal carrier;
s2, carrying out vibration grinding on the Mo oxide, the Pd oxide and the biomass charcoal carrier to obtain the biomass charcoal loaded with the Mo oxide and the Pd oxide, wherein the particle size of the biomass charcoal is 120-400 mu m;
in the biomass charcoal carrying the Mo oxide and the Pd oxide, the total mass of Mo and Pd accounts for 3.5% of the mass of the biomass charcoal carrier, based on the total mass of Mo and Pd. H in the acidic medium of the above acidification treatment+The mass concentration of the biomass charcoal is 3.5mol/L, the volume ratio of the biomass charcoal to the acidic medium is 1:10, the acidification temperature is 50 ℃, and the acidification time is 4.3 h.
Preparation of biomass slurry
Mixing the pretreated biomass, the prepared biomass carbon loaded with Mo oxide and Pd oxide, amorphous iron oxyhydroxide and carbon disulfide to obtain a mixture, adding the mixture into water for emulsification and pulping to form slurry, wherein the content of cotton straws in the slurry is 35 wt%, the viscosity of the slurry is 660mPa ∙ s (50 ℃) through detection, the total mass of the added biomass carbon loaded with Mo oxide and Pd oxide and amorphous iron oxyhydroxide (the particle size is 150-.
And (3) liquefaction reaction:
introducing hydrogen into the biomass slurry to react, and controlling the reaction pressure to be 18MPa and the reaction temperature to be 330 ℃ 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; heating the reaction raw materials to 330 ℃, then sending the reaction raw materials into a slurry bed reactor to perform hydrolysis, cracking and hydrogenation reactions, simultaneously injecting cold hydrogen into the slurry bed reactor, and controlling the total gas velocity in the slurry bed reactor to be 0.10 m/s; wherein the pressure of the high-pressure hydrogen is 21MPa, and the temperature of the high-pressure cold hydrogen is 80 ℃;
the cold hydrogen is injected through 4 injection ports which are arranged on the side wall of the slurry bed reactor in sequence along the height direction. The stock amount of the biomass charcoal loaded with Mo oxide and Pd oxide as 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 time of the liquefaction reaction is 45 min.
Example 4
A one-pot liquefaction process of biomass comprises the following steps:
pretreatment of biomass
Feeding cotton straws and soybean straws into a dryer, drying at 100 ℃ for 3.5h until the water content is lower than 2 wt%, then feeding into an ultrafine grinder for primary grinding treatment, wherein the median particle size after primary grinding is 290 mu m, then feeding the cotton straws and the soybean straws after primary grinding into a plodder, compressing and extruding at 45 ℃ and under the pressure of 4.2MPa for extrusion forming, then carrying out secondary grinding treatment, wherein the median particle size after secondary grinding is 44 mu m, and the bulk density after secondary grinding is 710kg/m3And then standby.
Preparation of biomass slurry
Mixing the pretreated biomass with amorphous iron oxyhydroxide (the particle size of which is 100-200 mu m) and sulfur to obtain a mixture, adding the mixture into water, shearing and pulping to form a slurry, wherein the total content of cotton straws and soybean straws in the slurry is 50 wt%, the viscosity of the slurry is 490mPa ∙ s (50 ℃) through detection, the mass of the amorphous iron oxyhydroxide in the slurry is 6 wt% of the mass of the pretreated biomass, and the mass of the added vulcanizing agent is 0.25 wt% of the mass of the pretreated biomass.
And (3) liquefaction reaction:
introducing hydrogen into the biomass slurry to react, and controlling the reaction pressure to be 18MPa and the reaction temperature to be 340 ℃ to prepare bio-oil;
the specific method for introducing the hydrogen comprises the following steps: injecting high-pressure hydrogen into the slurry twice, specifically: firstly injecting high-pressure hydrogen into the slurry until the volume ratio of the high-pressure hydrogen to the slurry is 50:1, then heating the slurry to 200 ℃, then secondly injecting the high-pressure hydrogen into the slurry, and controlling the volume ratio of the total volume of the high-pressure hydrogen injected twice to the volume ratio of the slurry to be 1300: 1, thereby forming a reaction feedstock; heating the reaction raw materials to 340 ℃, then sending the reaction raw materials into a slurry bed reactor to carry out hydrolysis, cracking and hydrogenation reactions, simultaneously injecting 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 is 20MPa, and the temperature of the high-pressure cold hydrogen is 105 ℃;
the cold hydrogen is injected through 4 injection ports which are arranged on the side wall of the slurry bed reactor in sequence along the height direction. The stock amount of amorphous iron oxyhydroxide as a catalyst in the slurry bed reactor was 9 wt% based on the mass of the liquid phase in the slurry bed reactor, and the time for the liquefaction reaction was 38 min.
Example 5
A one-pot liquefaction process of biomass comprises the following steps:
pretreatment of biomass
Feeding pea straws and sorghum straws into a dryer, drying for 3.8h at 105 ℃ 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 260 mu m, then feeding the pea straws and the sorghum straws after primary grinding into a briquetting machine, performing compression extrusion forming at 55 ℃ and under the pressure of 3MPa, then performing secondary grinding treatment, wherein the median particle size after secondary grinding is 33 mu m, and the bulk density after secondary grinding is 530kg/m3And then standby.
Preparation of biomass slurry
Mixing the pretreated biomass with amorphous alumina (with the particle size of 200-500 mu m) loaded with Ni oxide and Pd oxide and sulfur to obtain a mixture, and adding the mixture into water for homogenizing and pulping to form slurry; through detection, the total content of the pea straws and the sorghum straws in the slurry is 47 wt%, and the viscosity of the slurry is 750mPa ∙ s (50 ℃); in the slurry, the mass of amorphous alumina loaded with Ni oxide and Pd oxide is 2 wt% of the mass of the pretreated biomass, and the mass of the added sulfur is 0.3 wt% of the mass of the pretreated biomass.
And (3) liquefaction reaction:
introducing hydrogen into the biomass slurry to react, and controlling the reaction pressure to be 15MPa and the reaction temperature to be 360 ℃ to prepare bio-oil;
the specific method for introducing the hydrogen comprises the following steps: injecting high-pressure hydrogen into the slurry twice, specifically: firstly injecting high-pressure hydrogen into the slurry until the volume ratio of the high-pressure hydrogen to the slurry is 200:1, then heating the slurry to 280 ℃, then secondly injecting the high-pressure hydrogen into the slurry, and controlling the volume ratio of the total volume of the high-pressure hydrogen injected twice to the volume ratio of the slurry to be 650: 1, thereby forming a reaction feedstock; heating the reaction raw materials to 360 ℃, then sending the reaction raw materials into a slurry bed reactor to carry out hydrolysis, cracking and hydrogenation reactions, simultaneously injecting 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 is 19MPa, and the temperature of the high-pressure cold hydrogen is 95 ℃;
the cold hydrogen is injected through 4 injection ports which are arranged on the side wall of the slurry bed reactor in sequence along the height direction. The amount of the amorphous iron oxyhydroxide as a catalyst stored in the slurry bed reactor was 22 wt% based on the mass of the liquid phase in the slurry bed reactor, and the time for the liquefaction reaction was 46 min.
Example 6
A one-pot liquefaction process of biomass comprises the following steps:
pretreatment of biomass
Feeding wheat straw and flax straw into a dryer, drying at 80 deg.C for 4.5 hr until the water content is less than 2 wt%, then feeding into a superfine pulverizer to perform primary pulverization and ash removal treatment, the median particle diameter after primary pulverization is 110 μm, and then feeding the wheat straw after primary pulverization into a pulverizerFeeding the stalks and flax stalks into a plodder to perform compression extrusion forming at the temperature of 35 ℃ and under the pressure of 2.5MPa, and then performing secondary crushing treatment, wherein the median particle size after secondary crushing is 50 mu m, and the bulk density after secondary crushing is 450kg/m3And then standby.
Preparation of biomass slurry
Mixing the pretreated biomass with amorphous alumina (particle size of 200-500 μm) loaded with Mn oxide and Pd oxide, amorphous iron oxyhydroxide and sulfur to obtain a mixture, adding the mixture into water, and stirring to prepare slurry; forming a slurry, wherein the total content of wheat straws and flax straws in the slurry is 43 wt%, the viscosity of the slurry is 770mPa ∙ s (50 ℃), the total mass of amorphous alumina and amorphous iron oxyhydroxide loaded with Mn oxides and Pd oxides in the slurry is 3 wt% of the mass of the pretreated biomass, and the mass of added sulfur is 0.4 wt% of the mass of the pretreated biomass.
And (3) liquefaction 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 twice, specifically: firstly injecting high-pressure hydrogen into the slurry until the volume ratio of the high-pressure hydrogen to the slurry is 100:1, then heating the slurry to 250 ℃, then secondly injecting the high-pressure hydrogen into the slurry, and controlling the volume ratio of the total volume of the high-pressure hydrogen injected twice to the volume ratio of the slurry to be 1050: 1, thereby forming a reaction feedstock; heating the reaction raw materials to 380 ℃, then sending the reaction raw materials into a slurry bed reactor to perform hydrolysis, cracking and hydrogenation reactions, simultaneously injecting 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 is 21MPa, and the temperature of the high-pressure cold hydrogen is 105 ℃;
the cold hydrogen is injected through 3 injection ports which are arranged on the side wall of the slurry bed reactor in sequence along the height direction. The stock amount of amorphous iron oxyhydroxide as a catalyst in the slurry bed reactor was 27 wt% based on the mass of the liquid phase in the slurry bed reactor, and the time for the liquefaction reaction was 40 min.
Example 7
A one-pot liquefaction process of biomass comprises the following steps:
pretreatment of biomass
Sending corn straws and ramie straws into a dryer to be dried for 4 hours at 75 ℃ 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 280 mu m, then sending the corn straws and the ramie straws after primary pulverization into a plodder to be compressed and extruded and molded at the temperature of 55 ℃ and under the pressure of 2.2MPa, and then carrying out secondary pulverization treatment, wherein the median particle size of biomass after secondary pulverization is 50 mu m, and the bulk density after secondary pulverization is 430kg/m3And then standby.
Preparation of biomass slurry
Mixing the pretreated biomass, amorphous iron oxyhydroxide (the particle size is 100-200 mu m) and carbon disulfide to obtain a mixture, adding the mixture into water for dispersing and pulping to form slurry, wherein the total content of corn straws and ramie straws in the slurry is 41 wt%, and the viscosity of the slurry is 790mPa ∙ s (50 ℃); in the slurry, the mass of the amorphous iron oxyhydroxide is 3 wt% of the mass of the pretreated biomass, and the mass of the added carbon disulfide is 0.1 wt% of the mass of the pretreated biomass.
And (3) liquefaction 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: firstly injecting high-pressure hydrogen into the slurry until the volume ratio of the high-pressure hydrogen to the slurry is 150:1, then heating the slurry to 230 ℃, then secondly injecting the high-pressure hydrogen into the slurry, and controlling the volume ratio of the total volume of the high-pressure hydrogen injected twice to the volume ratio of the slurry to be 950: 1, thereby forming a reaction feedstock; heating the reaction raw materials to 390 ℃, then sending the reaction raw materials into a slurry bed reactor to carry out hydrolysis, cracking and hydrogenation reactions, simultaneously injecting cold hydrogen into the slurry bed reactor, and controlling the total gas velocity in the slurry bed reactor to be 0.06 m/s; wherein the pressure of the high-pressure hydrogen is 20MPa, and the temperature of the high-pressure cold hydrogen is 130 ℃;
the cold hydrogen is injected through 5 injection ports which are arranged on the side wall of the slurry bed reactor in sequence along the height direction. The stock amount of amorphous iron oxyhydroxide as a catalyst in the slurry bed reactor was 25 wt% based on the mass of the liquid phase in the slurry bed reactor, and the time for the liquefaction reaction was 55 min.
Example 8
A one-pot liquefaction process of biomass comprises the following steps:
pretreatment of biomass
Sending broad bean straws into a dryer, drying for 3.3h at 75 ℃ until the water content is lower than 2 wt%, then sending into a superfine pulverizer to perform primary grinding, wherein the median particle size after primary grinding is 120 mu m, then sending the primarily ground broad bean straws into a briquetting machine, performing compression extrusion molding at the temperature of 45 ℃ and under the pressure of 2.5MPa, and then performing secondary grinding treatment, wherein the median particle size of the biomass after secondary grinding is 40 mu m, and the bulk density after secondary grinding is 440kg/m3And then standby.
Preparation of the catalyst
S1, preparing a biomass charcoal carrier after alkalization treatment of the biomass charcoal;
s2, carrying out vibration grinding on the Mn oxide and the biomass charcoal carrier to obtain Mn oxide-loaded biomass charcoal with the particle size of 400-500 mu m, namely the catalyst;
in the catalyst, Mn accounts for 4% of the mass of the biomass charcoal carrier in terms of Mn mass. OH in the alkaline medium-The mass concentration of the biomass charcoal is 5mol/L, the volume ratio of the biomass charcoal to the alkaline medium is 1:5, the alkalization temperature is 80 ℃, and the alkalization time is 1 h.
Preparation of biomass slurry
Mixing the pretreated biomass with the prepared catalyst and sulfur to obtain a mixture, adding the mixture into water for emulsification and pulping to form slurry, wherein the total content of hemp straws and broad bean straws in the slurry is 50 wt%, the viscosity of the slurry is 750mPa ∙ s (50 ℃), the mass of the catalyst in the slurry is 8 wt% of the mass of the pretreated biomass, and the mass of the added sulfur is 0.2 wt% of the mass of the pretreated biomass.
And (3) liquefaction reaction:
introducing hydrogen into the biomass slurry to react, and controlling the reaction pressure to be 16MPa and the reaction temperature to be 330 ℃ to prepare bio-oil;
the specific method for introducing the hydrogen comprises the following steps: injecting high-pressure hydrogen into the slurry twice, specifically: firstly injecting high-pressure hydrogen into the slurry until the volume ratio of the high-pressure hydrogen to the slurry is 100:1, then heating the slurry to 220 ℃, then secondly injecting the high-pressure hydrogen into the slurry, and controlling the volume ratio of the total volume of the high-pressure hydrogen injected twice to the volume ratio of the slurry to be 1350: 1, thereby forming a reaction feedstock; heating the reaction raw materials to 330 ℃, then sending the reaction raw materials into a slurry bed reactor to perform hydrolysis, cracking and hydrogenation reactions, simultaneously injecting cold hydrogen into the slurry bed reactor, and controlling the total gas velocity in the slurry bed reactor to be 0.09 m/s; wherein the pressure of the high-pressure hydrogen is 16MPa, and the temperature of the high-pressure cold hydrogen is 78 ℃;
the cold hydrogen is injected through 5 injection ports which are arranged on the side wall of the slurry bed reactor in sequence along the height direction. The stock of the Mn oxide-loaded biomass charcoal as a catalyst in the slurry bed reactor accounts for 15 wt% of the mass of the liquid phase in the slurry bed reactor, and the liquefaction reaction time is 40 min.
Example 9
A one-pot liquefaction process of biomass comprises the following steps:
pretreatment of biomass
Feeding mung bean straw into a dryer, drying at 80 deg.C for 4 hr until the water content is less than 2 wt%, primarily pulverizing with a superfine pulverizer to obtain a median particle size of 200 μm, and feeding into a briquetting machine at 50 deg.C and 5MPaIs compressed and extruded under the pressure of (1), and then is secondarily crushed, wherein the median particle diameter of the secondarily crushed biomass is 45 mu m, and the bulk density of the secondarily crushed biomass is 780kg/m3And then standby.
Preparation of the catalyst
S1, preparing a biomass charcoal carrier after alkalization treatment of the biomass charcoal;
s2, sequentially carrying out plane grinding and ball milling on the Ni oxide and the biomass carbon carrier to obtain the biomass carbon loaded with the Ni oxide with the particle size of 200-400 mu m, namely the catalyst;
in the catalyst, Ni accounts for 1% of the biomass charcoal carrier by mass. OH in the alkaline medium-The mass concentration of the biomass charcoal is 0.5mol/L, the volume ratio of the biomass charcoal to the alkaline medium is 1:15, the alkalization temperature is 30 ℃, and the alkalization time is 10 hours.
Preparation of biomass slurry
Mixing the pretreated biomass with the prepared catalyst and sulfur to obtain a mixture, adding the mixture into water, shearing and pulping to form slurry, wherein the content of the mung bean straws in the slurry is 48 wt%, and the viscosity of the slurry is 420kg/m3 through detection; in the slurry, the mass of the catalyst is 1 wt% of the mass of the pretreated biomass, and the mass of the added sulfur is 0.2 wt% of the mass of the pretreated biomass.
And (3) liquefaction reaction:
introducing hydrogen into the biomass slurry to react, and controlling the reaction pressure to be 18MPa and the reaction temperature to be 350 ℃ 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; heating the reaction raw materials to 450 ℃, then sending the reaction raw materials into a slurry bed reactor to perform hydrolysis, cracking and hydrogenation reactions, simultaneously injecting cold hydrogen into the slurry bed reactor, and controlling the total gas velocity in the slurry bed reactor to be 0.2 m/s; wherein the pressure of the high-pressure hydrogen is 19MPa, and the temperature of the high-pressure cold hydrogen is 135 ℃;
the cold hydrogen is injected through 5 injection ports which are arranged on the side wall of the slurry bed reactor in sequence along the height direction. The stock amount of the biomass charcoal loaded with Ni oxide as the catalyst in the slurry bed reactor was 30 wt% based on the mass of the liquid phase in the slurry bed reactor, and the time for the liquefaction reaction was 55 min.
Examples of the experiments
The results of the evaluation of the effects of the processes provided in examples 1 to 9 of the present invention are shown in Table 1.
TABLE 1 comparison of product distributions for examples 1-9
Figure BDA0001522614910000221
As can be seen from Table 1, the biomass conversion rate obtained by the method of the present invention is 95-99%, the bio-oil yield is 60-80%, the amount of residue in the bio-oil is below 0.1 wt%, and the carbon content in the obtained oil phase is 80-90 wt%, the hydrogen content is 9-19 wt%, and the oxygen content is 1-3 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 (8)

1. A biomass one-pot liquefaction process is characterized by comprising the following steps:
preparing slurry containing a catalyst, a vulcanizing agent and biomass, introducing hydrogen into the slurry to react, and controlling the reaction pressure to be 15-20MPa and the reaction temperature to be 300-400 ℃ to finally prepare the 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 to obtain pretreated biomass, mixing the pretreated biomass with the catalyst and the vulcanizing agent to obtain a mixture, adding the mixture into water, and grinding and pulping to obtain the slurry with the straw concentration of 35-50 wt%;
in the slurry preparation step, the compression pressure of the straws is 2-5 MPa, and the temperature is 30-60 ℃;
the drying temperature of the straws is 70-110 ℃, 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。
2. The process for one-pot liquefaction of biomass according to claim 1, characterized in that said catalyst comprises one or more of amorphous iron oxyhydroxide, amorphous alumina loaded with active components or biomass char loaded with active components selected from one or more oxides of metals of group VIB, VIIB or VIII of the periodic table of the elements.
3. The process for one-pot liquefaction of biomass according to claim 2, characterized in that said active component is selected from one or more of the oxides of Mo, W, Fe, Co, Ni, Mn or Pd.
4. The one-pot biomass liquefaction process according to any one of claims 1 to 3, characterized in that the amount of the catalyst is 1 to 10 wt% of the mass of the pretreated biomass; the particle size of the catalyst is 5-500 mu m; the dosage of the vulcanizing agent is 0.1-0.4 wt% of the mass of the pretreated biomass.
5. The one-pot liquefaction process of biomass according to claim 1, characterized in that the specific method of introducing hydrogen into the slurry is:
injecting high-pressure hydrogen into the slurry, and controlling the volume ratio of the high-pressure hydrogen to the slurry to be (600-1500): 1, thereby forming a reaction feedstock;
heating the reaction raw material to 300-400 ℃, then sending the reaction raw material into a slurry bed reactor to perform hydrolysis, cracking and hydrogenation reactions, simultaneously injecting cold hydrogen into the slurry bed reactor, and controlling the total gas velocity in the slurry bed reactor to be 0.02-0.2 m/s;
the pressure of the high-pressure hydrogen is 15-22 MPa, and the temperature of the cold hydrogen is 60-135 ℃.
6. The one-pot biomass liquefaction process according to claim 5, characterized in that the total gas velocity in the slurry bed reactor is controlled to be 0.05-0.08 m/s.
7. The one-pot liquefaction process of biomass according to claim 5, characterized in that the high-pressure hydrogen is injected into the slurry in two portions, in particular:
injecting the high-pressure hydrogen into the slurry for the first time until the volume ratio of the high-pressure hydrogen to the slurry is 50-200:1, then heating the slurry to 200-280 ℃, and then injecting the high-pressure hydrogen into the slurry for the second time.
8. The process for one-pot liquefaction of biomass according to any one of claims 5 to 7, characterized in that 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; the reaction time is 30-60 min.
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