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WO2019128866A1 - 一种生物质或煤与生物质的一锅法液化工艺 - Google Patents

一种生物质或煤与生物质的一锅法液化工艺 Download PDF

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Publication number
WO2019128866A1
WO2019128866A1 PCT/CN2018/122665 CN2018122665W WO2019128866A1 WO 2019128866 A1 WO2019128866 A1 WO 2019128866A1 CN 2018122665 W CN2018122665 W CN 2018122665W WO 2019128866 A1 WO2019128866 A1 WO 2019128866A1
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Prior art keywords
biomass
slurry
coal
oil
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2018/122665
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English (en)
French (fr)
Inventor
林科
李林
郭立新
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing SJ Environmental Protection and New Material Co Ltd
Original Assignee
Beijing SJ Environmental Protection and New Material Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN201711420278.4A external-priority patent/CN108219818B/zh
Priority claimed from CN201711420263.8A external-priority patent/CN108264916B/zh
Priority claimed from CN201711421720.5A external-priority patent/CN108085042B/zh
Priority claimed from CN201711419221.2A external-priority patent/CN108251150B/zh
Priority claimed from CN201711430518.9A external-priority patent/CN108219819B/zh
Priority claimed from CN201711429908.4A external-priority patent/CN108264920A/zh
Priority to EP18896217.9A priority Critical patent/EP3608387B1/en
Priority to MYPI2019007761A priority patent/MY191775A/en
Priority to SG11202000174UA priority patent/SG11202000174UA/en
Application filed by Beijing SJ Environmental Protection and New Material Co Ltd filed Critical Beijing SJ Environmental Protection and New Material Co Ltd
Publication of WO2019128866A1 publication Critical patent/WO2019128866A1/zh
Priority to US16/537,527 priority patent/US10975312B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/1802—Organic compounds containing oxygen natural products, e.g. waxes, extracts, fatty oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C10L1/326—Coal-water suspensions
    • 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
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C10L2200/0484—Vegetable or animal oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/02—Combustion or pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/14—Injection, e.g. in a reactor or a fuel stream during fuel production
    • C10L2290/141—Injection, e.g. in a reactor or a fuel stream during fuel production of additive or catalyst
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/544—Extraction for separating fractions, components or impurities during preparation or upgrading of a fuel

Definitions

  • the invention relates to the technical field of bioenergy conversion, in particular to a one-pot liquefaction process of biomass or coal and biomass.
  • Biomass is a renewable energy source that has great potential and advantages in meeting energy demand, reducing environmental pollution, and improving energy structure. Biomass refers to all organic substances formed by photosynthesis of green plants directly or indirectly. It includes plants, animals, microorganisms and their excretions and metabolites. It is renewable, low in pollution and widely distributed. In recent years, the conversion and utilization of biomass energy has been moving in an efficient and clean direction.
  • Biomass liquefaction technology is an important part of it.
  • the liquefaction mechanism of biomass is as follows: the biomass is first cleaved into oligomers, and then dehydrated, dehydroxylated, dehydrogenated, deoxygenated and decarboxylated to form small molecular compounds, which are then subjected to condensation, cyclization, polymerization, etc. And generate new compounds.
  • biomass liquefaction technology mainly includes indirect liquefaction and direct liquefaction.
  • Direct liquefaction refers to hydrolysis, supercritical liquefaction or introduction of hydrogen, inert gas, etc. under the action of solvent or catalyst, under appropriate temperature and pressure.
  • the biomass is liquefied directly from the solid to a liquid.
  • Biomass direct liquefaction technology mainly includes pyrolysis liquefaction, catalytic liquefaction, pressurized hydroliquefaction, etc., especially the product with hydrogenation and pressure liquefaction has high yield and good quality, which generally includes drying, pulverizing, pulping and heating of solid materials.
  • Complex processes such as pressurization, reaction, and separation.
  • CN103242871A discloses a heavy oil-biomass hydrogenation co-liquefaction process which comprises pre-pulverizing dried biomass to 40-100 mesh and then mixing with heavy oil to form a slurry, and to the slurry
  • the catalyst and the vulcanizing agent are added, and then placed in a slurry bed hydrogenation reactor, the reaction temperature is controlled from 370 ° C to 430 ° C, the partial pressure of hydrogen is 4-8 MPa, and the hydrothermal pyrolysis reaction is carried out, and the reaction product is fractionated to obtain Bio-oil and coke.
  • the above process enables the conversion of biomass to bio-oil, but in the above technique, on the one hand, the slurry formed from biomass and heavy oil needs to be pumped into the slurry bed hydrogenation reactor, while most biomass (for example) Straw) has a low specific gravity due to its rich porosity, making it less soluble in the biomass liquefaction solvent, resulting in a lower concentration of biomass in the slurry (the biomass in the above technology only accounts for 5-20% by weight of the heavy oil).
  • biomass with porosity It is easy to float on the surface of the liquefied solvent, and the viscosity of the heavy oil as the solvent of the slurry is relatively large, so that the slurry is not easy to flow, which is easy to cause blockage of the conveying pipe, and it is difficult to achieve smooth transportation of the pump; however, the prior art attempts to add a dispersing agent to the slurry. To increase the concentration and dispersibility of biomass in the slurry, but the addition of dispersant often affects the quality of the produced bio-oil.
  • the biomass conversion rate is low in the above technology (the conversion rate is only about 90%).
  • the technical problem to be solved by the present invention is to overcome the defects of the prior biomass liquefaction process, that the pump conveys less biomass and the transportation is not stable, the biomass conversion rate is low, and the energy consumption is high, thereby providing a kind of health.
  • a one-pot liquefaction process for biomass comprising the following steps:
  • the biomass is straw, and the slurry is prepared by sequentially drying, initial pulverizing, compressing and secondary pulverizing the straw to obtain pretreated biomass, and then pretreating the pretreated biomass with the catalyst and vulcanizing.
  • the mixture is mixed to obtain a mixture, and the mixture is added to an oil to be ground and pulped to obtain the slurry having a straw concentration of 30 to 60% by weight.
  • the straw raw material in the invention may be cereal crop straw such as wheat, rice, corn, reed, sorghum, millet, etc., and may also be legume stalks such as soybean, adzuki bean, mung bean, broad bean, pea, etc., and may also be cotton, flax, ramie.
  • the fiber crop straw such as hemp can be a straw or a biomass material composed of a variety of straws.
  • the straw is compressed at a pressure of 0.5 to 3 MPa and a temperature of 30 to 60 °C.
  • the drying temperature of the straw is 50-70 ° C, the time is 3-5 h, the moisture content of the straw after drying is less than 2 wt%; the median particle size after initial pulverization is 100-300 ⁇ m; After the secondary pulverization, the median particle size is 30-50 ⁇ m, and the secondary pulverization has a bulk density of 400-500 kg/m 3 .
  • the viscosity of the slurry is 500-1400 mPa. s (50 ° C).
  • the straw is contained in an amount of 55 to 60% by weight.
  • the oil is one or more of waste animal and vegetable oil, waste mineral oil, mineral oil or distillate oil.
  • waste animal and vegetable oil is one or more of waste oil, hydrophobic oil or rancid oil;
  • the waste mineral oil is one or two of waste lubricating oil or waste lubricating oil;
  • the mineral oil is one or more of heavy oil, residual oil, eucalyptus oil or washing oil.
  • the grinding and pulping is agitating pulping, dispersing pulping, emulsification 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 carbon loaded with an active component selected from the group VIB of the Periodic Table of the Elements.
  • amorphous iron oxyhydroxide amorphous alumina loaded with an active component or biomass carbon loaded with an active component selected from the group VIB of the Periodic Table of the Elements.
  • the active component is selected from one or more of the oxides of Mo, W, Fe, Co, Ni, Mn or Pd.
  • the catalyst is used in an amount of 1 to 10% by weight, preferably 1 to 4% by weight based on the mass of the pretreated biomass; the catalyst has a particle diameter of 5 to 500 ⁇ m; and the amount of the vulcanizing agent is the pretreated biomass 0.1-0.4 wt% of mass.
  • the specific method for 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 raw material;
  • the reaction raw material is heated to 380-480 ° C and then sent to a slurry bed reactor to undergo hydrolysis, cracking and hydrogenation reaction, while simultaneously injecting cold hydrogen into the slurry bed reactor to control the slurry bed.
  • the total gas velocity in the reactor is 0.02 to 0.2 m/s, preferably 0.05 to 0.08 m/s;
  • the pressure of the high-pressure hydrogen gas is 13 to 25 MPa, and the temperature of the cold hydrogen gas is 60 to 135 °C.
  • the high-pressure hydrogen gas is injected into the slurry twice, specifically: the high-pressure hydrogen gas is injected into the slurry for the first time until the volume ratio of the high-pressure hydrogen gas to the slurry is 50-200: Then, the slurry is heated to 200 to 350 ° C, and the high pressure hydrogen gas is injected into the slurry a second time.
  • the cold hydrogen is injected through three to five injection ports arranged in the height direction on the side wall of the slurry bed reactor.
  • the amount of the catalyst in the slurry bed reactor is controlled in the slurry bed reactor in the liquid phase mass of 5 to 30 wt%;
  • the reaction time is 30 to 120 min.
  • the biomass carbon carrier is prepared
  • the active component is one or more selected from the group consisting of oxides of Mo, W, Fe, Co, Ni, Mn or Pd, the active component occupies the biomass carbon carrier based on the mass of the metal element 1% to 5% of the mass.
  • the mixing and grinding step of the active component and the biomass carbon carrier is: vibrating and/or planar grinding and/or ball milling of the active component and the biomass carbon carrier to obtain a particle size of 5 to 500 ⁇ m.
  • the biomass charcoal loaded with the active component is: vibrating and/or planar grinding and/or ball milling of the active component and the biomass carbon carrier to obtain a particle size of 5 to 500 ⁇ m.
  • the amount of the substance of H + in the acidified acidic medium is 0.5 mol / L ⁇ 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° C., the acidification time is 1 h to 10 h; the amount of the OH ⁇ substance in the alkalized alkaline medium is 0.5 mol/L to 5 mol/L; the biomass carbon and the alkaline medium volume
  • the ratio is 1:5 to 1:15, the alkalization temperature is 30 ° C to 80 ° C, and the alkalization time is 1 h to 10 h.
  • the vulcanizing agent in the present invention may be sulfur, carbon disulfide or dimethyl disulfide.
  • a one-pot liquefaction process for biomass comprising the following steps:
  • a slurry containing a catalyst, a vulcanizing agent and biomass is prepared, a hydrogen gas is introduced into the slurry to react, and a reaction pressure of 13 to 25 MPa and a reaction temperature of 300 to 500 ° C are controlled to finally obtain a bio-oil.
  • the catalyst comprises amorphous alumina loaded with a first active component or biomass carbon loaded with a first active component selected from the group consisting of metals of Group VIB, VIIB or VIII of the Periodic Table of the Elements One or more of the oxides.
  • the catalyst further comprises amorphous iron oxyhydroxide, and/or biomass carbon loaded with a second active component selected from the group consisting of oxides of Mo, W, Fe, Co, Ni or Pd.
  • amorphous iron oxyhydroxide and/or biomass carbon loaded with a second active component selected from the group consisting of oxides of Mo, W, Fe, Co, Ni or Pd.
  • the above catalysts may be used singly or in combination, and when used in combination, the mass ratio of the iron oxyhydroxide to the biomass carbon loaded with the second active component is 0.5 to 5.
  • the vulcanizing agent in the present invention may specifically be sulfur or dimethyl sulfide, but is not limited thereto, and any compound which can convert an active component in the catalyst from an oxide to a corresponding sulfide can be used.
  • the vulcanizing agent of the present invention is used in an amount of 4 to 10% by weight based on the mass of the catalyst.
  • the biomass is contained in an amount of 10 to 50% by weight, preferably 30 to 40% by weight.
  • a hydrolyzed hydrogenation process of biomass wherein the catalyst is used in an amount of from 1 to 10% by weight, preferably from 1 to 4% by weight based on the mass of the biomass; and the catalyst has a particle size of from 5 ⁇ m to 500 ⁇ m.
  • the preparation method of the slurry is:
  • the catalyst and the vulcanizing agent are separately added to liquid biomass to form the slurry, the liquid biomass being selected from one or more of vegetable oil, animal oil, waste oil or animal waste; or
  • the solid biomass is dried, pulverized and ash-removed, mixed with the catalyst and the vulcanizing agent to obtain a mixture, and the mixture is added to the oil to form the slurry;
  • the oil is vegetable oil, animal oil, coal One or more of tar, petroleum or bio-oil produced by the process;
  • the solid biomass raw material in the invention may be straw of crops such as wheat, rice, corn, cotton, etc., or may be economic crops such as reed, bamboo yellow grass, trees, leaves, fruits and vegetables, or algae, industrial. Wood, paper waste, etc.; it can be a biomass or a biomass material composed of a variety of biomass.
  • the dried solid biomass has a water content of 3 to 15% by weight, preferably 5 to 10% by weight;
  • the pulverized solid biomass has a particle size of from 1 to 5000 ⁇ m, preferably from 20 to 1500 ⁇ m.
  • the reaction raw material is heated to 320-450 ° C and then sent to a slurry bed reactor for hydrolysis, cracking and hydrogenation reaction, while cold hydrogen is injected into the slurry bed reactor to control the slurry bed.
  • the total gas velocity in the reactor is 0.02 to 0.2 m/s, preferably 0.05 to 0.08 m/s;
  • the pressure of the high pressure hydrogen gas is 13 to 27 MPa, and the temperature of the cold hydrogen gas is 60 to 135 °C.
  • the high pressure hydrogen gas is injected into the slurry twice, specifically:
  • the first high pressure hydrogen gas is injected into the slurry until the volume ratio of the high pressure hydrogen gas to the slurry is 50-200:1, and then the slurry is heated to 200-350 ° C, and then The high pressure hydrogen is injected a second time in the slurry.
  • the cold hydrogen is injected through three to five injection ports arranged in the height direction on the side wall of the slurry bed reactor.
  • the amount of the catalyst in the slurry bed reactor is controlled in the slurry bed reactor in the liquid phase mass of 5 to 30 wt%;
  • the reaction time is from 15 to 90 min.
  • the biomass carbon carrier is prepared
  • the second active component is one of oxides loaded with Mo, W, Fe, Co, Ni or Pd, and the second active component accounts for the second biomass carbon based on the mass of the metal element
  • the carrier is 1% to 5% by mass.
  • the step of mixing the second active component and the second biomass carbon carrier is performed by vibrating and/or planar grinding and/or planar grinding and/or polishing the second active component and the second biomass carbon carrier.
  • Ball milling yielded a biomass charcoal loaded with a second active component having a particle size of from 5 ⁇ m to 500 ⁇ m.
  • the concentration of the substance of H + in the acidified acidic medium is 0.5 mol/L to 5 mol/L; the volume ratio of the dry distillation biomass carbon to the acidic medium is 1:5 to 1:15, and the acidification temperature is 30 to 80 ° C, the acidification time is 1 h to 10 h; the amount of the substance of the OH - in the alkalized alkaline medium is 0.5 mol / L ⁇ 5 mol / L; the dry distillation biomass carbon and the alkaline
  • the volume ratio of the medium is 1:5 to 1:15, the alkalization temperature is 30 ° C to 80 ° C, and the alkalization time is 1 h to 10 h.
  • a one-pot liquefaction process for biomass comprising the following steps:
  • the biomass is a vegetable oil residue
  • the slurry is prepared by sequentially drying, initial pulverizing, compressing and secondary pulverizing the vegetable oil residue to obtain a pretreated biomass, and then the pretreated biomass and the catalyst.
  • the mixture is mixed with a vulcanizing agent, and the mixture is added to an oil to be ground and pulped to obtain the slurry having a vegetable oil residue concentration of 50 to 65 wt%.
  • the vegetable oil residue in the present invention may be one or more of palm oil residue, soybean oil residue, peanut oil residue, saponin oil residue, linseed oil residue, castor oil residue, rapeseed oil residue or olive oil residue;
  • the vegetable oil residue is compressed at a pressure of 3-5 MPa and a temperature of 40-60 °C.
  • the drying temperature of the vegetable oil residue is 80-110 ° C, the time is 2-6 h, the moisture content of the vegetable oil residue after drying is less than 2 wt%; the median particle size after initial pulverization is 100- 300 ⁇ m; after secondary pulverization, the median particle size is 30-50 ⁇ m, and after secondary pulverization, the bulk density is 1500-1600 kg/m 3 .
  • the viscosity of the slurry is 300-700 mPa. s (50 ° C).
  • the grinding and pulping is agitating pulping, dispersing pulping, emulsification pulping, shearing pulping or homogenizing pulping.
  • the vulcanizing agent in the present invention may be sulfur, carbon disulfide or dimethyl disulfide.
  • the oil in the preparation step of the slurry, the type of the catalyst, the amount of the catalyst, the specific method of introducing hydrogen into the slurry, the injection of cold hydrogen, and the inventory of the catalyst in the slurry bed reactor The reaction time, the preparation method of the biomass carbon loaded with the active component, and the like are the same as the first technical solution provided by the present invention.
  • a one-pot liquefaction process for biomass comprising the following steps:
  • the biomass is straw, and the slurry is prepared by sequentially drying, initial pulverizing, compressing and secondary pulverizing the straw to obtain pretreated biomass, and then the pretreated biomass and the catalyst and the
  • the vulcanizing agent is mixed to obtain a mixture, and the mixture is added to water to grind and slurry to obtain the slurry having a straw concentration of 35-50% by weight;
  • the straw is compressed at a pressure of 2 to 5 MPa and a temperature of 30 to 60 °C.
  • the drying temperature of the straw is 70-110 ° C, the time is 3-5 h, the moisture content of the straw after drying is less than 2 wt%;
  • the median particle size after the initial pulverization is 100-300 ⁇ m
  • the median particle size after secondary pulverization is 30-50 ⁇ m, and the bulk density after secondary pulverization is 400-800 kg/m 3 .
  • the viscosity of the slurry is 400-800 mPa. s (50 ° C).
  • the grinding and pulping is agitating pulping, dispersing pulping, emulsification pulping, shearing pulping or homogenizing pulping.
  • the reaction raw material is heated to 300-400 ° C and sent to a slurry bed reactor to undergo hydrolysis, cracking and hydrogenation reaction, while simultaneously injecting cold hydrogen into the slurry bed reactor to control the slurry bed.
  • the total gas velocity in the reactor is 0.02 to 0.2 m/s, preferably 0.05 to 0.08 m/s;
  • the pressure of the high-pressure hydrogen gas is 15 to 22 MPa, and the temperature of the cold hydrogen gas is 60 to 135 °C.
  • the high pressure hydrogen gas is injected into the slurry twice, specifically:
  • the first high pressure hydrogen gas is injected into the slurry until the volume ratio of the high pressure hydrogen gas to the slurry is 50-200:1, and then the slurry is heated to 200-280 ° C, and then The high pressure hydrogen is injected a second time in the slurry.
  • the cold hydrogen is injected through three to five injection ports arranged in the height direction on the side wall of the slurry bed reactor.
  • the amount of the catalyst in the slurry bed reactor is controlled to be 5 to 30% by weight of the liquid phase mass in the slurry bed reactor; the reaction time is 30 to 60 minutes.
  • the vulcanizing agent in the present invention may be sulfur, carbon disulfide or dimethyl disulfide.
  • the kind of the catalyst, the amount of the catalyst, the preparation method of the biomass carbon loaded with the active component, and the like are the same as those of the first technical solution provided by the present invention.
  • a one-pot liquefaction process for biomass comprising the following steps:
  • the biomass is a vegetable oil residue
  • the slurry is prepared by sequentially drying, initial pulverizing, compressing and secondary pulverizing the vegetable oil residue to obtain a pretreated biomass, and then the pretreated biomass and the catalyst. Mixing with the vulcanizing agent to obtain a mixture, and adding the mixture to water to grind and slurry to obtain the slurry having a vegetable oil residue concentration of 40-50% by weight;
  • the vegetable oil residue is compressed at a pressure of 0.5 to 3 MPa and a temperature of 30 to 50 °C.
  • the drying temperature of the vegetable oil residue is 80-110 ° C, the time is 2-6 h, the water content of the vegetable oil residue after drying is less than 2 wt%; the median particle size after the initial crushing is 50 -300 ⁇ m; the median particle size after secondary pulverization is 30-50 ⁇ m, and the bulk density after secondary pulverization is 1400-1600 kg/m 3 .
  • the viscosity of the slurry is 300-650 mPa. s (50 ° C).
  • the grinding and pulping is agitating pulping, dispersing pulping, emulsification pulping, shearing pulping or homogenizing pulping.
  • the reaction raw material is heated to 340-420 ° C and then sent to a slurry bed reactor to undergo hydrolysis, cracking and hydrogenation reaction, while simultaneously injecting cold hydrogen into the slurry bed reactor to control the slurry bed.
  • the total gas velocity in the reactor is 0.02 to 0.2 m/s, preferably 0.05 to 0.08 m/s;
  • the pressure of the high-pressure hydrogen gas is 15 to 22 MPa, and the temperature of the cold hydrogen gas is 60 to 135 °C.
  • the high pressure hydrogen gas is injected into the slurry twice, specifically:
  • the first high pressure hydrogen gas is injected into the slurry until the volume ratio of the high pressure hydrogen gas to the slurry is 50-200:1, and then the slurry is heated to 200-280 ° C, and then The high pressure hydrogen is injected a second time in the slurry.
  • the amount of the catalyst in the slurry bed reactor is controlled to be 5 to 30% by weight of the liquid phase mass in the slurry bed reactor; the reaction time is 30 to 60 minutes.
  • the vulcanizing agent in the present invention may be sulfur, carbon disulfide or dimethyl disulfide.
  • the kind of the catalyst, the amount of the catalyst, the injection of cold hydrogen, the preparation method of the biomass carbon loaded with the active component, and the like are the same as the first technical solution provided by the present invention.
  • a one-pot liquefaction process for coal and biomass comprising the following steps:
  • the pulverized biomass is compression-molded, the compression pressure is 2 to 5 MPa, and the compression temperature is 30 to 60 ° C;
  • the biomass after compression molding is pulverized again, and pulverized to a median diameter of 30 to 50 ⁇ m to obtain a biomass powder;
  • the compression pressure is 5-15 MPa
  • coal after compression molding is pulverized again, and pulverized to a median diameter of 30 to 50 ⁇ m to obtain coal powder;
  • Liquefaction reaction introducing hydrogen into the biomass coal slurry to react, and controlling the reaction pressure to 15-25 MPa, the reaction temperature is 380-460 ° C, and finally preparing a bio-oil;
  • the biomass powder and the coal powder are first subjected to ash removal and premixed with the catalyst and the vulcanizing agent, and then the obtained pre-mixing
  • the mixture is mixed with the oil, or the biomass powder, the pulverized coal, the catalyst, and the oil are directly mixed.
  • the concentration of the biomass is 20 to 30% by weight, and the concentration of the coal powder is 30 to 45% by weight.
  • the moisture content is controlled by drying and dehydrating, the drying and dehydrating temperature is 50-70 ° C, and the drying and dehydrating time is 3 to 5 h.
  • the compression molding is press forming, tablet forming or bead forming.
  • the compression molding is press forming, tablet forming or bead forming.
  • the bulk density of the biomass powder is controlled to be 300 to 500 kg/m 3 , and the bulk density of the coal powder is controlled to be 1000 to 1200 kg/m 3 .
  • the pulverization is a hammer mill pulverization, a ball mill pulverization, a rod mill pulverization, an ultrafine pulverization or a jet pulverization.
  • the grinding and pulping is agitating pulping, dispersing pulping, emulsification pulping, shearing pulping, homogenizing pulping or colloidal grinding pulping.
  • the grinding and pulping time is 2 to 8 minutes.
  • the biomass coal slurry has a viscosity of 550 to 1000 mPa ⁇ s (50 ° C).
  • the coal is low rank coal; the oil is made of hydrophobic oil, waste oil, rancid oil, waste lubricating oil, waste engine oil, heavy oil, residual oil, washing oil, eucalyptus oil, coal tar, petroleum, or the process.
  • the oil is made of hydrophobic oil, waste oil, rancid oil, waste lubricating oil, waste engine oil, heavy oil, residual oil, washing oil, eucalyptus oil, coal tar, petroleum, or the process.
  • One or more of the bio-oils is made of hydrophobic oil, waste oil, rancid oil, waste lubricating oil, waste engine oil, heavy oil, residual oil, washing oil, eucalyptus oil, coal tar, petroleum, or the process.
  • One or more of the bio-oils are made of hydrophobic oil, waste oil, rancid oil, waste lubricating oil, waste engine oil, heavy oil, residual oil, washing oil, eucalyptus oil, coal tar, petroleum, or the process.
  • the catalyst is used in an amount of 1 to 10% by weight, preferably 1 to 4% by weight based on the total amount of the biomass and coal; and the catalyst has a particle diameter of 5 to 500 ⁇ m.
  • the reaction raw material is heated to 320-450 ° C and then sent to a slurry bed reactor for liquefaction, cracking and hydrogenation reaction, while cold hydrogen is injected into the slurry bed reactor to control the slurry bed.
  • the total gas velocity in the reactor is 0.02 to 0.2 m/s, preferably 0.05 to 0.08 m/s;
  • the pressure of the high-pressure hydrogen gas is 13-27 MPa, and the temperature of the cold hydrogen is 60-135 °C.
  • the high pressure hydrogen gas is injected into the biomass coal slurry twice, specifically:
  • the high pressure hydrogen gas is injected into the biomass coal slurry for the first time until the volume ratio of the high pressure hydrogen gas to the biomass coal slurry is 50 to 200:1, and then the biomass coal slurry is The temperature is raised to 200 to 350 ° C, and then the high pressure hydrogen gas is injected into the biomass coal slurry a second time.
  • the cold hydrogen is injected through three to five injection ports arranged in the height direction on the side wall of the slurry bed reactor.
  • the amount of the catalyst in the slurry bed reactor is controlled in the slurry bed reactor in the liquid phase mass of 5 to 30 wt%;
  • the reaction time is 30 to 90 min.
  • the biomass used in the present invention may be solid, such as straw of crops such as wheat, rice, corn, cotton, etc., or may be economic crops such as reed, bamboo yellow grass, trees, leaves, fruits and vegetables, or algae.
  • Industrial wood, paper waste, etc. can also be liquid, such as liquid manure; can be a biomass or a mixture of biomass to form a biomass feedstock.
  • the catalyst type, composition, vulcanizing agent type, and preparation method of the biomass carbon loaded with the second active component are the same as the second technical solution.
  • a one-pot liquefaction process for coal and biomass comprising the following steps,
  • the pulverized biomass is compression-molded, the compression pressure is 2 to 5 MPa, and the compression temperature is 30 to 60 ° C;
  • the biomass after compression molding is pulverized again, and pulverized to a median diameter of 30 to 50 ⁇ m to obtain a biomass powder;
  • the compression pressure is 5-15 MPa
  • the coal after the contraction molding is pulverized again, and pulverized to a median diameter of 30 to 100 ⁇ m to obtain coal powder;
  • the biomass powder and the coal powder are first subjected to ash removal and premixed with the catalyst and the vulcanizing agent, and then the obtained pre-mixed
  • the mixture is mixed with the water, or alternatively, the biomass powder, the pulverized coal, the catalyst, and the water are directly mixed.
  • the concentration of the biomass is 15 to 30% by weight, and the concentration of the coal powder is 35 to 50% by weight.
  • the moisture content is controlled by drying and dehydrating, the drying and dehydrating temperature is 50-70 ° C, and the drying and dehydrating time is 3 to 5 h.
  • the bulk density of the biomass powder is controlled to be 300 to 500 kg/m 3 , and the bulk density of the coal powder is controlled to be 1200 to 1300 kg/m 3 .
  • the grinding and pulping time is 2 to 8 minutes.
  • the coal is low rank coal.
  • the catalyst is used in an amount of 1 to 10% by weight, preferably 1 to 4% by weight based on the total amount of the biomass and coal; and the catalyst has a particle diameter of 5 to 500 ⁇ m.
  • the specific method of introducing hydrogen, the stock of the catalyst in the slurry bed reactor, the reaction time, the type and composition of the catalyst, the type of the vulcanizing agent, the type of the biomass and the second active component supported thereon The preparation method of the biomass carbon is the same as the sixth technical scheme.
  • the first-pot biomass liquefaction process of the first biomass provided by the present invention wherein the slurry is prepared by sequentially drying, initial pulverizing, compressing and secondary pulverizing the straw, and then mixing with the catalyst and the vulcanizing agent to obtain a mixture.
  • the above mixture is added to the oil to be ground and pulped to obtain a slurry having a straw concentration of 30 to 60% by weight.
  • the first process of the present invention is to first compress and then smash the straw, and compress the biomass.
  • the loose straw is subjected to the stage of re-displacement and mechanical deformation such as collapse and closure, so that the volume of the straw is greatly reduced, thereby reducing the porosity of the straw, increasing its density and specific gravity, and facilitating dispersion in the oil.
  • the content of the oil in the product can be increased, and the concentration of the reaction material is increased.
  • the content of the straw in the slurry can be as high as 30 to 60% by weight, which is much higher than 5 to 16% by weight in the prior art.
  • the increase of biomass concentration in the slurry will inevitably increase the amount of biomass transported by the pump per unit time, thereby improving the efficiency and lowering of the entire biomass liquefaction process.
  • the increase in the specific gravity of the straw is also conducive to the suspension and dispersion of biomass in the slurry, thereby reducing the viscosity of the biomass slurry and achieving a smooth slurry in the slurry after biomass slurrying.
  • the flow avoids the blockage of the pipeline, realizes the smooth operation and transportation of the pump, and also enables the high-viscosity waste oil which cannot be used as a biomass liquefaction solvent in the prior art, such as waste engine oil, waste oil, rancid oil, etc. use.
  • the one-pot liquefaction process of the second biomass provided by the present invention firstly prepares a slurry containing a catalyst, a vulcanizing agent and a biomass, and then introduces hydrogen into the slurry to react, and controls the reaction pressure to 13 ⁇ 25 MPa, the reaction temperature is 300-500 ° C, and finally the bio-oil is prepared; the process of the invention causes the high-temperature and high-temperature hydrolysis of the biomass in the presence of an appropriate amount of water (ie, the water contained in the biomass itself), and Under the action of the amorphous alumina loaded with the metal oxide of Group VIB, VIIB or VIII as a catalyst, the hydrolyzed product further undergoes cracking and hydrogenation reaction, thereby realizing the conversion from biomass to bio-oil.
  • the biomass conversion rate is as high as 90 to 100%
  • the bio-oil yield is 60 to 86% or more
  • the coke yield is less than 0.1%.
  • the first-combustion liquefaction process of the third biomass provided by the present invention is characterized in that the slurry is prepared by sequentially drying, initial pulverizing, compressing and secondary pulverizing the vegetable oil residue, and then mixing with the catalyst and the vulcanizing agent to obtain a mixture.
  • the above mixture is added to the oil to be ground and pulped to obtain a slurry having a vegetable oil residue concentration of 50-65 wt%, and the first process of the invention is to first compress the vegetable oil residue and then perform secondary crushing, and compress the biomass.
  • the plant oil residue of the invention can be as high as 50-65 wt% in the slurry, and at the same time due to the increase of the concentration of vegetable oil residue in the slurry It will also inevitably increase the amount of biomass transported by the pump per unit time, thereby increasing the efficiency and reducing the efficiency of the entire biomass liquefaction process.
  • the increase in the specific gravity of vegetable oil residue is also conducive to the suspension and dispersion of biomass in the slurry, thereby reducing the viscosity of the biomass slurry and achieving a smooth slurry in the slurry after biomass slurrying.
  • the flow avoids the blockage of the pipeline, realizes the smooth operation and transportation of the pump, and also enables the high-viscosity waste oil which cannot be used as a biomass liquefaction solvent in the prior art, such as waste engine oil, waste oil, rancid oil, etc. use.
  • the invention prepares a slurry containing a catalyst, a vulcanizing agent and a biomass, and then introduces hydrogen into the slurry to react, and controls the reaction pressure to be 15-25 MPa and the reaction temperature is 380-480 ° C.
  • the process of the present invention is Under the action of hydrogen and catalyst, the biomass is cracked and hydrogenated, the conversion from biomass to bio-oil is realized, and the conversion rate of biomass is improved. In the process of the invention, the biomass conversion rate can be as high as 95-99%.
  • the slurry is prepared by sequentially drying, initial pulverizing, compressing and secondary pulverizing the straw, and then mixing with the catalyst and the vulcanizing agent to obtain a mixture.
  • the first process of the invention is to first compress and then smash the straw, and compress the biomass to make the loose straw successively After undergoing re-displacement and mechanical deformation, such as collapse and closure, the volume of straw is greatly reduced, thereby reducing the porosity of the straw, increasing its density and specific gravity, making it beneficial to disperse in water and improve its
  • the content in the water increases the concentration of the reaction material, and at the same time, the increase of the biomass concentration in the slurry will inevitably increase the amount of biomass transported by the pump per unit time, thereby improving the efficiency of the entire biomass liquefaction process and reducing the industry.
  • the increase in the specific gravity of the straw is also conducive to the suspension and dispersion of biomass in the slurry, thereby Reducing the viscosity of the biomass slurry to achieve a biomass slurry was slurried smoothly flow in the pipe, to avoid clogging the pipeline, to achieve stable operation of the pump with the delivery.
  • the invention prepares a slurry containing a catalyst, a vulcanizing agent and a biomass, and then introduces hydrogen into the slurry to react, and controls the reaction pressure to be 15-20 MPa and the reaction temperature is 300-400 ° C.
  • the process of the present invention is Under the action of hydrogen and catalyst, the biomass is cracked and hydrogenated, the conversion from biomass to bio-oil is realized, and the yield of bio-oil is improved.
  • the biomass conversion rate can be as high as 95-99%, the bio-oil yield is 60-80%, and the amount of residue in the bio-oil is below 0.1 wt%.
  • the one-pot liquefaction process of the fifth biomass provided by the present invention the slurry is prepared by sequentially drying, initial pulverizing, compressing and secondary pulverizing the vegetable oil residue, and then mixing with the catalyst and the vulcanizing agent to obtain a mixture.
  • the mixture is added to water to grind and slurry to obtain a slurry having a straw concentration of 40-50% by weight.
  • the first process of the present invention is to first compress and then smash the straw, and compress the biomass to make loose straw.
  • the invention prepares a slurry containing a catalyst, a vulcanizing agent and a biomass, and then introduces hydrogen into the slurry to react, and controls the reaction pressure to be 15-20 MPa and the reaction temperature is 340-420 ° C.
  • the process of the invention is Under the action of hydrogen and catalyst, the biomass is cracked and hydrogenated, the conversion from biomass to bio-oil is realized, and the yield of bio-oil is improved.
  • the biomass conversion rate can be as high as 95-99%, the bio-oil yield is 70-86%, and the amount of residue in the bio-oil is below 0.1 wt%.
  • the liquefaction of coal and biomass with water as a hydrogen supply solvent is realized for the first time.
  • the invention successfully prepares biomass and coal by dehydrating, pulverizing, compressing, re-pulverizing, primary slurrying, grinding and pulping of biomass and coal, and by optimizing the pulverized particle size and compression conditions.
  • a biomass coal water slurry having a content of 55 to 65 wt% and a viscosity of only 450 to 1100 mPa ⁇ s (50 ° C).
  • the first-pot biomass liquefaction process of the first biomass provided by the present invention can significantly enhance the rheology of the straw and reduce the biomass slurry by controlling the compression temperature at 30-60 ° C, and then compressing the straw at this temperature.
  • Viscosity, tested, the viscosity of the slurry formed by straw and oil in the process of the invention is 500-1400 mPa. s (50 ° C), thereby achieving a smooth flow of the slurry after biomass slurrying in the pipeline, avoiding blockage of the pipeline, and achieving smooth operation and transportation of the pump.
  • the one-pot liquefaction process of the third biomass provided by the invention can significantly enhance the rheology of the vegetable oil residue and reduce the biomass slurry by controlling the compression temperature at 40-60 ° C, and then compressing the vegetable oil residue at this temperature.
  • Viscosity, tested, the viscosity of the slurry formed by vegetable oil residue and oil in the process of the invention is 300-700 mPa. s (50 ° C), thereby achieving the smooth flow of the slurry after the slurry of the vegetable oil residue in the pipeline, avoiding the blockage of the pipeline, and achieving smooth operation and transportation of the pump.
  • the one-pot liquefaction process of the fourth biomass provided by the invention can significantly enhance the rheology of the straw and reduce the viscosity of the biomass slurry by controlling the compression temperature at 30-60 ° C, and then compressing the straw at this temperature.
  • the viscosity of the slurry formed by straw and oil in the process of the invention is 400-800 mPa. s (50 ° C), thereby achieving a smooth flow of the slurry after biomass slurrying in the pipeline, avoiding blockage of the pipeline, and achieving smooth operation and transportation of the pump.
  • the one-pot liquefaction process of the fifth biomass provided by the invention can significantly enhance the rheology of the vegetable oil residue and reduce the biomass slurry by controlling the compression temperature at 30-50 ° C, and then compressing the vegetable oil residue at this temperature.
  • Viscosity, tested, the viscosity of the slurry formed by vegetable oil residue and oil in the process of the invention is 300-650 mPa. s (50 ° C), thereby achieving a smooth flow of the slurry after biomass slurrying in the pipeline, avoiding blockage of the pipeline, and achieving smooth operation and transportation of the pump.
  • the sixth technical solution provided by the invention creatively realizes the mixing and liquefaction of coal, biomass and oil for the first time, and provides a one-pot liquefaction process of coal and biomass.
  • the invention successfully prepares biomass and coal by dehydrating, pulverizing, compressing, re-pulverizing, primary slurrying, grinding and pulping of biomass and coal, and by optimizing the pulverized particle size and compression conditions.
  • a biomass coal slurry having a content of 60 to 70% by weight and a viscosity of only 550 to 1000 mPa ⁇ s (50 ° C).
  • the liquefaction of coal and biomass with water as a hydrogen supply solvent is realized for the first time.
  • the invention successfully prepares biomass and coal by dehydrating, pulverizing, compressing, re-pulverizing, primary slurrying, grinding and pulping of biomass and coal, and by optimizing the pulverized particle size and compression conditions.
  • a biomass coal water slurry having a content of 55 to 65 wt% and a viscosity of only 450 to 1100 mPa ⁇ s (50 ° C).
  • the one-pot liquefaction process of coal and biomass can compress and close the pore structure inside the coal and biomass material, and plastic rheology and plastic deformation occur, thereby greatly improving the coal and biomass raw materials.
  • the density makes it well dispersed in the solvent oil; at the same time, the collapse and closure of the pore structure avoids the adsorption of solvent oil by coal and biomass, so that the solvent oil can fully exert its function as a dispersing agent; we find that compression Temperature has a great influence on the degree of plastic rheology and plastic deformation. The higher the temperature, the higher the density. However, if the temperature is too high, the material will be decomposed or cause other problems. Therefore, 30 ⁇ 60 °C is used for compression. temperature.
  • the re-pulverization operation after compression increases the contactable area of the raw material, so that the raw material can be in better contact with the catalyst and the solvent oil, and the hydrogen transfer can be enhanced, and the raw material is in contact with the hydrogen and the catalyst due to being in the pore structure. Thus the situation of the reaction.
  • the "crushing + compression + re-crushing" provided by the invention can be applied to all coal materials and biomass materials having pore structure inside, especially low-rank coal materials such as lignite, and porous and porous biomass materials such as straw and rice husk.
  • the prepared high-concentration biomass coal slurry has good slurryability and high fluidity, and can be directly transported by the pump, which can effectively improve the running stability of the conveying system, the utilization efficiency of the liquefaction device and the liquefaction efficiency, and satisfy the subsequent treatment process.
  • the feed requirement also realizes the clean and efficient utilization of inferior coal and biomass; the close proximity of coal and biomass makes the hydrogen produced by biomass pyrolysis a part of hydrogen source for pyrolysis of coal, reducing the pair Hydrogen consumption.
  • the common liquefaction process provided by the present invention enables high-viscosity waste oils, such as waste engine oil, waste oil, and rancid oil, which cannot be used as coal and biomass liquefaction solvents in the prior art, can also be utilized.
  • the reaction is carried out by introducing hydrogen into the biomass coal slurry, and the reaction pressure is 13-25 MPa, and the reaction temperature is 300-500 ° C, thereby finally producing bio-oil.
  • the process of the present invention causes the coal and biomass to be liquefied under high pressure and high temperature, and the liquefied product further occurs under the action of hydrogen and amorphous alumina supported with a metal oxide of Group VIB, VIIB or VIII as a catalyst. Cracking and hydrogenation reactions to achieve the conversion of coal and biomass to bio-oil.
  • the conversion ratio of coal to biomass can reach 90 to 99%, the yield of bio-oil can reach 60-80%, and the amount of residue is not higher than 2.5 wt%.
  • the reaction is carried out by introducing hydrogen into the biomass coal water slurry, and the reaction pressure is 15-25 MPa and the reaction temperature is 300-460 ° C, thereby finally preparing the bio-oil.
  • the process of the present invention causes high pressure and high temperature hydrolysis of coal and biomass in the presence of an appropriate amount of water (i.e., biomass and water contained in the coal itself), and is oxidized in the presence of hydrogen and with a Group VIB, VIIB or VIII metal.
  • the hydrolyzed product Under the action of the amorphous alumina of the material, the hydrolyzed product further undergoes cracking and hydrogenation reaction, thereby realizing the conversion of coal and biomass to bio-oil.
  • the conversion ratio of coal to biomass is as high as 90 to 95%
  • the yield of bio-oil is above 70 to 85%
  • the amount of coke is less than 5%.
  • the invention further cooperates with the screening process of the solid material, can ensure the uniform particle size of the solid particles used for preparing the biomass oil coal slurry, and makes the obtained biomass coal slurry have better stability, and is difficult to settle during transportation, avoiding Blockage of the transport pipeline and damage to the liquefaction equipment.
  • the preferred catalyst of the present invention is an amorphous alumina loaded with a metal oxide of Group VIB, VIIB or VIII or a combined catalyst of biomass carbon and amorphous iron oxide, which has the advantages that the noble metal has good hydrogenation performance after vulcanization. It can avoid coke, biochar or amorphous alumina has acidity and has cracking function; amorphous iron oxide has basicity, can promote liquefaction reaction, and iron has the function of hydrogenation catalysis after vulcanization, reducing precious metal Consumption.
  • the one-pot liquefaction process of coal and biomass provided by the invention is prepared by drying, compressing, pulverizing and removing ash of coal and biomass raw materials, and then mixing with catalyst to better utilize coal and biomass.
  • the surface energy of the powder allows the catalyst to adhere to the surface of the solid powder, so that the catalyst can provide hydrogen transfer to the coal and biomass liquefaction products in time, thereby ensuring that coke polycondensation does not occur during the entire process, thereby reducing the amount of residue. .
  • the catalyst is amorphous iron oxyhydroxide, amorphous alumina loaded with active component or biomass carbon loaded with active component.
  • a single catalyst or a combination catalyst the active component of which is selected from one or more of the oxides of the metal of Group VIB, VIIB or VIII of the Periodic Table of the Elements, the amorphous iron oxyhydroxide having a basicity capable of promoting the hydrolysis of biomass;
  • the material carbon and the amorphous alumina are acidic in nature and have a cracking function, and after being loaded by the active component, the cracking function of the catalyst is enhanced, thereby avoiding the generation of coke during the liquefaction of the biomass.
  • the one-pot liquefaction process of biomass or coal and biomass provided by the present invention by using a slurry bed reactor, the reaction raw materials are first sent from the bottom of the reactor to the slurry bed reactor to react, and at the same time Injecting cold hydrogen into the reactor, so that the difference in specific gravity caused by the gas, liquid and solid materials and the yield of the light oil after the reaction can be changed in the reactor to realize the difference of the flow velocity of each phase. Control, so that the biomass feedstock undergoes hydrolysis, cracking and hydrogenation reaction from bottom to top in the reactor. In this process, even if the biomass and catalyst solid particles rise with gas and light oil, the upper part is Under the action of cold hydrogen, it returns to the bottom and participates in the reaction again.
  • the hydrogen content in the slurry entering the reactor and the cold hydrogen injection amount are appropriately adjusted, thereby realizing unconverted biomass in the reactor.
  • the internal circulation and the balanced discharge of the catalyst ensure the sufficient progress of the hydrolysis, cracking, hydrogenation and the like, thereby contributing to the improvement of the biomass conversion rate. And oil phase yield.
  • the one-pot liquefaction process of biomass or coal and biomass provided by the present invention, by injecting high-pressure hydrogen into the slurry twice, that is, injecting high-pressure hydrogen gas before and after the slurry is heated, the previous injection of high-pressure hydrogen gas
  • the disturbance of the slurry in the heat exchanger can be increased to avoid deposition of solid biomass and catalyst.
  • the one-pot liquefaction process of biomass or coal and biomass provided by the present invention preferably the catalyst is amorphous alumina or biomass carbon supported on Group VIB, VIIB or VIII metal oxide and amorphous iron oxide.
  • the combination catalyst has the advantages that the noble metal has good hydrogenation performance after vulcanization, can avoid coke formation, the biomass carbon or the amorphous alumina has acidity and has a cracking function; the amorphous iron oxide has alkali and can promote the biomass. Hydrolysis, and after the sulfur is sulfided, it also has the function of hydrogenation catalysis, reducing the consumption of precious metals.
  • the one-pot liquefaction process of biomass or coal and biomass provided by the present invention, when the biomass raw material is solid, the solid biomass needs to be pretreated, dried, pulverized and ash removed, and then mixed with the catalyst.
  • the catalyst adheres to the surface of the solid biomass powder, so that the catalyst can provide hydrogen transfer to the biomass hydrolyzate in time, thereby ensuring that coke polycondensation does not occur during the entire process. , to achieve the purpose of reducing the amount of coke.
  • a one-pot liquefaction process for biomass comprising the following steps:
  • the wheat straw and corn stalk are sent to a dryer and dried at 50 ° C for 5 h to a water content of less than 2 wt %, and then sent to an ultrafine pulverizer for initial pulverization.
  • the median diameter after the initial pulverization is 100 ⁇ m, and then the initial
  • the pulverized wheat straw and corn stalk are sent to a plodder for compression extrusion at a temperature of 30 ° C and a pressure of 3 MPa, followed by secondary pulverization treatment, and the median diameter after secondary pulverization is 30 ⁇ m.
  • the bulk density of the wheat straw and the corn stover after the second pulverization was 500 kg/m 3 , and was used.
  • the biomass carbon is acidified, and the biomass carbon carrier is prepared;
  • Mo accounts for 1% by mass of the above biomass carbon carrier in terms of Mo mass.
  • the amount of H + in the acidified acid medium was 5 mol/L
  • the volume ratio of the biomass carbon to the acidic medium was 1:5
  • the acidification temperature was 80 ° C
  • the acidification time was 1 h.
  • the pretreated biomass, the catalyst prepared above and sulfur are mixed to obtain a mixture, and the mixture is added to a mixed oil of hydrophobic oil and residual oil to be stirred and slurried to form a slurry, and the wheat straw and corn stalk in the slurry are detected.
  • the total content is 60% by weight, and the viscosity of the slurry is 500Pa.
  • the catalyst added was 1 wt% of the mass of the pretreated biomass, and the vulcanizing agent added was 0.4 wt% of the mass of the pretreated biomass.
  • Hydrogen is introduced into the biomass slurry to react, the reaction pressure is controlled to 25 MPa, and the reaction temperature is 380 ° C to prepare a bio-oil;
  • the specific method for 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 1500:1 to form a reaction raw material; and heating the above-mentioned reaction raw material to 380 ° C and then feeding it to the slurry bed reactor Hydrolysis, cracking and hydrogenation reactions occur simultaneously, and cold hydrogen is injected into the slurry bed reactor to control the total gas velocity in the slurry bed reactor to be 0.2 m/s; wherein the pressure of the high pressure hydrogen gas is 27 MPa.
  • the temperature of the high pressure cold hydrogen is 135 ° C;
  • the cold hydrogen is injected through three injection ports arranged in the height direction on the side wall of the slurry bed reactor.
  • the amount of biomass carbon loaded with MO oxide as a catalyst in the slurry bed reactor accounted for 30% by weight of the liquid phase mass in the slurry bed reactor, and the liquefaction reaction time was 30 minutes.
  • a one-pot liquefaction process for biomass comprising the following steps:
  • the palm oil residue is sent to a dryer and dried at 80 ° C for 5 h to a water content of less than 2 wt %, and then sent to an ultrafine pulverizer for preliminary pulverization.
  • the median diameter after the initial pulverization is 100 ⁇ m, and then the initial pulverization is performed.
  • the palm oil residue is sent to a plodder for compression extrusion at a temperature of 50 ° C and a pressure of 5 MPa, followed by secondary pulverization treatment, and the median diameter after secondary pulverization is 30 ⁇ m, after secondary pulverization
  • the palm oil residue has a bulk density of 1600 kg/m 3 and is ready for use.
  • the biomass carbon is acidified, and the biomass carbon carrier is prepared;
  • Mo accounts for 1% by mass of the above biomass carbon carrier in terms of Mo mass.
  • the amount of H + in the acidified acid medium was 5 mol/L
  • the volume ratio of the biomass carbon to the acidic medium was 1:5
  • the acidification temperature was 80 ° C
  • the acidification time was 1 h.
  • the pretreated biomass, the catalyst prepared above and sulfur are mixed to obtain a mixture, and the mixture is added to a mixed oil of hydrophobic oil and residual oil to be stirred and slurried to form a slurry, and the total amount of palm oil residue in the slurry is detected.
  • the content is 60% by weight, and the viscosity of the slurry is 300Pa.
  • the catalyst added was 1 wt% of the mass of the pretreated biomass, and the vulcanizing agent added was 0.4 wt% of the mass of the pretreated biomass.
  • Hydrogen is introduced into the biomass slurry to react, the reaction pressure is controlled to 25 MPa, and the reaction temperature is 380 ° C to prepare a bio-oil;
  • the specific method for 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 1500:1 to form a reaction raw material; and heating the above-mentioned reaction raw material to 380 ° C and then feeding it to the slurry bed reactor Hydrolysis, cracking and hydrogenation reactions occur simultaneously, and cold hydrogen is injected into the slurry bed reactor to control the total gas velocity in the slurry bed reactor to be 0.2 m/s; wherein the pressure of the high pressure hydrogen gas is 27 MPa.
  • the temperature of the high pressure cold hydrogen is 135 ° C;
  • the cold hydrogen is injected through three injection ports arranged in the height direction on the side wall of the slurry bed reactor.
  • the amount of biomass carbon loaded with MO oxide as a catalyst in the slurry bed reactor accounted for 30% by weight of the liquid phase mass in the slurry bed reactor, and the liquefaction reaction time was 100 min.
  • a one-pot liquefaction process for biomass comprising the following steps:
  • the cotton straw is sent to a dryer and dried at 60 ° C for 4 h to a water content of less than 2 wt%, and then sent to an ultrafine pulverizer for preliminary pulverization.
  • the median diameter after the initial pulverization is 210 ⁇ m, and then the initial pulverization
  • the cotton straw is fed into a briquetting machine and subjected to compression extrusion at a temperature of 55 ° C and a pressure of 2.1 MPa, followed by secondary pulverization, and the median diameter after secondary pulverization is 40 ⁇ m, after secondary pulverization
  • the cotton straw has a bulk density of 440 kg/m 3 and is ready for use.
  • the biomass carbon is acidified, and the biomass carbon carrier is prepared;
  • the oxide of Mo, the oxide of Pd, and the above-mentioned biomass carbon carrier are subjected to vibration grinding to obtain a biomass carbon loaded with Mo oxide and Pd oxide having a particle diameter of 120-400 ⁇ m;
  • the total mass of Mo and Pd accounts for 3.5% of the mass of the above biomass carbon carrier based on the total mass of Mo and Pd.
  • the amount of H + in the acidified acid medium was 3.5 mol/L, the volume ratio of the biomass carbon to the acidic medium was 1:10, the acidification temperature was 50 ° C, and the acidification time was 4.3 h.
  • the pretreated biomass, the above-prepared biomass carbon loaded with Mo oxide and Pd oxide, amorphous iron oxyhydroxide and sulfur are mixed to obtain a mixture, and the mixture is added to a mixed oil of heavy oil and washing oil.
  • the total mass of the biomass carbon loaded with Mo oxide and Pd oxide and the amorphous iron oxyhydroxide (particle size 150-200 ⁇ m) is the pretreated biomass
  • the vulcanizing agent added was 0.2 wt% of the mass of the pretreated biomass.
  • Hydrogen is introduced into the biomass slurry to react, the reaction pressure is controlled to 20 MPa, and the reaction temperature is 400 ° C to prepare a bio-oil;
  • the specific method for 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 1000:1 to form a reaction raw material; heating the above-mentioned reaction raw material to 400 ° C and feeding it to the slurry bed reactor Hydrolysis, cracking and hydrogenation reactions occur simultaneously, and cold hydrogen is injected into the slurry bed reactor to control the total gas velocity in the slurry bed reactor to be 0.10 m/s; wherein the pressure of the high pressure hydrogen gas is 21 MPa.
  • the temperature of the high pressure cold hydrogen is 80 ° C;
  • the cold hydrogen is injected through four injection ports arranged in the height direction on the side wall of the slurry bed reactor.
  • the amount of biomass char supported as a catalyst with Mo oxide and Pd oxide in the slurry bed reactor accounted for 25% by weight of the liquid phase mass in the slurry bed reactor, and the liquefaction reaction time was 50 min.
  • a one-pot liquefaction process for biomass comprising the following steps:
  • the wheat straw and the flax straw are sent to a dryer and dried at 65 ° C for 4.5 h to a water content of less than 2 wt %, and then sent to an ultrafine pulverizer for preliminary pulverization treatment, and the median diameter after the initial pulverization is 180 ⁇ m, and then The initially pulverized wheat straw and flax straw are fed into a plodder at a temperature of 45 ° C and a pressure of 2.6 MPa for compression extrusion molding, followed by secondary pulverization treatment, and the median diameter after secondary pulverization is 36 ⁇ m, the bulk density after secondary pulverization was 440 kg/m 3 , and was used.
  • the pretreated biomass is mixed with amorphous iron oxyhydroxide (having a particle size of 100-200 ⁇ m) and dimethyl disulfide to obtain a mixture, and the mixture is added to an rancid oil shear slurry to form a slurry, which is tested.
  • the total content of wheat straw and flax straw in the slurry is 55 wt%, and the viscosity of the slurry is 620 mPa.
  • s (50 ° C) in the above slurry, the mass of amorphous iron oxyhydroxide is 6 wt% of the mass of the pretreated biomass, and the mass of the vulcanizing agent added is 0.25 wt% of the mass of the pretreated biomass.
  • Hydrogen is introduced into the biomass slurry to react, and the reaction pressure is 17 MPa and the reaction temperature is 440 ° C to prepare a bio-oil;
  • the specific method for introducing hydrogen gas is: injecting high-pressure hydrogen into the slurry twice, specifically: injecting high-pressure hydrogen into the slurry for the first time until the volume ratio of high-pressure hydrogen to slurry is 50:1, and then raising the slurry To 200 ° C, the second high pressure hydrogen gas is injected into the slurry, and the volume ratio of the total volume of the injected high pressure hydrogen gas to the slurry is 1300:1 to form a reaction raw material; the reaction raw material is heated to 440.
  • the slurry bed reactor After °C, it is sent to the slurry bed reactor to cause hydrolysis, cracking and hydrogenation reaction, and simultaneously injected cold hydrogen into the slurry bed reactor to control the total gas velocity in the slurry bed reactor to be 0.05 m/s;
  • the pressure of high pressure hydrogen is 16 MPa
  • the temperature of high pressure cold hydrogen is 105 ° C;
  • the cold hydrogen is injected through four injection ports arranged in the height direction on the side wall of the slurry bed reactor.
  • the amount of amorphous iron oxyhydroxide as a catalyst in the slurry bed reactor accounted for 9 wt% of the liquid phase mass in the slurry bed reactor, and the liquefaction reaction time was 110 min.
  • a one-pot liquefaction process for biomass comprising the following steps:
  • the olive oil residue is sent to a dryer and dried at 90 ° C for 3 hours to a water content of less than 2% by weight, and then sent to an ultrafine pulverizer for preliminary pulverization treatment.
  • the median diameter after the initial pulverization is 180 ⁇ m, and then the initial pulverization is performed.
  • the olive oil slag is sent to a plodder for compression extrusion at a temperature of 60 ° C and a pressure of 3.5 MPa, followed by secondary pulverization, and the median diameter after secondary pulverization is 36 ⁇ m, twice.
  • the pulverized bulk density was 1522 kg/m 3 and was used.
  • the pretreated biomass is mixed with amorphous iron oxyhydroxide (having a particle size of 100-200 ⁇ m) and dimethyl disulfide to obtain a mixture, and the mixture is added to an rancid oil shear slurry to form a slurry, which is tested.
  • the total content of the olive oil residue in the slurry is 55 wt%, and the viscosity of the slurry is 617 mPa. s (50 ° C), in the above slurry, the mass of amorphous iron oxyhydroxide is 6 wt% of the mass of the pretreated biomass, and the mass of the vulcanizing agent added is 0.25 wt% of the mass of the pretreated biomass.
  • Hydrogen is introduced into the biomass slurry to react, and the reaction pressure is 17 MPa and the reaction temperature is 440 ° C to prepare a bio-oil;
  • the specific method for introducing hydrogen gas is: injecting high-pressure hydrogen into the slurry twice, specifically: injecting high-pressure hydrogen into the slurry for the first time until the volume ratio of high-pressure hydrogen to slurry is 50:1, and then raising the slurry To 200 ° C, the second high pressure hydrogen gas is injected into the slurry, and the volume ratio of the total volume of the injected high pressure hydrogen gas to the slurry is 1300:1 to form a reaction raw material; the reaction raw material is heated to 440.
  • the slurry bed reactor After °C, it is sent to the slurry bed reactor to cause hydrolysis, cracking and hydrogenation reaction, and simultaneously injected cold hydrogen into the slurry bed reactor to control the total gas velocity in the slurry bed reactor to be 0.05 m/s;
  • the pressure of high pressure hydrogen is 16 MPa
  • the temperature of high pressure cold hydrogen is 105 ° C;
  • the cold hydrogen is injected through four injection ports arranged in the height direction on the side wall of the slurry bed reactor.
  • the amount of amorphous iron oxyhydroxide as a catalyst in the slurry bed reactor accounted for 9 wt% of the liquid phase mass in the slurry bed reactor, and the liquefaction reaction time was 110 min.
  • a one-pot liquefaction process for biomass comprising the following steps:
  • the rapeseed oil residue is sent to a dryer and dried at 80 ° C for 2 hours to a water content of less than 2 wt%, and then sent to an ultrafine pulverizer for preliminary pulverization.
  • the median diameter after the initial pulverization is 200 ⁇ m, and then the initial pulverization is performed.
  • the rapeseed oil residue is sent to a briquetting machine for compression extrusion at a temperature of 40 ° C and a pressure of 3 MPa, followed by secondary pulverization, and the median diameter of the biomass after secondary pulverization is 45 ⁇ m.
  • the bulk density after the secondary pulverization was 1600 kg/m 3 , which was used.
  • biomass carbon is alkalized to obtain a biomass carbon carrier
  • the oxide of Ni and the above-mentioned biomass carbon carrier are sequentially subjected to plane grinding and ball milling to obtain a biomass carbon loaded with Ni oxide having a particle diameter of 200-400 ⁇ m, which is a catalyst;
  • Ni accounts for 1% by mass of the biomass carbon carrier based on the mass of Ni.
  • the amount of the substance of OH - in the alkalized alkaline medium was 0.5 mol/L, the volume ratio of the above biomass carbon to the alkaline medium was 1:15, the alkalization temperature was 30 ° C, and the alkalization time was 10 h.
  • the pretreated biomass is mixed with the catalyst prepared above and carbon disulfide to obtain a mixture, and the mixture is added to an rancid oil to be sheared and slurried to form a slurry.
  • the content of the rapeseed oil residue in the slurry is 59% by weight.
  • the viscosity of the slurry is 305 mPa. s (50 ° C), in the above slurry, the mass of the catalyst is 1 wt% of the mass of the pretreated biomass, and the mass of the vulcanizing agent added is 0.25 wt% of the mass of the pretreated biomass.
  • Hydrogen is introduced into the biomass slurry to react, the reaction pressure is controlled to 15 MPa, and the reaction temperature is 380 ° C to prepare a bio-oil;
  • the specific method for 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 600:1 to form a reaction raw material; and heating the above-mentioned reaction raw material to 380 ° C and then feeding it to the slurry bed reactor Hydrolysis, cracking and hydrogenation reactions occur simultaneously, and cold hydrogen is injected into the slurry bed reactor to control the total gas velocity in the slurry bed reactor to be 0.2 m/s; wherein the pressure of the high pressure hydrogen gas is 18 MPa.
  • the temperature of the high pressure cold hydrogen is 135 ° C;
  • the cold hydrogen is injected through five injection ports arranged in the height direction on the side wall of the slurry bed reactor.
  • the amount of Ni oxide-loaded biomass carbon as a catalyst in the slurry bed reactor accounted for 30% by weight of the liquid phase mass in the slurry bed reactor, and the liquefaction reaction time was 90 minutes.
  • a one-pot liquefaction process for biomass comprising the following steps:
  • the rice straw and the reed straw are sent to a dryer and dried at 70 ° C for 5 h to a water content of less than 2 wt %, and then sent to an ultrafine pulverizer for initial pulverization.
  • the median diameter after the initial pulverization is 100 ⁇ m, and then the initial The pulverized rice straw and the reed straw are sent to a plodder for compression extrusion at a temperature of 60 ° C and a pressure of 2 MPa, followed by secondary pulverization treatment, and the median diameter after secondary pulverization is 30 ⁇ m.
  • the bulk density of rice straw and reed straw after secondary pulverization was 400 kg/m 3 , which was used for future use.
  • the biomass carbon is acidified, and the biomass carbon carrier is prepared;
  • Mo accounts for 1% by mass of the above biomass carbon carrier in terms of Mo mass.
  • the amount of H + in the acidified acid medium was 5 mol/L
  • the volume ratio of the biomass carbon to the acidic medium was 1:5
  • the acidification temperature was 80 ° C
  • the acidification time was 1 h.
  • the pretreated biomass, the catalyst prepared above and sulfur are mixed to obtain a mixture, and the mixture is added to water and stirred to form a slurry.
  • the total content of the rice straw and the reed straw in the slurry is 50% by weight.
  • the viscosity of the slurry is 800mPa. s (50 ° C), in the above slurry, the catalyst added was 1 wt% of the mass of the pretreated biomass, and the sulfur added was 0.4 wt% of the mass of the pretreated biomass.
  • Hydrogen is introduced into the biomass slurry to react, the reaction pressure is controlled to 20 MPa, and the reaction temperature is 300 ° C to prepare a bio-oil;
  • the specific method for 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 1500:1, thereby forming a reaction raw material; heating the above-mentioned reaction raw material to 320 ° C and feeding it to the slurry bed reactor Hydrolysis, cracking and hydrogenation reactions occur simultaneously, and cold hydrogen is injected into the slurry bed reactor to control the total gas velocity in the slurry bed reactor to be 0.2 m/s; wherein the pressure of the high pressure hydrogen gas is 22 MPa.
  • the temperature of the high pressure cold hydrogen is 135 ° C;
  • the cold hydrogen is injected through three injection ports arranged in the height direction on the side wall of the slurry bed reactor.
  • the amount of biomass carbon loaded with MO oxide as a catalyst in the slurry bed reactor accounted for 30% by weight of the liquid phase mass in the slurry bed reactor, and the liquefaction reaction time was 30 minutes.
  • a one-pot liquefaction process for biomass comprising the following steps:
  • the olive oil residue is sent to a dryer and dried at 100 ° C for 4.0 h to a water content of less than 2 wt %, and then sent to an ultrafine pulverizer for preliminary pulverization treatment.
  • the median diameter after the initial pulverization is 290 ⁇ m, and then the initial The pulverized olive oil slag is sent to a plodder and subjected to compression extrusion at a temperature of 35 ° C and a pressure of 2.7 MPa, followed by secondary pulverization treatment, and the median diameter after secondary pulverization is 44 ⁇ m.
  • the bulk density after the secondary pulverization was 1510 kg/m 3 , which was used.
  • the pretreated biomass is mixed with amorphous iron oxyhydroxide (having a particle size of 100-200 ⁇ m) and sulfur to obtain a mixture, and the mixture is added to water to be sheared and slurried to form a slurry, and the olive oil residue in the slurry is detected.
  • the content is 50% by weight, and the viscosity of the slurry is 465 mPa. s (50 ° C), in the above slurry, the mass of amorphous iron oxyhydroxide is 6 wt% of the mass of the pretreated biomass, and the mass of the vulcanizing agent added is 0.25 wt% of the mass of the pretreated biomass.
  • Hydrogen is introduced into the biomass slurry to react, the reaction pressure is controlled to 18 MPa, and the reaction temperature is 340 ° C to prepare a bio-oil;
  • the specific method for introducing hydrogen gas is: injecting high-pressure hydrogen into the slurry twice, specifically: injecting high-pressure hydrogen into the slurry for the first time until the volume ratio of high-pressure hydrogen to slurry is 50:1, and then raising the slurry Up to 200 ° C, the second high pressure hydrogen gas is injected into the slurry, and the volume ratio of the total volume of the injected high pressure hydrogen gas to the slurry is 1300:1 to form a reaction raw material; the reaction raw material is heated to 340.
  • the slurry bed reactor After °C, it is sent to the slurry bed reactor to cause hydrolysis, cracking and hydrogenation reaction, and simultaneously injected cold hydrogen into the slurry bed reactor to control the total gas velocity in the slurry bed reactor to be 0.05 m/s;
  • the pressure of high pressure hydrogen is 20 MPa
  • the temperature of high pressure cold hydrogen is 105 ° C;
  • the cold hydrogen is injected through four injection ports arranged in the height direction on the side wall of the slurry bed reactor.
  • the amount of amorphous iron oxyhydroxide as a catalyst in the slurry bed reactor accounted for 9 wt% of the liquid phase mass in the slurry bed reactor, and the liquefaction reaction time was 40 min.
  • a one-pot liquefaction process for biomass comprising the following steps:
  • the soybean oil residue is sent to a dryer and dried at 95 ° C for 3.5 h to a water content of less than 2 wt %, and then sent to an ultrafine pulverizer for preliminary pulverization and ash removal treatment, and the median diameter after initial pulverization is 110 ⁇ m.
  • the initially pulverized soybean oil slag is sent to a plodder at a temperature of 38 ° C and a pressure of 2.5 MPa for compression extrusion molding, followed by secondary pulverization treatment, and the secondary particle diameter after secondary pulverization is 50 ⁇ m.
  • the bulk density is 1500 kg/m 3 , and it is used.
  • the pretreated biomass is mixed with amorphous alumina (having a particle size of 200-500 ⁇ m) loaded with Mn oxide and Pd oxide, amorphous iron oxyhydroxide and sulfur to obtain a mixture, and the mixture is added to water and stirred for pulping.
  • amorphous alumina having a particle size of 200-500 ⁇ m
  • Mn oxide and Pd oxide loaded with Mn oxide and Pd oxide
  • amorphous iron oxyhydroxide and sulfur to obtain a mixture
  • the mixture is added to water and stirred for pulping.
  • the total mass of amorphous alumina and amorphous iron oxyhydroxide supported with Mn oxide and Pd oxide is 3 wt% of the mass of the pretreated biomass, and the sulfur to be added The mass is 0.4 wt% of the pretreated biomass mass.
  • Hydrogen is introduced into the biomass slurry to react, and the reaction pressure is 20 MPa and the reaction temperature is 420 ° C to prepare a bio-oil;
  • the specific method for introducing hydrogen gas is: injecting high-pressure hydrogen into the slurry twice, specifically: injecting high-pressure hydrogen into the slurry for the first time until the volume ratio of high-pressure hydrogen to slurry is 100:1, and then raising the slurry To 250 ° C, the second high pressure hydrogen gas is injected into the slurry, and the volume ratio of the total volume of the injected high pressure hydrogen gas to the slurry is 1050:1 to form a reaction raw material; the reaction raw material is heated to 420.
  • the slurry bed reactor After °C, it is sent to the slurry bed reactor to cause hydrolysis, cracking and hydrogenation reaction, and simultaneously injected cold hydrogen into the slurry bed reactor to control the total gas velocity in the slurry bed reactor to be 0.07 m/s;
  • the pressure of high pressure hydrogen is 21 MPa
  • the temperature of high pressure cold hydrogen is 105 ° C;
  • the cold hydrogen is injected through three injection ports arranged in the height direction on the side wall of the slurry bed reactor.
  • the amount of amorphous iron oxyhydroxide as a catalyst in the slurry bed reactor accounted for 27% by weight of the liquid phase mass in the slurry bed reactor, and the liquefaction reaction time was 35 minutes.
  • a one-pot liquefaction process for biomass comprising the following steps:
  • the wheat straw is sent to a dryer and dried at 50 ° C for 5 hours to a water content of less than 2 wt%, and then sent to an ultrafine pulverizer for preliminary pulverization.
  • the median diameter after the initial pulverization is 100 ⁇ m, and then the initial pulverization is carried out.
  • the wheat straw is fed into a plodder at a temperature of 30 ° C and a pressure of 3 MPa for compression extrusion molding, followed by secondary pulverization treatment, and the secondary particle diameter after secondary pulverization is 30 ⁇ m, and the wheat after secondary pulverization
  • the bulk density of the straw is 500kg/m 3 , which is reserved.
  • the biomass carbon is acidified, and the biomass carbon carrier is prepared;
  • Mo accounts for 1% by mass of the above biomass carbon carrier in terms of Mo mass.
  • the amount of H + in the acidified acid medium was 5 mol/L
  • the volume ratio of the biomass carbon to the acidic medium was 1:5
  • the acidification temperature was 80 ° C
  • the acidification time was 1 h.
  • the pretreated biomass, the catalyst prepared above and sulfur are mixed to obtain a mixture, and the mixture is added to a mixed oil of hydrophobic oil and residual oil to be stirred and slurried to form a slurry, and the total content of wheat straw in the slurry is detected. 5wt%, the viscosity of the slurry is 500Pa. s (50 ° C), in the above slurry, the catalyst added was 1 wt% of the mass of the pretreated biomass, and the vulcanizing agent added was 0.4 wt% of the mass of the pretreated biomass.
  • Hydrogen is introduced into the biomass slurry to react, the reaction pressure is controlled to 25 MPa, and the reaction temperature is 380 ° C to prepare a bio-oil;
  • the specific method for 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 1500:1 to form a reaction raw material; and heating the above-mentioned reaction raw material to 380 ° C and then feeding it to the slurry bed reactor Hydrolysis, cracking and hydrogenation reactions occur simultaneously, and cold hydrogen is injected into the slurry bed reactor to control the total gas velocity in the slurry bed reactor to be 0.2 m/s; wherein the pressure of the high pressure hydrogen gas is 27 MPa.
  • the temperature of the high pressure cold hydrogen is 135 ° C;
  • the cold hydrogen is injected through three injection ports arranged in the height direction on the side wall of the slurry bed reactor.
  • the amount of biomass carbon loaded with MO oxide as a catalyst in the slurry bed reactor accounted for 30% by weight of the liquid phase mass in the slurry bed reactor, and the liquefaction reaction time was 30 minutes.
  • the biomass conversion obtained by the method of the present invention is 95-99%, the oil phase yield is 60-86%, the residue amount is less than 0.1 wt%, and the carbon content in the obtained oil phase is 80-90 wt%, a hydrogen content of 9-19 wt%, and an oxygen content of 0.1-3 wt%.
  • This embodiment provides a method for preparing a second catalyst, comprising the following steps:
  • the dry distillation biomass carbon is acidified or alkalized to obtain a second biomass carbon carrier; specifically: the acid concentration of the H + substance in the acidified acid medium is 5 mol / L; The volume ratio of the material carbon to the acidic medium is 1:15, the acidification temperature is 80 ° C, and the acidification time is 10 h; the amount of the substance of the OH - in the alkalized alkaline medium is 0.5 mol/L; The volume ratio of the dry distillation biomass carbon to the alkaline medium is 1:5, the alkalization temperature is 30 ° C, and the alkalization time is 10 h.
  • the second active component and the second biomass carbon carrier are subjected to vibration grinding and/or planar grinding and/or ball milling to obtain a second catalyst having a particle diameter of 100 ⁇ m to 200 ⁇ m.
  • the second active component is an oxide loaded with Mo and W, and the second active component accounts for 5% by mass of the second biomass carbon carrier.
  • the corn stalk is sent to a dryer to be dried to a water content of 3 wt%, and then pulverized in a pulverizer to a particle size of 1 to 50 ⁇ m, and then ash is removed to obtain straw granules;
  • the reeds are sent to a dryer to be dried to a water content of 5 wt%, and then pulverized in a pulverizer to a particle size of 20 to 1000 ⁇ m, and then ash is removed to obtain reed granules;
  • the biomass carbon (having a particle diameter of 100 ⁇ m - 150 ⁇ m) loaded with W oxide and Ni oxide, and the amorphous iron oxyhydroxide and the reed granules and sulfur of the step (1) are 2:2 by mass ratio: Mixing 100:0.4 to obtain a mixture, adding the mixture to vegetable oil to form a slurry containing 30% by weight of biomass;
  • the wheat straw is sent to a dryer to be dried to a water content of 7 wt%, and then pulverized in a pulverizer to a particle size of 1500 to 2000 ⁇ m, and then ash is removed to obtain straw granules;
  • the biomass carbon (having a particle diameter of 50 ⁇ m to 100 ⁇ m) loaded with Pd oxide and Ni oxide, and the amorphous iron oxyhydroxide and the straw particles and sulfur of the step (1) are 2:3 by mass ratio: Mixing 100:0.3 to obtain a mixture, adding the mixture to low temperature animal oil to form a slurry containing 25 wt% of biomass;
  • the wood chips are sent to a dryer to be dried to a water content of 10% by weight, and then pulverized in a pulverizer to a particle size of 4000 to 5000 ⁇ m, and then ash is removed to obtain wood chips;
  • the total gas velocity in the reactor is controlled to be 0.1 m/s and the inventory of the catalyst in the reactor is 30 wt% of the liquid phase mass in the reactor.
  • the material discharged from the slurry bed reactor is discharged. It is sent to the separation system for gas, liquid and residue three-phase separation to obtain biomass gas, bio-oil and residue respectively; the hydrogen in the system is recycled, and together with the fresh supplementary hydrogen, enters each hydrogen injection point of step (3).
  • the leaves are sent to a dryer to be dried to a water content of 15% by weight, and then pulverized in a pulverizer to a particle size of 4000-5000 ⁇ m, and then ash-removed to obtain leaf granules;
  • Example 2 The catalyst prepared in Example 1 and the amorphous iron oxyhydroxide are mixed with the wood particles of the step (1) and sulfur at a mass ratio of 1:0.2:100:0.25 to obtain a mixture, and the mixture is added to the low temperature. Forming a slurry containing 20% by weight of biomass in vegetable oil;
  • the one-pot liquefaction process of biomass provided in this experimental example includes the following steps:
  • the reeds are sent to a dryer to be dried to a water content of 5 wt%, and then pulverized in a pulverizer to a particle size of 20 to 1000 ⁇ m, and then ash is removed to obtain reed granules;
  • the biomass carbon (having a particle diameter of 100 ⁇ m - 150 ⁇ m) loaded with W oxide and Ni oxide, and the amorphous iron oxyhydroxide and the reed granules and sulfur of the step (1) are 2:2 by mass ratio: Mixing 100:0.4 to obtain a mixture, adding the mixture to vegetable oil to form a slurry containing 30% by weight of biomass;
  • Hydrolysis, cracking and hydrogenation reaction were carried out under the conditions of a reaction pressure of 10 MPa and a reaction temperature of 200 ° C, and during the reaction, 120 ° C was injected through four injection ports arranged in the height direction on the side wall of the reactor.
  • Cold hydrogen the total gas velocity in the reactor is controlled to be 0.06 m/s and the catalyst in the reactor is 25 wt% of the liquid phase mass in the reactor.
  • the material discharged from the slurry bed reactor is discharged. It is sent to the separation system for gas, liquid and residue three-phase separation to obtain biomass gas, bio-oil and residue respectively; the hydrogen in the system is recycled, and together with the fresh supplementary hydrogen, enters each hydrogen injection point of step (3).
  • Conversion rate of coal to biomass (mass of liquefaction reaction product - mass of vulcanizing agent - mass of catalyst - mass of solvent oil) / (mass and biomass of coal and biomass)
  • Bio-oil yield mass of oil phase obtained after separation of liquefied reaction product / (mass and biomass of coal and biomass)
  • Residue content residue quality / (mass and biomass quality).
  • This embodiment provides a method for preparing a second catalyst, comprising the following steps:
  • the biomass charcoal is acidified at a ratio of 15:1 at 80 ° C for 10 h to obtain a biomass charcoal carrier; as an alternative, OH can also be used.
  • An alkaline medium having a concentration of 0.5 mol/L was subjected to acidification treatment at 30 ° C for 5 hours at a volume ratio of 5:1.
  • the oxide of Mo and W and the biomass carbon carrier are vibrated together, that is, the loading of the active component on the biomass carbon carrier is carried out to obtain a second catalyst having a particle diameter of 100 ⁇ m to 200 ⁇ m.
  • the second active component accounts for 5% by mass of the biomass carbon carrier based on the mass of the metal element.
  • the corn stalk is taken, dried and dehydrated to a water content of less than 2 wt%, pulverized to a median diameter of 100 ⁇ m, and then sent to a plodder for extrusion molding, and the molding pressure is 2 MPa to obtain a straw compressed material;
  • the straw compressed material was sent to a hammer mill and pulverized to obtain a straw pulverized material having a particle size of 50 ⁇ m, which was used.
  • the lignite is taken, dried and dehydrated, pulverized to a median particle size of 100 ⁇ m, and then sent to a briquetting machine for extrusion molding, and the molding pressure is 5 MPa to obtain a brown coal compressed material;
  • the lignite compressed material was sent to a ball mill and pulverized to obtain a lignite pulverized material having a median diameter of 30 ⁇ m, which was used.
  • the straw pulverized material and the lignite pulverized material are subjected to ash removal, and the ratio of amorphous alumina (having a particle diameter of 5 ⁇ m to 50 ⁇ m) loaded with Mo oxide and Co oxide and sulfur at a mass ratio of 100:5:0.3 Mixing to obtain a mixture, the mixture is added to the rancid oil to form a biomass coal slurry; in the biomass coal slurry, the straw content is 20% by weight, the brown coal content is 45wt%;
  • the corn stalk is taken, dried and dehydrated to a water content of 1 wt%, pulverized to a median diameter of 100 ⁇ m, and then sent to a press machine for extrusion molding, and the molding pressure is 2 MPa to obtain a straw compressed material;
  • the straw compressed material was sent to a hammer mill and pulverized to obtain a straw pulverized material having a particle size of 50 ⁇ m, which was used.
  • the lignite is taken, dried and dehydrated, pulverized to a median particle size of 50 ⁇ m, and then sent to a briquetting machine for extrusion molding, and the molding pressure is 5 MPa to obtain a brown coal compressed material;
  • the lignite compressed material was sent to a ball mill and pulverized to obtain a lignite pulverized material having a median diameter of 30 ⁇ m, which was used.
  • the straw pulverized material and the lignite pulverized material are ash-removed, and the ratio of amorphous alumina (having a particle diameter of 5 ⁇ m to 50 ⁇ m) loaded with Mo oxide and Co oxide and sulfur at a mass ratio of 100:5:0.3 Mixing to obtain a mixture, the mixture is added to water to form a biomass coal water slurry; in the biomass coal water slurry, the straw content is 15% by weight, the brown coal content is 40% by weight;
  • Reeds were taken, dried to a water content of 1 wt%, and then sent to a jet mill for pulverization to obtain a repulver primary pulverized material having a particle diameter D 50 of 200 ⁇ m.
  • the reed primary pulverized material is sent to a briquetting machine or a plodder for extrusion molding, and the molding pressure is 3 MPa to obtain a reed compressed material.
  • the reed compressed material is sent to a jet mill to be subjected to secondary pulverization to obtain a secondary pulverized material of reed, and the particle diameter D 50 is 40 ⁇ m, which is ready for use.
  • the secondary pulverized material of reed and coal is mixed with biomass carbon loaded with W oxide and Ni oxide (having a particle diameter of 100 ⁇ m - 150 ⁇ m) and iron oxyhydroxide and sulfur at a mass ratio of 100:2:2:0.4.
  • the mixture was mixed to obtain a mixture, and the mixture was added to water to form a biomass coal water slurry; in the biomass coal water slurry, the content of the reed was 20% by weight, and the content of the coal was 40% by weight.
  • Palm oil residue and lignite were taken, dried and dehydrated, pulverized to a median particle size of 100 ⁇ m, and then fed together into a briquetting press to form a molding pressure of 5 MPa to obtain a palm oil residue and a brown coal compressed material.
  • the compressed material was sent to a ball mill and pulverized to obtain palm oil slag having a median diameter of 50 ⁇ m and a pulverized material of lignite, which were used.
  • the biomass coal water slurry is prepared with water; the content of palm oil residue in the biomass coal water slurry is 20% by weight, and the content of the coal is 45% by weight.
  • the material discharged from the bed reactor is sent to the separation system for gas, liquid and residue three-phase separation to obtain biomass gas, bio-oil and residue respectively; the hydrogen in the system is recycled, and together with the fresh supplementary hydrogen, enters the above-mentioned respective injections. Hydrogen point.
  • Soybean oil slag is taken, dried and dehydrated, and then sent to an ultrafine pulverizer for pulverization treatment to obtain a primary pulverized material of soybean oil residue, and the particle diameter D 50 is 250 ⁇ m.
  • soybean oil slag compressed material is sent to an ultrafine pulverizer for secondary pulverization to obtain a secondary pulverized material of soybean oil slag, and the particle diameter D 50 is 45 ⁇ m, which is ready for use.
  • the first pulverized material of Shendong Changyan coal is sent to a briquetting machine or a plodder for extrusion molding, and the molding pressure is 10 MPa, and the Shendong long flame coal compressed material is obtained.
  • the catalyst prepared in Example 1 is used, and the secondary pulverized material of soybean oil residue and coal is mixed with the above catalyst, iron oxyhydroxide and sulfur at a mass ratio of 100:1:0.2:0.25 to obtain a mixture.
  • the mixture is added to the waste lubricating oil to form a biomass coal slurry; in the biomass coal slurry, the soybean oil residue is 20% by weight, and the coal content is 40% by weight.
  • the material discharged from the slurry bed reactor is sent to the separation system for gas, liquid and residue three-phase separation to obtain biomass gas, bio-oil and residue respectively; the hydrogen in the system is recycled, and together with the fresh supplementary hydrogen, enters the above-mentioned Each hydrogen injection point.
  • Palm oil residue and lignite are taken, dried and dehydrated to a water content of less than 2% by weight, and then sent to a briquetting machine or a press machine for extrusion molding at a molding pressure of 5 MPa to obtain a palm oil residue and a brown coal compressed material.
  • the compressed material is sent to a ball mill and pulverized to obtain palm oil residue and brown coal pulverized material, which are ready for use.
  • the biomass coal slurry is prepared with the waste oil; the content of the palm oil residue in the biomass coal slurry is 25 wt%, and the content of the coal is 40 wt%.
  • the material discharged from the bed reactor is sent to the separation system for gas, liquid and residue three-phase separation to obtain biomass gas, bio-oil and residue respectively; the hydrogen in the system is recycled, and together with the fresh supplementary hydrogen, enters the above-mentioned respective injections. Hydrogen point.
  • Reeds were taken, dried to a water content of 1 wt%, and then sent to a jet mill for pulverization to obtain a repulver primary pulverized material having a particle diameter D 50 of 300 ⁇ m.
  • the reed primary pulverized material is sent to a briquetting machine or a plodder for extrusion molding, and the molding pressure is 5 MPa to obtain a reed compressed material.
  • the reed compressed material is sent to a jet mill to perform secondary pulverization to obtain a secondary pulverized material of reed, and the particle diameter D 50 is 30 ⁇ m, which is ready for use.
  • the first pulverized material of Shendong Changyan coal is sent to a briquetting machine or a plodder for extrusion molding, and the molding pressure is 15 MPa, and the Shendong long flame coal compressed material is obtained.
  • the secondary pulverized material of reed and coal is mixed with biomass carbon loaded with W oxide and Ni oxide (having a particle diameter of 100 ⁇ m - 150 ⁇ m) and iron oxyhydroxide and sulfur at a mass ratio of 100:2:2:0.4.
  • the mixture was mixed to obtain a mixture, and the mixture was added to waste engine oil to form a biomass coal slurry; in the biomass coal slurry, the content of the reed was 30% by weight, and the content of the coal was 30% by weight.
  • the one-pot liquefaction process of coal and biomass provided in this experimental example includes the following steps:
  • Reeds were taken and dried to a water content of 1.5 wt%, and then sent to a jet mill for pulverization to obtain a repulver primary pulverized material having a particle diameter D 50 of 200 ⁇ m.
  • the reed primary pulverized material is sent to a briquetting machine or a plodder for extrusion molding, and the molding pressure is 3 MPa to obtain a reed compressed material.
  • the reed compressed material is sent to a jet mill to be subjected to secondary pulverization to obtain a secondary pulverized material of reed, and the particle diameter D 50 is 40 ⁇ m, which is ready for use.
  • the secondary pulverized material of reed and coal and the water-soluble dispersive hydrogenation catalyst after vulcanization are mixed at a mass ratio of 100:4.4 to obtain a mixture, and the mixture is added to water to form a biomass coal water slurry;
  • the content of the reed is 20% by weight, and the content of the coal is 45% by weight.
  • the one-pot liquefaction process for coal and biomass provided in this comparative example includes the following steps:
  • Reeds were taken, dried to a water content of 1 wt%, and then sent to a jet mill for pulverization to obtain a repulver primary pulverized material having a particle diameter D 50 of 300 ⁇ m.
  • the reed primary pulverized material is sent to a briquetting machine or a plodder for extrusion molding, and the molding pressure is 5 MPa to obtain a reed compressed material.
  • the reed compressed material is sent to a jet mill to perform secondary pulverization to obtain a secondary pulverized material of reed, and the particle diameter D 50 is 30 ⁇ m, which is ready for use.
  • the secondary pulverized material of reed and coal and the oil-soluble dispersive hydrogenation catalyst are mixed at a mass ratio of 100:2:2:0.4 to obtain a mixture, and the mixture is added to waste engine oil to form a biomass coal slurry;
  • the content of the reed is 30% by weight, and the content of the coal is 30% by weight.

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Abstract

一种生物质或煤与生物质的一锅法液化工艺，首先配制含有催化剂、硫化剂和生物质（和煤）的浆液，而后向浆液中通入氢气以发生反应；上述浆液的配制步骤为：将生物质（和煤）依次进行干燥、初粉碎、压缩和二次粉碎，而后与催化剂、硫化剂混合得到混合物，将上述混合物加入至油品中研磨制浆，制得生物质浆液。通过将秸秆先压缩后二次粉碎的处理工艺，使秸秆的体积大幅降低，有利于其在油品中的分散，增加了反应物料的浓度，提高了泵在单位时间内对生物质的输送量，同时提高了生物质的转化率。

Description

一种生物质或煤与生物质的一锅法液化工艺 技术领域
本发明涉及生物能源转化技术领域，具体涉及一种生物质或煤与生物质的一锅法液化工艺。
背景技术
煤炭、原油、天然气、油页岩等化石非再生能源随着社会经济的快速发展而日趋枯竭，以及它们燃烧后产生的CO 2、SO 2、NO x等污染物所造成的日益严重的环境污染，这使得人类不得不认真考虑获取能源的途径和改善环境的方法。生物质是一种可再生能源，其在满足能源需求、减少环境污染、改善能源结构方面都具备巨大的潜力和优势，生物质是指一切直接或间接可利用的绿色植物光合作用形成的有机物质，包括植物、动物、微生物及其排泄与代谢物，它具有可再生性、低污染性、广泛分布性。近些年来，对生物质能源的转化和利用一直朝着高效、清洁的方向前进，生物质液化技术是其中的重要组成部分。生物质的液化机理如下：生物质首先裂解成低聚体，然后再经脱水、脱羟基、脱氢、脱氧和脱羧基而形成小分子化合物，小分子化合物接着通过缩合、环化、聚合等反应而生成新的化合物。目前生物质液化技术主要有间接液化和直接液化两类，其中直接液化是指在溶剂或催化剂的作用下，采用水解、超临界液化或通入氢气、惰性气体等，在适当的温度、压力下将生物质直接从固体液化成液体。生物质直接液化技术主要有热解液化、催化液化、加压加氢液化等，尤其以加氢加压液化的产品收率高，品质好，其一般包括固体物料干燥、粉碎、制浆、升温、加压、反应、分离等复杂工序。例如，中国专利文献CN103242871A公开了一种重油-生物质加氢共液化工艺，该工艺通过将经过干燥的生物质预粉碎至40-100目后再与重油混合形成浆料，并向此浆料中加入催化剂和硫化剂，而后置于浆态床加氢反应器中，控制反应温度为370℃-430℃，氢分压为4-8MPa，进行加氢热裂解反应，反应产物经分馏后得到生物油和焦炭。
上述工艺实现了由生物质向生物油的转换，但上述技术中，一方面，由生物质和重油形成的浆料需要由泵输送至浆态床加氢反应器中，而多数生物质(例如秸秆)因具有丰富的孔隙率造成其比重较低，使之较难溶于生物质液化溶剂中，造成浆液中生物质的浓度较低(上述技术中生物质仅占重油质量的5～20wt％)，从而导致泵在单位时间内对 生物质的输送量有限，造成上述加氢共液化工艺的生产效率较低、工业成本较高、能耗较大；另一方面，具有孔隙率的生物质易漂浮于液化溶剂表面，加之作为浆料溶剂的重油粘度较大，使得上述浆料不易流动，易造成输送管道的堵塞从而难以实现泵的平稳运输；现有技术虽然尝试在浆液中加入分散剂来提高生物质在浆液中的浓度及分散性，但分散剂的加入往往会影响制得的生物油的品质。此外，上述技术中生物质转化率较低(其转化率仅为90％左右)。为此，如何对现有的生物质液化工艺进行改进以增加浆液中生物质的浓度、提高单位时间内泵对生物质的输送量、实现泵的平稳运输、降低能耗、提高生物质转化率这对于本领域技术人员而言依旧是一个亟待解决的技术难题。
发明内容
因此，本发明要解决的技术问题在于克服现有的生物质液化工艺中，泵对生物质的输送量少且运输不平稳、生物质转化率低、能耗高的缺陷，进而提供一种生物质或煤与生物质的一锅法液化工艺。
为此，本发明解决上述问题所采用的技术方案如下：
本发明提供的第一种技术方案:
一种生物质的一锅法液化工艺，包括如下步骤：
配制含有催化剂、硫化剂和生物质的浆液，向所述浆液中通入氢气以发生反应，并控制反应压力为15-25MPa、反应温度为380-480℃，最终制得生物油；
所述生物质为秸秆，所述浆液的配制步骤为，将秸秆依次进行干燥、初粉碎、压缩和二次粉碎，得到预处理生物质，而后将所述预处理生物质与所述催化剂和硫化剂混合得到混合物，将所述混合物加入至油品中研磨制浆，得到秸秆浓度为30～60wt％的所述浆液。
本发明中的秸秆原料可以是麦子、水稻、玉米、芦苇、高粱、谷子等谷类作物秸秆，也可以是大豆、小豆、绿豆、蚕豆、豌豆等豆科植物秸秆，还可以是棉花、亚麻、苎麻、大麻等纤维作物秸秆，可以是一种秸秆也可以是多种秸秆共同组成的生物质原料。
所述浆液的配制步骤中，将所述秸秆进行压缩的压力为0.5～3MPa、温度为30-60℃。
所述浆液的配制步骤中，所述秸秆的干燥温度为50-70℃、时间为3-5h，所述秸秆干燥后的含水率低于2wt％；初粉碎后中位粒度为100-300μm；经二次粉碎后中位粒度为30-50μm、二次粉碎后堆密度为400-500kg/m 3。
所述浆液的粘度为500-1400mPa﹒s(50℃)。
在所述浆液中，所述秸秆的含量为55～60wt％。
所述浆液的配制步骤中，所述油品为废弃动植物油脂、废矿物油、矿物油或馏分油中的一种或多种。
进一步地，所述废弃动植物油脂为地沟油、潲水油或酸败油中的一种或多种；
所述废矿物油为废润滑油或废机油中的一种或两种；
所述矿物油为重油、渣油、蒽油或洗油中的一种或多种。
所述研磨制浆为搅拌制浆、分散制浆、乳化制浆、剪切制浆或均质制浆。
所述催化剂包括无定型羟基氧化铁、负载有活性组分的无定型氧化铝或负载有活性组分的生物质炭中的一种或多种，所述活性组分选自元素周期表第VIB、VIIB或VIII族金属的氧化物中的一种或多种。
所述活性组分选自Mo、W、Fe、Co、Ni、Mn或Pd的氧化物中的一种或多种。
所述催化剂的用量为所述预处理生物质质量的1～10wt％，优选为1～4wt％；所述催化剂的粒径为5-500μm；所述硫化剂的用量为所述预处理生物质质量的0.1-0.4wt％。
向所述浆液中通入氢气的具体方法为：向所述浆液中注入高压氢气，并控制所述高压氢气与所述浆液的体积比为(600～1500)：1，从而形成反应原料；
将所述反应原料升温至380-480℃后送入浆态床反应器内以发生水解、裂化及加氢反应，同时向所述浆态床反应器内注入冷氢，控制所述浆态床反应器内的总气速为0.02～0.2m/s，优选为0.05～0.08m/s；
其中，所述高压氢气的压力为13～25MPa，所述冷氢的温度为60～135℃。
将所述高压氢气分两次注入至所述浆液中，具体为：在向所述浆液中第一次注入所述高压氢气，直至所述高压氢气与所述浆液的体积比为50-200:1，而后将所述浆液升温至200～350℃，再向所述浆液中第二次注入所述高压氢气。
所述冷氢经由所述浆态床反应器侧壁上的沿高度方向依次设置的3～5个注入口注入。
所述催化剂在所述浆态床反应器内的存量控制在所述浆态床反应器内液相质量的 5～30wt％；
所述反应的时间为30～120min。
负载有活性组分的生物质炭的制备方法：
S1、生物质炭经酸化或碱化处理后，制得生物质炭载体；
S2、将活性组分和所述生物质炭载体混合研磨，制得负载有活性组分的生物质炭。
所述活性组分为选自Mo、W、Fe、Co、Ni、Mn或Pd的氧化物中的一种或多种，以金属元素质量计，所述活性组分占所述生物质炭载体质量的1％～5％。
所述将活性组分和所述生物质炭载体混合研磨步骤为：将所述活性组分和所述生物质炭载体经振动研磨和/或平面研磨和/或球磨得到粒径为5～500μm的负载有活性组分的生物质炭。
所述酸化处理的酸性介质中H +的物质的量浓度为0.5mol/L～5mol/L；所述生物质炭与所述酸性介质体积比为1:5～1:15，酸化温度为30～80℃，酸化时间为1h～10h；所述碱化处理的碱性介质中OH -的物质的量浓度为0.5mol/L～5mol/L；所述生物质炭与所述碱性介质体积比为1:5～1:15，碱化温度为30℃～80℃，碱化时间为1h～10h。
本发明中的硫化剂可为硫磺、二硫化碳或二甲基二硫醚。
本发明还提供了第二种技术方案：
一种生物质的一锅法液化工艺，包括如下步骤：
配制含有催化剂、硫化剂和生物质的浆液，向所述浆液中通入氢气以发生反应，并控制反应压力为13～25MPa、反应温度为300～500℃，最终制得生物油。
所述催化剂包括负载有第一活性组分的无定型氧化铝或负载有第一活性组分的生物质碳，所述第一活性组分选自元素周期表第VIB、VIIB或VIII族金属的氧化物中的一种或多种。
所述催化剂还包括无定型羟基氧化铁，和/或负载有第二活性组分的生物质碳，所述第二活性组分选自Mo、W、Fe、Co、Ni或Pd的氧化物中的一种或多种；
在所述催化剂中，上述催化剂可以单一使用，也可以混合使用，当混合使用时，所述羟基氧化铁与所述负载有第二活性组分的生物质碳的质量比为0.5～5。
本发明中的硫化剂具体可以是硫磺，也可以是二甲基硫醚，但并不局限于此，任何可使催化剂中的活性组分由氧化物转化为相应硫化物的化合物均可用作本发明的硫化 剂。在本发明中，硫化剂的用量为催化剂质量的4～10wt％。
所述生物质的含量为10～50wt％，优选为30～40wt％。
一种生物质的水解加氢工艺，所述催化剂的用量为所述生物质质量的1～10wt％，优选为1～4wt％；所述催化剂的粒径为5μm-500μm。
所述浆液的配制方法为：
将所述催化剂和所述硫化剂分别加入至液态生物质中以形成所述浆液，所述液态生物质选自植物油、动物油、地沟油或动物粪便中的一种或多种；或者
固体生物质经干燥、粉碎及除灰后与所述催化剂和所述硫化剂混合得到混合物，将所述混合物加入至油品中，从而形成所述浆液；所述油品为植物油、动物油、煤焦油、石油或本工艺制得的生物油中的一种或多种；
本发明中的固体生物质原料可以是麦子、水稻、玉米、棉花等农作物的秸秆，也可以是芦苇、竹黄草、树木、树叶、瓜果蔬菜等经济作物，还可以是藻类、工业上的木质、纸质废弃物等；可以是一种生物质也可以是多种生物质共同组成的生物质原料。
经干燥后的固体生物质的含水量为3～15wt％，优选为5～10wt％；
经粉碎后的固体生物质的粒度为1～5000μm，优选为20～1500μm。
所述通入氢气的具体方法为：
向所述浆液中注入高压氢气，并控制所述高压氢气与所述浆液的体积比为(600～1500)：1，从而形成反应原料；
将所述反应原料升温至320～450℃后送入浆态床反应器内以发生水解、裂化及加氢反应，同时向所述浆态床反应器内注入冷氢，控制所述浆态床反应器内的总气速为0.02～0.2m/s，优选为0.05～0.08m/s；
其中，所述高压氢气的压力为13～27MPa，所述冷氢的温度为60～135℃。
将所述高压氢气分两次注入至所述浆液中，具体为：
在向所述浆液中第一次注入所述高压氢气，直至所述高压氢气与所述浆液的体积比为50-200:1，而后将所述浆液升温至200～350℃，再向所述浆液中第二次注入所述高压氢气。
所述冷氢经由所述浆态床反应器侧壁上的沿高度方向依次设置的3～5个注入口注入。
所述催化剂在所述浆态床反应器内的存量控制在所述浆态床反应器内液相质量的5～30wt％；
所述反应的时间为15～90min。
负载有第二活性组分的生物质炭的制备方法：
S1、干馏生物质炭经酸化或碱化处理后，制得生物质炭载体；
S2、将第二活性组分和所述生物质炭载体混合研磨，制得负载有第二活性组分的生物质炭。
所述第二活性组分为负载有Mo、W、Fe、Co、Ni或Pd的氧化物中的一种，以金属元素质量计，所述第二活性组分占所述第二生物质炭载体质量的1％～5％。
所述将第二活性组分和所述第二生物质炭载体混合研磨步骤为：将所述第二活性组分和所述第二生物质炭载体经振动研磨和/或平面研磨和/或球磨得到粒径为5μm～500μm的负载有第二活性组分的生物质炭。
所述酸化处理的酸性介质中H +的物质的量浓度为0.5mol/L～5mol/L；所述干馏生物质炭与所述酸性介质体积比为1:5～1:15，酸化温度为30～80℃，酸化时间为1h～10h；所述碱化处理的碱性介质中OH -的物质的量浓度为0.5mol/L～5mol/L；所述干馏生物质炭与所述碱性介质体积比为1:5～1:15，碱化温度为30℃～80℃，碱化时间为1h～10h。
本发明还提供第三种技术方案：
一种生物质的一锅法液化工艺，包括如下步骤：
配制含有催化剂、硫化剂和生物质的浆液，向所述浆液中通入氢气以发生反应，并控制反应压力为15-25MPa、反应温度为380-480℃，最终制得生物油；
所述生物质为植物油渣，所述浆液的配制步骤为，将植物油渣依次进行干燥、初粉碎、压缩和二次粉碎，得到预处理生物质，而后将所述预处理生物质与所述催化剂和硫化剂混合得到混合物，将所述混合物加入至油品中研磨制浆，得到植物油渣浓度为50-65wt％的所述浆液。
本发明中的植物油渣可以是棕榈油渣、大豆油渣、花生油渣、皂角油渣、亚麻油渣、蓖麻油渣、菜子油渣或橄榄油渣中的一种或多种等；
所述浆液的配制步骤中，将所述植物油渣进行压缩的压力为3-5MPa、温度为40-60℃。
所述浆液的配制步骤中，所述植物油渣的干燥温度为80-110℃、时间为2-6h，所述植物油渣干燥后的含水率低于2wt％；初粉碎后中位粒度为100-300μm；经二次粉碎后中位粒度为30-50μm、二次粉碎后堆密度为1500-1600kg/m 3。
所述浆液的粘度为300-700mPa﹒s(50℃)。
所述研磨制浆为搅拌制浆、分散制浆、乳化制浆、剪切制浆或均质制浆。
本发明中的硫化剂可为硫磺、二硫化碳或二甲基二硫醚。
所述浆液的配制步骤中的油品，催化剂的种类，催化剂的用量，向所述浆液中通入氢气的具体方法，冷氢的注入，所述催化剂在所述浆态床反应器内的存量，反应时间，负载有活性组分的生物质炭的制备方法等均与本发明提供的第一种技术方案相同。
本发明还提供第四种技术方案：
一种生物质的一锅法液化工艺，包括如下步骤：
配制含有催化剂、硫化剂和生物质的浆液，向所述浆液中通入氢气以发生反应，并控制反应压力为15-20MPa、反应温度为300-400℃，最终制得生物油；
所述生物质为秸秆，所述浆液的配制步骤为，将秸秆依次进行干燥、初粉碎、压缩和二次粉碎，得到预处理生物质，而后将所述预处理生物质与所述催化剂和所述硫化剂混合得到混合物，将所述混合物加入至水中研磨制浆，得到秸秆浓度为35-50wt％的所述浆液；
所述浆液的配制步骤中，将所述秸秆进行压缩的压力为2～5MPa、温度为30-60℃。
所述浆液的配制步骤中，所述秸秆的干燥温度为70-110℃、时间为3-5h，所述秸秆干燥后的含水率低于2wt％；初粉碎后的中位粒度为100-300μm；经二次粉碎后的中位粒度为30-50μm、二次粉碎后堆密度为400-800kg/m 3。
所述浆液的粘度为400-800mPa﹒s(50℃)。
所述研磨制浆为搅拌制浆、分散制浆、乳化制浆、剪切制浆或均质制浆。
向所述浆液中通入氢气的具体方法为：
向所述浆液中注入高压氢气，并控制所述高压氢气与所述浆液的体积比为 (600～1500)：1，从而形成反应原料；
将所述反应原料升温至300-400℃后送入浆态床反应器内以发生水解、裂化及加氢反应，同时向所述浆态床反应器内注入冷氢，控制所述浆态床反应器内的总气速为0.02～0.2m/s，优选为0.05～0.08m/s；
其中，所述高压氢气的压力为15～22MPa，所述冷氢的温度为60～135℃。
将所述高压氢气分两次注入至所述浆液中，具体为：
在向所述浆液中第一次注入所述高压氢气，直至所述高压氢气与所述浆液的体积比为50-200:1，而后将所述浆液升温至200～280℃，再向所述浆液中第二次注入所述高压氢气。
所述冷氢经由所述浆态床反应器侧壁上的沿高度方向依次设置的3～5个注入口注入。
所述催化剂在所述浆态床反应器内的存量控制在所述浆态床反应器内液相质量的5～30wt％；所述反应的时间为30～60min。
本发明中的硫化剂可为硫磺、二硫化碳或二甲基二硫醚。
所述催化剂的种类，催化剂的用量，负载有活性组分的生物质炭的制备方法等均与本发明提供的第一种技术方案相同。
本发明还提供第五种技术方案：
一种生物质的一锅法液化工艺，包括如下步骤：
配制含有催化剂、硫化剂和生物质的浆液，向所述浆液中通入氢气以发生反应，并控制反应压力为15-20MPa、反应温度为340-420℃，最终制得生物油；
所述生物质为植物油渣，所述浆液的配制步骤为，将植物油渣依次进行干燥、初粉碎、压缩和二次粉碎，得到预处理生物质，而后将所述预处理生物质与所述催化剂和所述硫化剂混合得到混合物，将所述混合物加入至水中研磨制浆，得到植物油渣浓度为40-50wt％的所述浆液；
所述浆液的配制步骤中，将所述植物油渣进行压缩的压力为0.5-3MPa、温度为30-50℃。
所述浆液的配制步骤中，所述植物油渣的干燥温度为80-110℃、时间为2-6h，所述植物油渣干燥后的含水率低于2wt％；初粉碎后的中位粒度为50-300μm；经二次粉碎后的中位粒度为30-50μm、二次粉碎后堆密度为1400-1600kg/m 3。
所述浆液的粘度为300-650mPa﹒s(50℃)。
所述研磨制浆为搅拌制浆、分散制浆、乳化制浆、剪切制浆或均质制浆。
向所述浆液中通入氢气的具体方法为：
向所述浆液中注入高压氢气，并控制所述高压氢气与所述浆液的体积比为(600～1500)：1，从而形成反应原料；
将所述反应原料升温至340-420℃后送入浆态床反应器内以发生水解、裂化及加氢反应，同时向所述浆态床反应器内注入冷氢，控制所述浆态床反应器内的总气速为0.02～0.2m/s，优选为0.05～0.08m/s；
其中，所述高压氢气的压力为15～22MPa，所述冷氢的温度为60～135℃。
将所述高压氢气分两次注入至所述浆液中，具体为：
在向所述浆液中第一次注入所述高压氢气，直至所述高压氢气与所述浆液的体积比为50-200:1，而后将所述浆液升温至200～280℃，再向所述浆液中第二次注入所述高压氢气。
所述催化剂在所述浆态床反应器内的存量控制在所述浆态床反应器内液相质量的5～30wt％；所述反应的时间为30～60min。
本发明中的硫化剂可为硫磺、二硫化碳或二甲基二硫醚。
所述催化剂的种类，催化剂的用量，冷氢的注入，负载有活性组分的生物质炭的制备方法等均与本发明提供的第一种技术方案相同。
本发明还提供第六种技术方案：
一种煤与生物质的一锅法液化工艺，包括如下步骤：
生物质煤浆料的配制：
收集生物质并控制含水率低于2wt％，然后粉碎至中位粒径为100～300μm；
将粉碎后的生物质进行压缩成型，压缩压力为2～5MPa，压缩温度为30～60℃；
将压缩成型后的生物质再次粉碎处理，粉碎至中位粒径为30～50μm，得生物质粉末；
收集煤并控制含水率低于2wt％，然后粉碎至中位粒径为50～100μm，压缩温度为30～60℃；
对粉碎后的煤进行压缩成型，压缩压力为5～15MPa；
对压缩成型后的煤再次粉碎处理，粉碎至中位粒径为30～50μm，得煤粉；
将所述生物质粉末、所述煤粉、催化剂、硫化剂与油品按比例进行配比混合、研磨制浆得到生物质煤浆料，所述生物质粉末和所述煤粉共占所述生物质煤浆料的60～70wt％；
液化反应：向所述生物质煤浆料中通入氢气以发生反应，并控制反应压力为15～25MPa、反应温度为380～460℃，最终制得生物油；
在生物质煤浆料的配制步骤中，进行所述混合时，为先将所述生物质粉末和所述煤粉进行除灰并与所述催化剂和硫化剂进行预混合后，再将所得预混料与所述油品混合，或者，为直接将所述生物质粉末、所述煤粉、所述催化剂与所述油品混合。
所述生物质煤浆料中，生物质的浓度为20～30wt％，煤粉的浓度为30～45wt％。
采用烘干脱水控制含水率，所述烘干脱水温度均为50～70℃，烘干脱水时间为3～5h。
所述压缩成型为压块成型、压片成型或压条成型。所述压缩成型为压块成型、压片成型或压条成型。
生物质煤浆料的配制步骤中控制所述生物质粉末的堆密度为300～500kg/m 3，控制所述煤粉的堆密度为1000～1200kg/m 3。
所述粉碎为锤片式磨粉碎、球磨粉碎、棒磨粉碎、超微粉碎或气流粉碎。
所述研磨制浆为搅拌制浆、分散制浆、乳化制浆、剪切制浆、均质制浆或胶体磨制浆。
所述研磨制浆的时间为2～8min。
所述生物质煤浆料的粘度为550～1000mPa·s(50℃)。
所述煤为低阶煤；所述油品为潲水油、地沟油、酸败油、废润滑油、废机油、重油、渣油、洗油、蒽油、煤焦油、石油、或本工艺制得的生物油中的一种或多种。
所述催化剂的用量为所述生物质与煤的用量总和的1～10wt％，优选为1～4wt％；所述催化剂的粒径为5～500μm。
所述通入氢气的具体方法为：
向所述生物质煤浆料中注入高压氢气，并控制所述高压氢气与所述生物质煤浆料的体积比为(600～1500)：1，从而形成反应原料；
将所述反应原料升温至320～450℃后送入浆态床反应器内以发生液化、裂化及加氢反应，同时向所述浆态床反应器内注入冷氢，控制所述浆态床反应器内的总气速为0.02～0.2m/s，优选为0.05～0.08m/s；
其中，所述高压氢气的压力均为13～27MPa，所述冷氢的温度为60～135℃。
将所述高压氢气分两次注入至所述生物质煤浆料中，具体为：
向所述生物质煤浆料中第一次注入所述高压氢气，直至所述高压氢气与所述生物质煤浆料的体积比为50～200:1，而后将所述生物质煤浆料升温至200～350℃，而后再向所述生物质煤浆料中第二次注入所述高压氢气。
所述冷氢经由所述浆态床反应器侧壁上沿高度方向依次设置的3～5个注入口注入。
所述催化剂在所述浆态床反应器内的存量控制在所述浆态床反应器内液相质量的5～30wt％；
所述反应的时间为30～90min。
本发明中所用的生物质可以为固态的，例如麦子、水稻、玉米、棉花等农作物的秸秆，也可以是芦苇、竹黄草、树木、树叶、瓜果蔬菜等经济作物，还可以是藻类、工业上的木质、纸质废弃物等；也可以为液态的，如液态粪便等；可以为一种生物质也可以是多种生物质共同组成的生物质原料。
其中，所述催化剂种类、组成，硫化剂种类，负载有第二活性组分的生物质炭的制备方法与第二种技术方案相同。
本发明还提供第七种技术方案：
一种煤与生物质的一锅法液化工艺，包括以下步骤，
生物质水煤浆的配制：
收集生物质并控制含水率低于2wt％，然后粉碎至中位粒径为100～300μm；
将粉碎后的生物质进行压缩成型，压缩压力为2～5MPa，压缩温度为30～60℃；
将压缩成型后的生物质再次粉碎处理，粉碎至中位粒径为30～50μm，得生物质粉末；
收集煤并控制含水率低于2wt％，然后粉碎至中位粒径为50～100μm，压缩温度为30～60℃；
对粉碎后的煤进行压缩成型，压缩压力为5～15MPa；
对圧缩成型后的煤再次粉碎处理，粉碎至中位粒径为30～100μm，得煤粉；
将所述生物质粉末、所述煤粉、催化剂、硫化剂与水混合、研磨制浆得到生物质水 煤浆，所述生物质粉末和所述煤粉共占所述生物质水煤浆的55～65wt％；
液化反应：向所述生物质水煤浆中通入氢气以发生反应，并控制反应压力为15～25MPa、反应温度为300～460℃，最终制得生物油；
在生物质水煤浆的配制步骤中，进行所述混合时，为先将所述生物质粉末和所述煤粉进行除灰并与所述催化剂和硫化剂进行预混合后，再将所得预混料与所述水混合，或者，为直接将所述生物质粉末、所述煤粉、所述催化剂与所述水混合。
所述生物质水煤浆中，生物质的浓度为15～30wt％，煤粉的浓度为35～50wt％。
采用烘干脱水控制含水率，所述烘干脱水温度均为50～70℃，烘干脱水时间为3～5h。
生物质水煤浆的配制步骤中控制所述生物质粉末的堆密度为300～500kg/m 3，控制所述煤粉的堆密度为1200～1300kg/m 3。
所述研磨制浆的时间为2～8min。
所述煤为低阶煤。
在所述生物质水煤浆中，所述催化剂的用量为所述生物质与煤的用量总和的1～10wt％，优选为1～4wt％；所述催化剂的粒径为5～500μm。
其中，所述通入氢气的具体方法，催化剂在浆态床反应器内的存量，反应的时间，催化剂的种类、组成，硫化剂的种类，生物质的种类和负载有第二活性组分的生物质炭的制备方法均与第六种技术方案相同。
本发明的上述技术方案具有如下优点：
1、本发明提供的第一种生物质的一锅法液化工艺，其浆液的配制步骤为，将秸秆依次进行干燥、初粉碎、压缩和二次粉碎，而后与催化剂、硫化剂混合得到混合物，将上述混合物加入至油品中研磨制浆，得到秸秆浓度为30～60wt％的浆液，本发明首创性的将秸秆进行了先压缩后二次粉碎的处理工艺，通过将生物质进行压缩处理，使松散的秸秆先后经历坍塌、闭合等重新排位、机械变形的阶段，使得秸秆的体积大幅度降低，由此可减少秸秆的孔隙率，增大其密度和比重，使之有利于分散在油品中，并可提高其在油品中的含量，增加了反应物料的浓度，本发明秸秆在浆液中的含量可高达30～60wt％，远远高于现有技术中的5～16wt％，同时由于浆液中生物质浓度的增加也必然会提高泵在单位时间内对生物质的输送量，从而提高整个生物质液化工艺的效率、降低了工业成本和能耗；此外，秸秆比重的增加还有利于生物质在浆液中的悬浮与分散，由此可降低生物质浆液的粘度，实现了生物质成浆后的浆液在管道中的顺利流动，避免了管道的堵塞，实现了泵的平稳运转与输送，同时也使得现有技术中不能作为生物质液 化溶剂的高粘度废油，例如废机油、地沟油、酸败油等，也能够得到利用。
本发明提供的第二种生物质的一锅法液化工艺，首先通过配制含有催化剂、硫化剂和生物质的浆液，再向所述浆液中通入氢气以发生反应，并控制反应压力为13～25MPa、反应温度为300～500℃，最终制得生物油；本发明的工艺在适量水(即生物质自身所含的水)的存在下使得生物质发生高压高温水解，并在临氢及以负载有第VIB、VIIB或VIII族金属氧化物的无定型氧化铝为催化剂的作用下，水解产物进一步发生裂化、加氢反应，从而实现由生物质向生物油的转化。在本发明所述的工艺中，生物质转化率高达90～100％，生物油的收率在60～86％以上，且生焦量不足0.1％。
本发明提供的第三种生物质的一锅法液化工艺，其浆液的配制步骤为，将植物油渣依次进行干燥、初粉碎、压缩和二次粉碎，而后与催化剂、硫化剂混合得到混合物，将上述混合物加入至油品中研磨制浆，得到植物油渣浓度为50-65wt％的浆液，本发明首创性的将植物油渣进行了先压缩后二次粉碎的处理工艺，通过将生物质进行压缩处理，使松散的植物油渣先后经历坍塌、闭合等重新排位、机械变形的阶段，使得植物油渣的体积大幅度降低，由此可减少植物油渣的孔隙率，增大其密度和比重，使之有利于分散在油品中，并可提高其在油品中的含量，增加了反应物料的浓度，本发明植物油渣在浆液中的含量可高达50-65wt％，同时由于浆液中植物油渣浓度的增加也必然会提高泵在单位时间内对生物质的输送量，从而提高整个生物质液化工艺的效率、降低了工业成本和能耗；此外，植物油渣比重的增加还有利于生物质在浆液中的悬浮与分散，由此可降低生物质浆液的粘度，实现了生物质成浆后的浆液在管道中的顺利流动，避免了管道的堵塞，实现了泵的平稳运转与输送，同时也使得现有技术中不能作为生物质液化溶剂的高粘度废油，例如废机油、地沟油、酸败油等，也能够得到利用。
本发明通过配制含有催化剂、硫化剂和生物质的浆液，再向所述浆液中通入氢气以发生反应，并控制反应压力为15～25MPa、反应温度为380～480℃，本发明的工艺在临氢及催化剂的作用下，使得生物质发生裂化、加氢反应，实现了由生物质向生物油的转化，并提高了生物质的转化率，在本发明工艺中，生物质转化率可高达95-99％。
本发明提供的第四种生物质的一锅法液化工艺，浆液的配制步骤为，将秸秆依次进行干燥、初粉碎、压缩和二次粉碎，而后与催化剂、硫化剂混合得到混合物，将上述混合物加入至水中研磨制浆，得到秸秆浓度为35-50wt％的浆液，本发明首创性的将秸秆进行了先压缩后二次粉碎的处理工艺，通过将生物质进行压缩处理，使松散的秸秆先后经历坍塌、闭合等重新排位、机械变形的阶段，使得秸秆的体积大幅度降低，由此可减 少秸秆的孔隙率，增大其密度和比重，使之有利于分散在水中，并可提高其在水中的含量，增加了反应物料的浓度，同时由于浆液中生物质浓度的增加也必然会提高泵在单位时间内对生物质的输送量，从而提高整个生物质液化工艺的效率、降低了工业成本和能耗；此外，秸秆比重的增加还有利于生物质在浆液中的悬浮与分散，由此可降低生物质浆液的粘度，实现了生物质成浆后的浆液在管道中的顺利流动，避免了管道的堵塞，实现了泵的平稳运转与输送。
本发明通过配制含有催化剂、硫化剂和生物质的浆液，再向所述浆液中通入氢气以发生反应，并控制反应压力为15～20MPa、反应温度为300～400℃，本发明的工艺在临氢及催化剂的作用下，使得生物质发生裂化、加氢反应，实现了由生物质向生物油的转化，并提高了生物油的收率，在本发明工艺中，生物质转化率可高达95-99％，生物油收率为60-80％，生物油中的残渣量在0.1wt％以下。
本发明提供的第五种生物质的一锅法液化工艺，浆液的配制步骤为，将植物油渣依次进行干燥、初粉碎、压缩和二次粉碎，而后与催化剂、硫化剂混合得到混合物，将上述混合物加入至水中研磨制浆，得到秸秆浓度为40-50wt％的浆液，本发明首创性的将秸秆进行了先压缩后二次粉碎的处理工艺，通过将生物质进行压缩处理，使松散的秸秆先后经历坍塌、闭合等重新排位、机械变形的阶段，使得秸秆的体积大幅度降低，由此可减少秸秆的孔隙率，增大其密度和比重，使之有利于分散在水中，并可提高其在水中的含量，增加了反应物料的浓度，同时由于浆液中生物质浓度的增加也必然会提高泵在单位时间内对生物质的输送量，从而提高整个生物质液化工艺的效率、降低了工业成本和能耗；此外，植物油渣比重的增加还有利于生物质在浆液中的悬浮与分散，由此可降低生物质浆液的粘度，实现了生物质成浆后的浆液在管道中的顺利流动，避免了管道的堵塞，实现了泵的平稳运转与输送。
本发明通过配制含有催化剂、硫化剂和生物质的浆液，再向所述浆液中通入氢气以发生反应，并控制反应压力为15～20MPa、反应温度为340-420℃，本发明的工艺在临氢及催化剂的作用下，使得生物质发生裂化、加氢反应，实现了由生物质向生物油的转化，并提高了生物油的收率，在本发明工艺中，生物质转化率可高达95-99％，生物油收率为70-86％，生物油中的残渣量在0.1wt％以下。
本发明提供的第七种技术方案，创造性的首次实现了煤与生物质以水为供氢溶剂的混炼液化。本发明通过对生物质、煤进行脱水、粉碎、压缩、再粉碎、初次成浆、研磨制浆这一工艺流程，并通过对粉碎的粒径和压缩条件的优选，成功制得了生物质和煤含 量达到55～65wt％，而粘度仅为450～1100mPa·s(50℃)的生物质水煤浆。
2、本发明提供的第一种生物质的一锅法液化工艺，通过将压缩温度控制在30-60℃，再此温度下对秸秆进行压缩可显著增强秸秆的流变性，降低生物质浆液的粘度，经测试，本发明工艺中由秸秆和油品形成的浆液的粘度为500-1400mPa﹒s(50℃)，由此实现了生物质成浆后的浆液在管道中的顺利流动，避免了管道的堵塞，实现了泵的平稳运转与输送。
本发明提供的第三种生物质的一锅法液化工艺，通过将压缩温度控制在40-60℃，再此温度下对植物油渣进行压缩可显著增强植物油渣的流变性，降低生物质浆液的粘度，经测试，本发明工艺中由植物油渣和油品形成的浆液的粘度为300-700mPa﹒s(50℃)，由此实现了植物油渣成浆后的浆液在管道中的顺利流动，避免了管道的堵塞，实现了泵的平稳运转与输送。
本发明提供的第四种生物质的一锅法液化工艺，通过将压缩温度控制在30-60℃，再此温度下对秸秆进行压缩可显著增强秸秆的流变性，降低生物质浆液的粘度，经测试，本发明工艺中由秸秆和油品形成的浆液的粘度为400-800mPa﹒s(50℃)，由此实现了生物质成浆后的浆液在管道中的顺利流动，避免了管道的堵塞，实现了泵的平稳运转与输送。
本发明提供的第五种生物质的一锅法液化工艺，通过将压缩温度控制在30-50℃，再此温度下对植物油渣进行压缩可显著增强植物油渣的流变性，降低生物质浆液的粘度，经测试，本发明工艺中由植物油渣和油品形成的浆液的粘度为300-650mPa﹒s(50℃)，由此实现了生物质成浆后的浆液在管道中的顺利流动，避免了管道的堵塞，实现了泵的平稳运转与输送。
本发明提供的第六种技术方案，创造性的首次实现了煤、生物质及油的混炼液化，提供了一种煤与生物质的一锅法液化工艺。本发明通过对生物质、煤进行脱水、粉碎、压缩、再粉碎、初次成浆、研磨制浆这一工艺流程，并通过对粉碎的粒径和压缩条件的优选，成功制得了生物质和煤含量达到60-70wt％，而粘度仅为550-1000mPa·s(50℃)的生物质煤浆料。
本发明提供的第七种技术方案，创造性的首次实现了煤与生物质以水为供氢溶剂的混炼液化。本发明通过对生物质、煤进行脱水、粉碎、压缩、再粉碎、初次成浆、研磨制浆这一工艺流程，并通过对粉碎的粒径和压缩条件的优选，成功制得了生物质和煤含 量达到55～65wt％，而粘度仅为450～1100mPa·s(50℃)的生物质水煤浆。
本发明提供的煤与生物质的一锅法液化工艺，压缩处理能够使得煤与生物质材料内部的孔隙结构坍塌、闭合，发生塑性流变和塑性变形，从而大大提高了煤与生物质原料的密度，使其能够良好的分散于溶剂油中；同时，孔隙结构的坍塌和闭合避免了煤与生物质对溶剂油的吸附，使得溶剂油能够充分发挥其作为分散剂的作用；我们发现，压缩温度对于塑性流变和塑性变形的程度有很大影响，温度越高得到的密度越大，然而温度过高则会导致物料发生分解或带来其他问题，所以采用30～60℃作为压缩时的温度。压缩后的再次粉碎操作，增加了原料的可接触面积，使得原料与催化剂以及溶剂油可更好的接触，能够加强氢的传递，大大减少原料因处于孔隙状结构内而无法与氢和催化剂接触从而反应的情况。
本发明提供的“粉碎+压缩+再次粉碎”能够适用于所有内部具有孔隙结构的煤材料和生物质材料，尤其是对褐煤等低阶煤原料，以及秸秆、稻壳等多孔疏松的生物质原料；制得的高浓度生物质煤浆料的成浆性好，流动性高，可直接用泵平稳输送，不仅能够有效提高输送系统运行平稳性、液化装置利用效率和液化效率，满足后续处理工艺的进料要求，还实现了劣质煤与生物质的清洁高效利用；煤与生物质的紧密相邻使得生物质热解所产生的氢可作为煤热解加氢的部分氢源，减少了对氢的消耗。通过本发明提供的共同液化工艺使得现有技术中不能作为煤与生物质液化溶剂的高黏废油，例如废机油、地沟油、酸败油等，也能够得到利用。
本发明提供的第六种技术方案中，通过向所述生物质煤浆料中通入氢气以发生反应，并控制反应压力为13～25MPa、反应温度为300～500℃，最终制得生物油；本发明的工艺使得煤和生物质在高压高温下发生液化，并在临氢及以负载有第VIB、VIIB或VIII族金属氧化物的无定型氧化铝为催化剂的作用下，液化产物进一步发生裂化、加氢反应，从而实现由煤与生物质向生物油的转化。在本发明所述的工艺中，煤与生物质转化率可达90～99％，生物油的收率可达60～80％，且残渣量不高于2.5wt％。本发明提供的第七种技术方案中，通过向所述生物质水煤浆中通入氢气以发生反应，并控制反应压力为15～25MPa、反应温度为300～460℃，最终制得生物油；本发明的工艺在适量水(即生物质与煤自身所含的水)的存在下使得煤和生物质发生高压高温水解，并在临氢及以负载有第VIB、VIIB或VIII族金属氧化物的无定型氧化铝为催化剂的作用下，水解产物进一步发生裂化、加氢反应，从而实现由煤与生物质向生物油的转化。在本发明所述的工艺中，煤与生物质转化率高达90～95％，生物油的收率在70～85％以上，且生焦量不 足5％。
本发明进一步配合对固料进行筛选的过程，能够保证用于配制生物质油煤浆的固体颗粒粒径均一，使所得生物质煤浆料稳定性更好，不易在运输过程中发生沉降，避免了对运输管道的堵塞和对液化设备的损坏。
本发明优选催化剂为负载有第VIB、VIIB或VIII族金属氧化物的无定型氧化铝或生物质炭与无定型氧化铁的组合催化剂，其优点在于：贵金属硫化后有较好的加氢性能，能够避免生焦，生物质炭或无定型氧化铝具有酸性，具备裂解功能；无定型氧化铁具有碱性，能够促进液化反应，并且铁在硫化后，同样具备加氢催化的功能，降低贵金属的消耗。
本发明提供的煤与生物质的一锅法液化工艺，通过将煤与生物质原料进行干燥、压缩、粉碎及除灰等预处理，而后再与催化剂混合，以更好地利用煤和生物质粉体的表面能使得催化剂附着在固体粉体的表面，这样催化剂便可及时地为煤和生物质液化产物提供氢转移，从而确保整个工艺过程中不会产生焦炭缩聚，达到降低残渣量的目的。
3、本发明提供的生物质或煤与生物质的一锅法液化工艺，优选催化剂为无定型羟基氧化铁、负载有活性组分的无定型氧化铝或负载有活性组分的生物质炭的单一催化剂或组合催化剂，其活性组分选自元素周期表第VIB、VIIB或VIII族金属的氧化物中的一种或多种，无定型羟基氧化铁具有碱性，能够促进生物质水解；生物质炭和无定型氧化铝本身具有酸性，具备裂解功能，而被活性组分负载后，增强了催化剂的裂解功能，从而能够避免生物质液化过程中焦炭的产生。
4、本发明提供的生物质或煤与生物质的一锅法液化工艺，通过采用浆态床反应器，先将反应原料由反应器底部送入浆态床反应器中以发生反应，同时再向反应器内注入冷氢，如此在反应器内可以依靠气体、液体、固体各物料的不同比重并配合反应后轻质油品的产量所引起的比重差变化，实现各相态流速的差异性控制，使得生物质原料在反应器内由下至上发生水解、裂化、加氢反应，在此过程中即便比重大的生物质和催化剂固体颗粒随着气体和轻质油品上升，但在上部的冷氢作用下又回返至底部再次参与反应，根据反应器上、中、下部的物料密度适当调整进入反应器的浆液中的氢气含量及冷氢注入量，从而实现未转化的生物质在反应器内部的循环以及催化剂的平衡排出，由此可确保水解、裂化、加氢等反应的充分进行，从而有利于提高生物质转化率和油相收率。
5、本发明提供的生物质或煤与生物质的一锅法液化工艺，通过将高压氢气分两次 注入至浆液中，即在对浆液升温前后各注入一次高压氢气，前一次高压氢气的注入可增大换热器内浆液的扰动，从而避免固体生物质和催化剂的沉积。
6、本发明提供的生物质或煤与生物质的一锅法液化工艺，优选催化剂为负载有第VIB、VIIB或VIII族金属氧化物的无定型氧化铝或生物质碳与无定型氧化铁的组合催化剂，其优点在于：贵金属硫化后有较好的加氢性能，能够避免生焦，生物质碳或无定型氧化铝具有酸性，具备裂解功能；无定型氧化铁具有碱性，能够促进生物质水解，并且铁在硫化后，同样具备加氢催化的功能，降低贵金属的消耗。
7、本发明提供的生物质或煤与生物质的一锅法液化工艺，当生物质原料为固体时需要先对固体生物质进行干燥、粉碎及除灰等预处理，而后再与催化剂混合，以更好地利用生物质粉体的表面能使得催化剂附着在固体生物质粉体的表面，这样催化剂便可及时地为生物质水解产物提供氢转移，从而确保整个工艺过程中不会产生焦炭缩聚，达到降低生焦量的目的。
具体实施方式
下面将对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。此外，下面所描述的本发明不同实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互结合。
实施例1
一种生物质的一锅法液化工艺，包括如下步骤：
生物质的预处理
将麦子秸秆和玉米秸秆送入干燥机中在50℃下干燥5h至含水量低于2wt％，然后送入超微粉碎机进行初粉碎，初粉碎后的中位粒径为100μm，而后将初粉碎后的麦子秸秆和玉米秸秆送入压条机中在30℃的温度、3MPa的压力下进行压缩挤压成型，之后进行二次粉碎处理，经二次粉碎后的中位粒径为30μm，经二次粉碎后的麦子秸秆和玉米秸秆的堆密度为500kg/m 3，备用。
催化剂的制备
S1、生物质炭经酸化处理后，制得生物质炭载体；
S2、将Mo的氧化物和上述生物质炭载体振动研磨，得到粒径为400～500μm的负载有Mo氧化物的生物质炭，即为催化剂；
在上述催化剂中，以Mo质量计，Mo占上述生物质炭载体质量的1％。上述酸化处理的酸性介质中H +的物质的量浓度为5mol/L，上述生物质炭与酸性介质体积比为1:5，酸化温度为80℃，酸化时间为1h。
生物质浆液的配制
将上述预处理生物质、上述制得的催化剂和硫磺混合得到混合物，将上述混合物加入至潲水油和渣油的混合油中搅拌制浆，形成浆液，经检测，该浆液中麦子秸秆和玉米秸秆的总含量为60wt％，该浆液的粘度为500Pa﹒s(50℃)，在上述浆液中，所投加的催化剂为预处理生物质质量的1wt％，所投加的硫化剂为预处理生物质质量的0.4wt％。
液化反应：
向生物质浆液中通入氢气以发生反应，控制反应压力为25MPa、反应温度为380℃，制得生物油；
通入氢气的具体方法为：向浆液中注入高压氢气，并控制高压氢气与浆液的体积比为1500：1，从而形成反应原料；将上述反应原料升温至380℃后送入浆态床反应器内以发生水解、裂化及加氢反应，同时向上述浆态床反应器内注入冷氢，控制浆态床反应器内的总气速为0.2m/s；其中，高压氢气的压力为27MPa，高压冷氢的温度为135℃；
所述冷氢经由浆态床反应器侧壁上的沿高度方向依次设置的3个注入口注入。作为催化剂的负载有Mo氧化物的生物质炭在浆态床反应器内的存量占浆态床反应器内液相质量的30wt％，该液化反应的时间为30min。
实施例2
一种生物质的一锅法液化工艺，包括如下步骤：
生物质的预处理
将棕榈油渣送入干燥机中在80℃下干燥5h至含水量低于2wt％，然后送入超微粉碎机进行初粉碎，初粉碎后的中位粒径为100μm，而后将初粉碎后的棕榈油渣送入压条机中在50℃的温度、5MPa的压力下进行压缩挤压成型，之后进行二次粉碎处理，经二次粉碎后的中位粒径为30μm，经二次粉碎后的棕榈油渣的堆密度为1600kg/m 3，备用。
催化剂的制备
S1、生物质炭经酸化处理后，制得生物质炭载体；
S2、将Mo的氧化物和上述生物质炭载体振动研磨，得到粒径为400～500μm的负载有Mo氧化物的生物质炭，即为催化剂；
在上述催化剂中，以Mo质量计，Mo占上述生物质炭载体质量的1％。上述酸化处理的酸性介质中H +的物质的量浓度为5mol/L，上述生物质炭与酸性介质体积比为1:5，酸化温度为80℃，酸化时间为1h。
生物质浆液的配制
将上述预处理生物质、上述制得的催化剂和硫磺混合得到混合物，将上述混合物加入至潲水油和渣油的混合油中搅拌制浆，形成浆液，经检测，该浆液中棕榈油渣的总含量为60wt％，该浆液的粘度为300Pa﹒s(50℃)，在上述浆液中，所投加的催化剂为预处理生物质质量的1wt％，所投加的硫化剂为预处理生物质质量的0.4wt％。
液化反应：
向生物质浆液中通入氢气以发生反应，控制反应压力为25MPa、反应温度为380℃，制得生物油；
通入氢气的具体方法为：向浆液中注入高压氢气，并控制高压氢气与浆液的体积比为1500：1，从而形成反应原料；将上述反应原料升温至380℃后送入浆态床反应器内以发生水解、裂化及加氢反应，同时向上述浆态床反应器内注入冷氢，控制浆态床反应器内的总气速为0.2m/s；其中，高压氢气的压力为27MPa，高压冷氢的温度为135℃；
所述冷氢经由浆态床反应器侧壁上的沿高度方向依次设置的3个注入口注入。作为催化剂的负载有Mo氧化物的生物质炭在浆态床反应器内的存量占浆态床反应器内液相质量的30wt％，该液化反应的时间为100min。
实施例3
一种生物质的一锅法液化工艺，包括如下步骤：
生物质的预处理
将棉花秸秆送入干燥机中在60℃下干燥4h至含水量低于2wt％，然后送入超微粉碎机进行初粉碎，初粉碎后的中位粒径为210μm，而后将初粉碎后的棉花秸秆送入压块 机中在55℃的温度、2.1MPa的压力下进行压缩挤压成型，之后进行二次粉碎，经二次粉碎后的中位粒径为40μm，经二次粉碎后的棉花秸秆的堆密度为440kg/m 3，备用。
负载有Mo氧化物和Pd氧化物的生物质炭的制备
S1、生物质炭经酸化处理后，制得生物质炭载体；
S2、将Mo的氧化物、Pd的氧化物和上述生物质炭载体经过振动研磨，得到粒径为120-400μm的负载有Mo氧化物和Pd氧化物的生物质炭；
在上述负载有Mo氧化物和Pd氧化物的生物质炭中，以Mo和Pd的总质量计，Mo和Pd的总质量占上述生物质炭载体质量的3.5％。上述酸化处理的酸性介质中H +的物质的量浓度为3.5mol/L，上述生物质炭与酸性介质体积比为1:10，酸化温度为50℃，酸化时间为4.3h。
生物质浆液的配制
将上述预处理生物质、上述制得的负载有Mo氧化物和Pd氧化物的生物质炭、无定型羟基氧化铁和硫磺混合得到混合物，将上述混合物加入至重油和洗油的混合油乳化制浆，形成浆液，经检测，该浆液中棉花秸秆的含量为30wt％，该浆液的粘度为725mPa﹒s(50℃)，在上述浆液中，所投加的负载有Mo氧化物和Pd氧化物的生物质炭和无定型羟基氧化铁(粒径为150-200μm)的总质量为预处理生物质质量的6wt％，所投加的硫化剂为预处理生物质质量的0.2wt％。
液化反应：
向生物质浆液中通入氢气以发生反应，控制反应压力为20MPa、反应温度为400℃，制得生物油；
通入氢气的具体方法为：向浆液中注入高压氢气，并控制高压氢气与浆液的体积比为1000：1，从而形成反应原料；将上述反应原料升温至400℃后送入浆态床反应器内以发生水解、裂化及加氢反应，同时向上述浆态床反应器内注入冷氢，控制浆态床反应器内的总气速为0.10m/s；其中，高压氢气的压力为21MPa，高压冷氢的温度为80℃；
所述冷氢经由浆态床反应器侧壁上的沿高度方向依次设置的4个注入口注入。作为催化剂的负载有Mo氧化物和Pd氧化物的生物质炭在浆态床反应器内的存量占浆态床反应器内液相质量的25wt％，该液化反应的时间为50min。
实施例4
一种生物质的一锅法液化工艺，包括如下步骤：
生物质的预处理
将麦子秸秆和亚麻秸秆送入干燥机中在65℃下干燥4.5h至含水量低于2wt％，然后送入超微粉碎机进行初粉碎处理，初粉碎后的中位粒径为180μm，而后将初粉碎后的麦子秸秆和亚麻秸秆送入压条机中在45℃的温度、2.6MPa的压力下进行压缩挤压成型，之后进行二次粉碎处理，经二次粉碎后的中位粒径为36μm，经二次粉碎后的堆密度为440kg/m 3，备用。
生物质浆液的配制
将上述预处理生物质与无定型羟基氧化铁(其粒度为100-200μm)、二甲基二硫醚混合，得到混合物，将上述混合物加入至酸败油剪切制浆，形成浆液，经检测，该浆液中麦子秸秆和亚麻秸秆的总含量为55wt％，该浆液的粘度为620mPa﹒s(50℃)，在上述浆液中，无定型羟基氧化铁的质量为预处理生物质质量的6wt％，所投加的硫化剂的质量为预处理生物质质量的0.25wt％。
液化反应：
向生物质浆液中通入氢气以发生反应，控制反应压力为17MPa、反应温度为440℃，制得生物油；
通入氢气的具体方法为：向浆液中分两次注入高压氢气，具体为：在向浆液中第一次注入高压氢气，直至高压氢气与浆液的体积比为50:1，而后将上述浆液升温至200℃，再向上述浆液中第二次注入上述高压氢气，并控制两次注入的高压氢气的总体积与浆液的体积比为1300：1，从而形成反应原料；将上述反应原料升温至440℃后送入浆态床反应器内以发生水解、裂化及加氢反应，同时向上述浆态床反应器内注入冷氢，控制浆态床反应器内的总气速为0.05m/s；其中，高压氢气的压力为16MPa，高压冷氢的温度为105℃；
所述冷氢经由浆态床反应器侧壁上的沿高度方向依次设置的4个注入口注入。作为催化剂的无定型羟基氧化铁在浆态床反应器内的存量占浆态床反应器内液相质量的9wt％，该液化反应的时间为110min。
实施例5
一种生物质的一锅法液化工艺，包括如下步骤：
生物质的预处理
将橄榄油渣送入干燥机中在90℃下干燥3h至含水量低于2wt％，然后送入超微粉碎机进行初粉碎处理，初粉碎后的中位粒径为180μm，而后将初粉碎后的橄榄油渣送入压条机中在60℃的温度、3.5MPa的压力下进行压缩挤压成型，之后进行二次粉碎处理，经二次粉碎后的中位粒径为36μm，经二次粉碎后的堆密度为1522kg/m 3，备用。
生物质浆液的配制
将上述预处理生物质与无定型羟基氧化铁(其粒度为100-200μm)、二甲基二硫醚混合，得到混合物，将上述混合物加入至酸败油剪切制浆，形成浆液，经检测，该浆液中橄榄油渣的总含量为55wt％，该浆液的粘度为617mPa﹒s(50℃)，在上述浆液中，无定型羟基氧化铁的质量为预处理生物质质量的6wt％，所投加的硫化剂的质量为预处理生物质质量的0.25wt％。
液化反应：
向生物质浆液中通入氢气以发生反应，控制反应压力为17MPa、反应温度为440℃，制得生物油；
通入氢气的具体方法为：向浆液中分两次注入高压氢气，具体为：在向浆液中第一次注入高压氢气，直至高压氢气与浆液的体积比为50:1，而后将上述浆液升温至200℃，再向上述浆液中第二次注入上述高压氢气，并控制两次注入的高压氢气的总体积与浆液的体积比为1300：1，从而形成反应原料；将上述反应原料升温至440℃后送入浆态床反应器内以发生水解、裂化及加氢反应，同时向上述浆态床反应器内注入冷氢，控制浆态床反应器内的总气速为0.05m/s；其中，高压氢气的压力为16MPa，高压冷氢的温度为105℃；
所述冷氢经由浆态床反应器侧壁上的沿高度方向依次设置的4个注入口注入。作为催化剂的无定型羟基氧化铁在浆态床反应器内的存量占浆态床反应器内液相质量的9wt％，该液化反应的时间为110min。
实施例6
一种生物质的一锅法液化工艺，包括如下步骤：
生物质的预处理
将菜子油渣送入干燥机中在80℃下干燥2h至含水量低于2wt％，然后送入超微粉碎机进行初粉碎，初粉碎后的中位粒径为200μm，而后将初粉碎后的菜子油渣送入压块机中在40℃的温度、3MPa的压力下进行压缩挤压成型，之后进行二次粉碎，经二次粉碎后的生物质的中位粒径为45μm，经二次粉碎后的堆密度为1600kg/m 3，备用。
催化剂的制备
S1、生物质炭经碱化处理后，制得生物质炭载体；
S2、将Ni的氧化物和上述生物质炭载体依次经过平面研磨和球磨，得到粒径为200-400μm的负载有Ni氧化物的生物质炭，即为催化剂；
在上述催化剂中，以Ni质量计，Ni占上述生物质炭载体质量的1％。上述碱化处理的碱性介质中OH -的物质的量浓度为0.5mol/L，上述生物质炭与碱性介质体积比为1:15，碱化温度为30℃，碱化时间为10h。
生物质浆液的配制
将上述预处理生物质与上述制得的催化剂和二硫化碳混合得到混合物，将上述混合物加入至酸败油中剪切制浆，形成浆液，经检测，该浆液中菜子油渣的含量为59wt％，该浆液的粘度为305mPa﹒s(50℃)，在上述浆液中，催化剂的质量为预处理生物质质量的1wt％，所投加的硫化剂的质量为预处理生物质质量的0.25wt％。
液化反应：
向生物质浆液中通入氢气以发生反应，控制反应压力为15MPa、反应温度为380℃，制得生物油；
通入氢气的具体方法为：向浆液中注入高压氢气，并控制高压氢气与浆液的体积比为600：1，从而形成反应原料；将上述反应原料升温至380℃后送入浆态床反应器内以发生水解、裂化及加氢反应，同时向上述浆态床反应器内注入冷氢，控制浆态床反应器内的总气速为0.2m/s；其中，高压氢气的压力为18MPa，高压冷氢的温度为135℃；
所述冷氢经由浆态床反应器侧壁上的沿高度方向依次设置的5个注入口注入。作为催化剂的负载有Ni氧化物的生物质炭在浆态床反应器内的存量占浆态床反应器内液相 质量的30wt％，该液化反应的时间为90min。
实施例7
一种生物质的一锅法液化工艺，包括如下步骤：
生物质的预处理
将水稻秸秆和芦苇秸秆送入干燥机中在70℃下干燥5h至含水量低于2wt％，然后送入超微粉碎机进行初粉碎，初粉碎后的中位粒径为100μm，而后将初粉碎后的水稻秸秆和芦苇秸秆送入压条机中在60℃的温度、2MPa的压力下进行压缩挤压成型，之后进行二次粉碎处理，经二次粉碎后的中位粒径为30μm，经二次粉碎后的水稻秸秆和芦苇秸秆的堆密度为400kg/m 3，备用。
催化剂的制备
S1、生物质炭经酸化处理后，制得生物质炭载体；
S2、将Mo的氧化物和上述生物质炭载体振动研磨，得到粒径为400～500μm的负载有Mo氧化物的生物质炭，即为催化剂；
在上述催化剂中，以Mo质量计，Mo占上述生物质炭载体质量的1％。上述酸化处理的酸性介质中H +的物质的量浓度为5mol/L，上述生物质炭与酸性介质体积比为1:5，酸化温度为80℃，酸化时间为1h。
生物质浆液的配制
将上述预处理生物质、上述制得的催化剂和硫磺混合得到混合物，将上述混合物加入至水中搅拌制浆，形成浆液，经检测，该浆液中水稻秸秆和芦苇秸秆的总含量为50wt％，该浆液的粘度为800mPa﹒s(50℃)，在上述浆液中，所投加的催化剂为预处理生物质质量的1wt％，所投加的硫磺为预处理生物质质量的0.4wt％。
液化反应：
向生物质浆液中通入氢气以发生反应，控制反应压力为20MPa、反应温度为300℃，制得生物油；
通入氢气的具体方法为：向浆液中注入高压氢气，并控制高压氢气与浆液的体积比为1500：1，从而形成反应原料；将上述反应原料升温至320℃后送入浆态床反应器内以发生水解、裂化及加氢反应，同时向上述浆态床反应器内注入冷氢，控制浆态床反应 器内的总气速为0.2m/s；其中，高压氢气的压力为22MPa，高压冷氢的温度为135℃；
所述冷氢经由浆态床反应器侧壁上的沿高度方向依次设置的3个注入口注入。作为催化剂的负载有Mo氧化物的生物质炭在浆态床反应器内的存量占浆态床反应器内液相质量的30wt％，该液化反应的时间为30min。
实施例8
一种生物质的一锅法液化工艺，包括如下步骤：
生物质的预处理
将橄榄油渣送入干燥机中在100℃下干燥4.0h至含水量低于2wt％，然后送入超微粉碎机进行初粉碎处理，初粉碎后的中位粒径为290μm，而后将初粉碎后的橄榄油渣送入压条机中在35℃的温度、2.7MPa的压力下进行压缩挤压成型，之后进行二次粉碎处理，经二次粉碎后的中位粒径为44μm，经二次粉碎后的堆密度为1510kg/m 3，备用。
生物质浆液的配制
将上述预处理生物质与无定型羟基氧化铁(其粒度为100-200μm)、硫磺混合，得到混合物，将上述混合物加入水中剪切制浆，形成浆液，经检测，该浆液中橄榄油渣的含量为50wt％，该浆液的粘度为465mPa﹒s(50℃)，在上述浆液中，无定型羟基氧化铁的质量为预处理生物质质量的6wt％，所投加的硫化剂的质量为预处理生物质质量的0.25wt％。
液化反应：
向生物质浆液中通入氢气以发生反应，控制反应压力为18MPa、反应温度为340℃，制得生物油；
通入氢气的具体方法为：向浆液中分两次注入高压氢气，具体为：在向浆液中第一次注入高压氢气，直至高压氢气与浆液的体积比为50:1，而后将上述浆液升温至200℃，再向上述浆液中第二次注入上述高压氢气，并控制两次注入的高压氢气的总体积与浆液的体积比为1300：1，从而形成反应原料；将上述反应原料升温至340℃后送入浆态床反应器内以发生水解、裂化及加氢反应，同时向上述浆态床反应器内注入冷氢，控制浆态床反应器内的总气速为0.05m/s；其中，高压氢气的压力为20MPa，高压冷氢的温度为105℃；
所述冷氢经由浆态床反应器侧壁上的沿高度方向依次设置的4个注入口注入。作为催化剂的无定型羟基氧化铁在浆态床反应器内的存量占浆态床反应器内液相质量的9wt％，该液化反应的时间为40min。
实施例9
一种生物质的一锅法液化工艺，包括如下步骤：
生物质的预处理
将大豆油渣送入干燥机中在95℃下干燥3.5h至含水量低于2wt％，然后送入超微粉碎机进行初粉碎及除灰处理，初粉碎后的中位粒径为110μm，而后将初粉碎后的大豆油渣送入压条机中在38℃的温度、2.5MPa的压力下进行压缩挤压成型，之后进行二次粉碎处理，经二次粉碎后的中位粒径为50μm，经二次粉碎后的堆密度为1500kg/m 3，备用。
生物质浆液的配制
将上述预处理生物质与负载有Mn氧化物和Pd氧化物的无定型氧化铝(粒度为200-500μm)、无定型羟基氧化铁和硫磺混合，得到混合物，将上述混合物加入至水中搅拌制浆；形成浆液，经检测，该浆液中大豆油渣的含量为42wt％，该浆液的粘度为481mPa﹒s(50℃)，在上述浆液中，负载有Mn氧化物和Pd氧化物的无定型氧化铝和无定型羟基氧化铁的总质量为预处理生物质质量的3wt％，所投加的硫磺的质量为预处理生物质质量的0.4wt％。
液化反应：
向生物质浆液中通入氢气以发生反应，控制反应压力为20MPa、反应温度为420℃，制得生物油；
通入氢气的具体方法为：向浆液中分两次注入高压氢气，具体为：在向浆液中第一次注入高压氢气，直至高压氢气与浆液的体积比为100:1，而后将上述浆液升温至250℃，再向上述浆液中第二次注入上述高压氢气，并控制两次注入的高压氢气的总体积与浆液的体积比为1050：1，从而形成反应原料；将上述反应原料升温至420℃后送入浆态床反应器内以发生水解、裂化及加氢反应，同时向上述浆态床反应器内注入冷氢，控制浆态床反应器内的总气速为0.07m/s；其中，高压氢气的压力为21MPa，高压冷氢的温度为105℃；
所述冷氢经由浆态床反应器侧壁上的沿高度方向依次设置的3个注入口注入。作为催化剂的无定型羟基氧化铁在浆态床反应器内的存量占浆态床反应器内液相质量的27wt％，该液化反应的时间为35min。
实施例10
一种生物质的一锅法液化工艺，包括如下步骤：
生物质的预处理
将麦子秸秆送入干燥机中在50℃下干燥5h至含水量低于2wt％，然后送入超微粉碎机进行初粉碎，初粉碎后的中位粒径为100μm，而后将初粉碎后的麦子秸秆送入压条机中在30℃的温度、3MPa的压力下进行压缩挤压成型，之后进行二次粉碎处理，经二次粉碎后的中位粒径为30μm，经二次粉碎后的麦子秸秆的堆密度为500kg/m 3，备用。
催化剂的制备
S1、生物质炭经酸化处理后，制得生物质炭载体；
S2、将Mo的氧化物和上述生物质炭载体振动研磨，得到粒径为400～500μm的负载有Mo氧化物的生物质炭，即为催化剂；
在上述催化剂中，以Mo质量计，Mo占上述生物质炭载体质量的1％。上述酸化处理的酸性介质中H +的物质的量浓度为5mol/L，上述生物质炭与酸性介质体积比为1:5，酸化温度为80℃，酸化时间为1h。
生物质浆液的配制
将上述预处理生物质、上述制得的催化剂和硫磺混合得到混合物，将上述混合物加入至潲水油和渣油的混合油中搅拌制浆，形成浆液，经检测，该浆液中麦子秸秆的总含量为55wt％，该浆液的粘度为500Pa﹒s(50℃)，在上述浆液中，所投加的催化剂为预处理生物质质量的1wt％，所投加的硫化剂为预处理生物质质量的0.4wt％。
液化反应：
向生物质浆液中通入氢气以发生反应，控制反应压力为25MPa、反应温度为380℃，制得生物油；
通入氢气的具体方法为：向浆液中注入高压氢气，并控制高压氢气与浆液的体积比为1500：1，从而形成反应原料；将上述反应原料升温至380℃后送入浆态床反应器内 以发生水解、裂化及加氢反应，同时向上述浆态床反应器内注入冷氢，控制浆态床反应器内的总气速为0.2m/s；其中，高压氢气的压力为27MPa，高压冷氢的温度为135℃；
所述冷氢经由浆态床反应器侧壁上的沿高度方向依次设置的3个注入口注入。作为催化剂的负载有Mo氧化物的生物质炭在浆态床反应器内的存量占浆态床反应器内液相质量的30wt％，该液化反应的时间为30min。
实验例
对本发明上述实施例1～9所提供工艺的效果进行评价，结果分别如表1所示。
表1 实施例1-9的产物分布对比
Figure PCTCN2018122665-appb-000001
从表1可以看出，采用本发明的方法得到的生物质转化率为95-99％，油相收率为60-86％，残渣量小于0.1wt％，且得到的油相中碳含量为80-90wt％、氢含量为9-19wt％，氧含量为0.1-3wt％。
实施例11
本实施例提供了一种第二催化剂的制备方法，包括如下步骤：
S1、干馏生物质炭经酸化或碱化处理后，制得第二生物质炭载体；具体为：所述酸化处理的酸性介质中H +的物质的量浓度为5mol/L；所述干馏生物质炭与所述酸性介质体积比为1:15，酸化温度为80℃，酸化时间为10h；所述碱化处理的碱性介质中OH -的物质的量浓度为0.5mol/L；所述干馏生物质炭与所述碱性介质体积比为1:5，碱化温度为30℃，碱化时间为10h。
S2、将所述第二活性组分和所述第二生物质炭载体经振动研磨和/或平面研磨和/或球磨得到粒径为100μm～200μm的第二催化剂。
所述第二活性组分为负载有Mo和W的氧化物，以金属元素质量计，所述第二活性组分占所述第二生物质炭载体质量的5％。
实施例12
本实施例提供的生物质的一锅法液化工艺包括如下步骤：
(1)将玉米秸秆送入干燥机中干燥至含水量为3wt％，而后在粉碎机中粉碎至粒度为1～50μm，再经除灰后得到秸秆颗粒；
(2)将负载有Mo氧化物和Co氧化物的无定型氧化铝(其粒径为5μm-50μm)与步骤(1)的秸秆颗粒及硫磺按质量比为5：100：0.3的比例混匀得到混合物，将该混合物加入至中低温煤焦油中形成含生物质10wt％的浆液；
(3)向所述浆液中第一次注入60℃、13MPa的氢气至高压氢气与浆液的体积比为50：1，而后在换热器中将该浆液升温至200℃，再向其中第二次注入200℃、13MPa的氢气，并控制这两次注入的氢气与浆液的体积比达到800：1以形成反应原料，再将该反应原料升温至450℃后送入浆态床反应器中，在反应压力为13MPa、反应温度为500℃的条件下发生水解、裂化及加氢反应，并在此反应过程中通过反应器侧壁上的沿高度方向依次设置的3个注入口注入105℃的冷氢，控制反应器内的总气速为0.02m/s及催化剂在反应器内的存量为反应器内液、固相质量的30wt％，待反应90min后，将从浆态床反应器排出的物料送入分离系统进行气、液、残渣三相分离，分别得到生物质气体、生物油及残渣；系统中的氢气循环使用，与新鲜的补充氢气一同进入步骤(3)的各个注氢点。
实施例13
本实施例提供的生物质的一锅法液化工艺包括如下步骤：
(1)将芦苇送入干燥机中干燥至含水量为5wt％，而后在粉碎机中粉碎至粒度为20～1000μm，再经除灰后得到芦苇颗粒；
(2)将负载有W氧化物和Ni氧化物的生物质炭(其粒径为100μm-150μm)以及无定型羟基氧化铁与步骤(1)的芦苇颗粒及硫磺按质量比为2：2：100：0.4的比例混匀得到混合物，将该混合物加入至植物油中形成含生物质30wt％的浆液；
(3)向所述浆液中第一次注入70℃、20MPa的氢气至高压氢气与浆液的体积比为100：1，而后在换热器中将该浆液升温至250℃，再向其中第二次注入250℃、20MPa的氢气，并控制这两次注入的氢气与浆液的体积比达到900：1以形成反应原料，再将该反应原料升温至430℃后送入浆态床反应器中，在反应压力为20MPa、反应温度为450℃的条件下发生水解、裂化及加氢反应，并在此反应过程中通过反应器侧壁上的沿高度方向依次设置的4个注入口注入120℃的冷氢，控制反应器内的总气速为0.06m/s及催化剂在反应器内的存量为反应器内液、固相质量的25wt％，待反应60min后，将从浆态床反应器排出的物料送入分离系统进行气、液、残渣三相分离，分别得到生物质气体、生物油及残渣；系统中的氢气循环使用，与新鲜的补充氢气一同进入步骤(3)的各个注氢点。
实施例14
本实施例提供的生物质的一锅法液化工艺包括如下步骤：
(1)将麦子秸秆送入干燥机中干燥至含水量为7wt％，而后在粉碎机中粉碎至粒度为1500～2000μm，再经除灰后得到秸秆颗粒；
(2)将负载有Pd氧化物和Ni氧化物的生物质碳(其粒径为50μm-100μm)以及无定型羟基氧化铁与步骤(1)的秸秆颗粒及硫磺按质量比为2：3：100：0.3的比例混匀得到混合物，将该混合物加入至低温动物油中形成含生物质25wt％的浆液；
(3)向所述浆液中第一次注入100℃、17MPa的氢气至高压氢气与浆液的体积比为150：1，而后在换热器中将该浆液升温至300℃，再向其中第二次注入300℃、17MPa的氢气，并控制这两次注入的氢气与浆液的体积比达到600：1以形成反应原料，再将该反应原料升温至440℃后送入浆态床反应器中，在反应压力为20MPa、反应温度为 450℃的条件下发生水解、裂化及加氢反应，并在此反应过程中通过反应器侧壁上的沿高度方向依次设置的4个注入口注入90℃的冷氢，控制反应器内的总气速为0.08m/s及催化剂在反应器内的存量为反应器内液、固相质量的20wt％，待反应40min后，将从浆态床反应器排出的物料送入分离系统进行气、液、残渣三相分离，分别得到生物质气体、生物油及残渣；系统中的氢气循环使用，与新鲜的补充氢气一同进入步骤(3)的各个注氢点。
实施例15
本实施例提供的生物质的一锅法液化工艺包括如下步骤：
(1)将木屑送入干燥机中干燥至含水量为10wt％，而后在粉碎机中粉碎至粒度为4000～5000μm，再经除灰后得到木屑颗粒；
(2)将无定型羟基氧化铁(其粒径为150μm-200μm)与步骤(1)的木屑颗粒及硫磺按质量比为10：100：0.2的比例混匀得到混合物，将该混合物加入至低温动物油中形成含生物质40wt％的浆液；
(3)向所述浆液中第一次注入130℃、27MPa的氢气至高压氢气与浆液的体积比为200：1，而后在换热器中将该浆液升温至350℃，再向其中第二次注入300℃、27MPa的氢气，并控制这两次注入的氢气与浆液的体积比达到1000：1以形成反应原料，再将该反应原料升温至300℃后送入浆态床反应器中，在反应压力为27MPa、反应温度为300℃的条件下发生水解、裂化及加氢反应，并在此反应过程中通过反应器侧壁上的沿高度方向依次设置的5个注入口注入115℃的冷氢，控制反应器内的总气速为0.1m/s及催化剂在反应器内的存量为反应器内液相质量的30wt％，待反应50min后，将从浆态床反应器排出的物料送入分离系统进行气、液、残渣三相分离，分别得到生物质气体、生物油及残渣；系统中的氢气循环使用，与新鲜的补充氢气一同进入步骤(3)的各个注氢点。
实施例16
本实施例提供的生物质的一锅法液化工艺包括如下步骤：
(1)将树叶送入干燥机中干燥至含水量为15wt％，而后在粉碎机中粉碎至粒度为4000-5000μm，再经除灰后得到树叶颗粒；
(2)实施例1制备得到的催化剂以及无定型羟基氧化铁与步骤(1)的木屑颗粒及硫磺按质量比为1：0.2：100：0.25的比例混匀得到混合物，将该混合物加入至低温植物油中形成含生物质20wt％的浆液；
(3)向所述浆液中第一次注入135℃、25MPa的氢气至高压氢气与浆液的体积比为200：1，而后在换热器中将该浆液升温至350℃，再向其中第二次注入350℃、25MPa的氢气，并控制这两次注入的氢气与浆液的体积比达到650：1以形成反应原料，再将该反应原料升温至400℃后送入浆态床反应器中，在反应压力为25MPa、反应温度为450℃的条件下发生水解、裂化及加氢反应，并在此反应过程中通过反应器侧壁上的沿高度方向依次设置的5个注入口注入100℃的冷氢，控制反应器内的总气速为0.1m/s及催化剂在反应器内的存量为反应器内液相质量的25wt％，待反应15min后，将从浆态床反应器排出的物料送入分离系统进行气、液、残渣三相分离，分别得到生物质气体、生物油及残渣；系统中的氢气循环使用，与新鲜的补充氢气一同进入步骤(3)的各个注氢点。
对比例
本实验例提供的生物质的一锅法液化工艺包括如下步骤：
(1)将芦苇送入干燥机中干燥至含水量为5wt％，而后在粉碎机中粉碎至粒度为20～1000μm，再经除灰后得到芦苇颗粒；
(2)将负载有W氧化物和Ni氧化物的生物质炭(其粒径为100μm-150μm)以及无定型羟基氧化铁与步骤(1)的芦苇颗粒及硫磺按质量比为2：2：100：0.4的比例混匀得到混合物，将该混合物加入至植物油中形成含生物质30wt％的浆液；
(3)向所述浆液中第一次注入70℃、20MPa的氢气至高压氢气与浆液的体积比为100：1，而后在换热器中将该浆液升温至250℃，再向其中第二次注入250℃、20MPa的氢气，并控制这两次注入的氢气与浆液的体积比达到900：1以形成反应原料，再将该反应原料升温至430℃后送入浆态床反应器中，在反应压力为10MPa、反应温度为200℃的条件下发生水解、裂化及加氢反应，并在此反应过程中通过反应器侧壁上的沿高度方向依次设置的4个注入口注入120℃的冷氢，控制反应器内的总气速为0.06m/s及催化剂在反应器内的存量为反应器内液相质量的25wt％，待反应60min后，将从浆态床反应器排出的物料送入分离系统进行气、液、残渣三相分离，分别得到生物质气体、 生物油及残渣；系统中的氢气循环使用，与新鲜的补充氢气一同进入步骤(3)的各个注氢点。
实验例
对本发明上述实施例12～16和对比例所提供工艺的效果进行评价，结果分别如表1所示。
由表1中可以明确的得出实施例12～16中的生物质转化率、生物质油收率明显优于对比例，而生焦量明显低于对比例；
实施例12～16中的生物质油中的C、H的含量明显高于对比例，而O的含量明显低于对比例；通过实施例12～16与对比例的比较，本发明的公开的生物质的一锅法液化工艺明显优于现有生物质的液化工艺。
表2 工艺效果
Figure PCTCN2018122665-appb-000002
以下是本发明提供的煤与生物质的一锅法液化工艺的实施例，下述各实施例和对比例中所述煤与生物质的转化率、生物油收率以及残渣含量的计算公式如下：
煤与生物质的转化率＝(液化反应产物的质量-硫化剂的质量-催化剂的质量-溶剂油 的质量)/(煤与生物质的质量和)
生物油收率＝液化反应产物进行分离后得到的油相的质量/(煤与生物质的质量和)
残渣含量＝残渣质量/(煤与生物质的质量和)。
实施例17
本实施例提供了一种第二催化剂的制备方法，包括如下步骤：
制备生物质炭载体：
采用H +浓度为5mol/L的酸性介质，于80℃下以15:1的体积比对生物质炭进行酸化处理10h，即得到生物质炭载体；作为另一种替代方式，也可以采用OH -浓度为0.5mol/L的碱性介质，于30℃下以5:1的体积比对生物质炭进行酸化处理10h。
负载第二活性组分：
将Mo与W的氧化物和所述生物质炭载体共同进行振动研磨，即实现活性组分在生物质炭载体上的负载，得到粒径为100μm～200μm的第二催化剂。以金属元素质量计，所述第二活性组分占所述生物质炭载体质量的5％。
实施例18
本实施例提供的煤与生物质的一锅法液化工艺包括如下步骤：
秸秆的预处理：
取玉米秸秆，将其烘干脱水至含水量低于2wt％，粉碎至中位粒径为100μm，然后送入压条机进行挤压成型，成型压力为2MPa，得到秸秆压缩料；
将秸秆压缩料送入锤片粉碎机，进行粉碎，得到粒度为50μm的秸秆粉碎料，待用。
煤原料的预处理：
取褐煤，将其烘干脱水，粉碎至中位粒径为100μm，然后送入压块机进行挤压成型，成型压力为5MPa，得到褐煤压缩料；
将褐煤压缩料送入球磨机，进行粉碎，得到中位粒径为30μm的褐煤粉碎料，待用。
生物质煤浆料的配制和液化反应：
将上述秸秆粉碎料和褐煤粉碎料进行除灰后与负载有Mo氧化物和Co氧化物的无定型氧化铝(其粒径为5μm～50μm)以及硫磺按质量比为100：5：0.3的比例混匀得到混合物，将该混合物加入至酸败油中形成生物质煤浆料；在所述生物质煤浆料中，所述秸秆的含量为20wt％，所述褐煤的含量为45wt％；
向得到的生物质煤浆料中注入相当于其体积50倍的60℃、15MPa的高压氢气，而后在换热器中将该生物质煤浆料升温至200℃，再向其中注入200℃、15MPa的氢气， 并控制这两次注入的氢气与生物质煤浆料的体积比达到800：1以形成反应原料，接着将该反应原料升温至450℃后送入浆态床反应器中，在反应压力为15MPa、反应温度为460℃的条件下发生液化、裂化及加氢反应，并在此反应过程中通过反应器侧壁上的沿高度方向依次设置的3个注入口注入105℃的冷氢，控制反应器内的总气速为0.02m/s及催化剂在反应器内的存量为反应器内液、固相质量的30wt％，待反应70min后，将从浆态床反应器排出的物料送入分离系统进行气、液、固三相分离，分别得到生物质气体、生物油及残渣；系统中的氢气循环使用，与新鲜的补充氢气一同进入上述的各个注氢点。
实施例19
本实施例提供的煤与生物质的一锅法液化工艺包括如下步骤：
秸秆的预处理：
取玉米秸秆，将其烘干脱水至含水量为1wt％，粉碎至中位粒径为100μm，然后送入压条机进行挤压成型，成型压力为2MPa，得到秸秆压缩料；
将秸秆压缩料送入锤片粉碎机，进行粉碎，得到粒度为50μm的秸秆粉碎料，待用。
煤原料的预处理：
取褐煤，将其烘干脱水，粉碎至中位粒径为50μm，然后送入压块机进行挤压成型，成型压力为5MPa，得到褐煤压缩料；
将褐煤压缩料送入球磨机，进行粉碎，得到中位粒径为30μm的褐煤粉碎料，待用。
生物质水煤浆的配制和液化反应：
将上述秸秆粉碎料和褐煤粉碎料进行除灰后与负载有Mo氧化物和Co氧化物的无定型氧化铝(其粒径为5μm-50μm)以及硫磺按质量比为100：5：0.3的比例混匀得到混合物，将该混合物加入至水中形成生物质水煤浆；在所述生物质水煤浆中，所述秸秆的含量为15wt％，所述褐煤的含量为40wt％；
向得到的生物质水煤浆中注入相当于其体积50倍的60℃、13MPa的高压氢气，而后在换热器中将该生物质水煤浆升温至200℃，再向其中注入200℃、13MPa的氢气，并控制这两次注入的氢气与生物质水煤浆的体积比达到800：1以形成反应原料，接着将该反应原料升温至450℃后送入浆态床反应器中，在反应压力为15MPa、反应温度为300℃的条件下发生水解、裂化及加氢反应，并在此反应过程中通过反应器侧壁上的沿高度方向依次设置的3个注入口注入105℃的冷氢，控制反应器内的总气速为0.02m/s及催化剂在反应器内的存量为反应器内液、固相质量的30wt％，待反应60min后，将 从浆态床反应器排出的物料送入分离系统进行气、液、固三相分离，分别得到生物质气体、生物油及残渣；系统中的氢气循环使用，与新鲜的补充氢气一同进入上述的各个注氢点。
实施例20
本实施例提供的煤与生物质的一锅法液化工艺包括如下步骤：
生物质原料的预处理：
(1)取芦苇，将其烘干至含水量为1wt％，然后送入气流粉碎机进行粉碎处理，得到芦苇一次粉碎料，粒径D 50为200μm。
(2)将芦苇一次粉碎料送入压块机或压条机进行挤压成型，成型压力为3MPa，得到芦苇压缩料。
(3)将芦苇压缩料送入气流粉碎机，进行二次粉碎，得到芦苇二次粉碎料，粒径D 50为40μm，待用。
煤原料的预处理：
(1)取神东长焰煤，将其烘干脱水，然后送入球磨机进行粉碎处理，得到神东长焰煤一次粉碎料，粒径D 50为50μm。
(2)将神东长焰煤一次粉碎料送入压块机或压条机进行挤压成型，成型压力为12MPa，得到神东长焰煤压缩料。
(3)将神东长焰煤压缩料送入球磨机，进行二次粉碎，得到神东长焰煤二次粉碎料，粒径D 50为80μm，待用。
生物质水煤浆的配制和液化反应：
将芦苇和煤的二次粉碎料与负载有W氧化物和Ni氧化物的生物质炭(其粒径为100μm-150μm)以及羟基氧化铁和硫磺按质量比为100：2：2：0.4的比例混匀得到混合物，将该混合物加入至水中形成生物质水煤浆；在所述生物质水煤浆中，所述芦苇的含量为20wt％，所述煤的含量为40wt％。
向所述生物质水煤浆中注入70℃、20MPa的氢气至高压氢气与生物质水煤浆的体积比为100：1，而后在换热器中将该生物质水煤浆升温至250℃，再向其中注入250℃、20MPa的氢气，并控制这两次注入的氢气总量与生物质水煤浆的体积比达到900：1以形成反应原料，再将该反应原料升温至430℃后送入浆态床反应器中，在反应压力为20MPa、反应温度为450℃的条件下发生水解、裂化及加氢反应，并在此反应过程中通过反应器侧壁上的沿高度方向依次设置的4个注入口注入120℃的冷氢，控制反应器内 的总气速为0.06m/s及催化剂在反应器内的存量为反应器内液、固相质量的25wt％，待反应60min后，将从浆态床反应器排出的物料送入分离系统进行气、液、残渣三相分离，分别得到生物质气体、生物油及残渣；系统中的氢气循环使用，与新鲜的补充氢气一同进入上述各个注氢点。
实施例21
本实施例提供的煤与生物质的一锅法液化工艺包括如下步骤：
生物质与煤原料的处理：
取棕榈油油渣以及褐煤，烘干脱水，粉碎至中位粒径为100μm，然后共同送入压块机挤压成型，成型压力为5MPa，得到棕榈油油渣以及褐煤的压缩料。将上述压缩料送入球磨机，进行粉碎，得到中位粒径为50μm的棕榈油油渣以及褐煤的粉碎料，待用。
生物质水煤浆的配制和水解加氢反应：
将上述粉碎料与负载有Mo氧化物和Ni氧化物的无定型氧化铝(其粒径为350μm-500μm)以及硫磺按质量比为100：1：0.1的比例混匀得到混合物，再将上述混合物与水配制生物质水煤浆；所述生物质水煤浆中棕榈油油渣的含量为20wt％，所述煤的含量为45wt％。
向所述生物质水煤浆中注入90℃、20MPa的氢气至高压氢气与生物质水煤浆的体积比为150：1，而后在换热器中将该生物质水煤浆升温至300℃，再向其中注入300℃、20MPa的氢气，并控制这两次注入的氢气与生物质水煤浆的体积比达到800：1以形成反应原料，再将该反应原料升温至430℃后送入浆态床反应器中，在反应压力为20MPa、反应温度为460℃的条件下发生水解、裂化及加氢反应，并在此反应过程中通过反应器侧壁上的沿高度方向依次设置的5个注入口注入120℃的冷氢，控制反应器内的总气速为0.07m/s及催化剂在反应器内的存量为反应器内液相质量的30wt％，待反应40min后，将从浆态床反应器排出的物料送入分离系统进行气、液、残渣三相分离，分别得到生物质气体、生物油及残渣；系统中的氢气循环使用，与新鲜的补充氢气一同进入上述的各个注氢点。
实施例22
本实施例提供的煤与生物质的一锅法液化工艺包括如下步骤：
生物质原料的预处理：
(1)取大豆油油渣，将其烘干脱水，然后送入超微粉碎机进行粉碎处理，得到大豆油油渣一次粉碎料，粒径D 50为250μm。
(2)将大豆油油渣一次粉碎料送入压块机或压条机进行挤压成型，成型压力为5MPa，得到大豆油油渣压缩料。
(3)将大豆油油渣压缩料送入超微粉碎机，进行二次粉碎，得到大豆油油渣二次粉碎料，粒径D 50为45μm，待用。
煤原料的预处理：
(1)取神东长焰煤，将其烘干脱水，然后送入球磨机进行粉碎处理，得到神东长焰煤一次粉碎料，粒径D 50为60μm。
(2)将神东长焰煤一次粉碎料送入压块机或压条机进行挤压成型，成型压力为10MPa，得到神东长焰煤压缩料。
(3)将神东长焰煤压缩料送入球磨机，进行二次粉碎，得到神东长焰煤二次粉碎料，粒径D 50为40μm，待用。
生物质煤浆料的配制和液化反应：
本实施例采用实施例1制备得到的催化剂，将大豆油油渣和煤的二次粉碎料与上述催化剂、羟基氧化铁以及硫磺按质量比为100：1：0.2：0.25的比例混匀得到混合物，将该混合物加入至废润滑油中形成生物质煤浆料；在所述生物质煤浆料中，所述大豆油油渣的含量为20wt％，所述煤的含量为40wt％。
向所述生物质煤浆料中注入135℃、25MPa的氢气至高压氢气与生物质煤浆料的体积比为200：1，而后在换热器中将该生物质煤浆料升温至350℃，再向其中注入350℃、25MPa的氢气，并控制这两次注入的氢气总量与生物质煤浆料的体积比达到650：1以形成反应原料，再将该反应原料升温至400℃后送入浆态床反应器中，在反应压力为25MPa、反应温度为450℃的条件下发生液化、裂化及加氢反应，并在此反应过程中通过反应器侧壁上的沿高度方向依次设置的5个注入口注入100℃的冷氢，控制反应器内的总气速为0.1m/s及催化剂在反应器内的存量为反应器内液相质量的25wt％，待反应15min后，将从浆态床反应器排出的物料送入分离系统进行气、液、残渣三相分离，分别得到生物质气体、生物油及残渣；系统中的氢气循环使用，与新鲜的补充氢气一同进入上述的各个注氢点。
实施例23
本实施例提供的煤与生物质的一锅法液化工艺包括如下步骤：
生物质与煤原料的处理：
取棕榈油油渣以及褐煤，烘干脱水至水含量低于2wt％，然后共同送入压块机或压 条机进行挤压成型，成型压力为5MPa，得到棕榈油油渣以及褐煤的压缩料。将上述压缩料送入球磨机，进行粉碎，得到棕榈油油渣以及褐煤的粉碎料，待用。
生物质煤浆料的配制和液化加氢反应：
将上述粉碎料与负载有Mo氧化物和Ni氧化物的无定型氧化铝(其粒径为350μm-500μm)以及硫磺按质量比为100：1：0.1的比例混匀得到混合物，再将上述混合物与地沟油配制生物质煤浆料；所述生物质煤浆料中棕榈油油渣的含量为25wt％，所述煤的含量为40wt％。
向所述生物质煤浆料中注入90℃、20MPa的氢气至高压氢气与生物质煤浆料的体积比为150：1，而后在换热器中将该生物质煤浆料升温至300℃，再向其中注入300℃、20MPa的氢气，并控制这两次注入的氢气与生物质煤浆料的体积比达到800：1以形成反应原料，再将该反应原料升温至430℃后送入浆态床反应器中，在反应压力为20MPa、反应温度为420℃的条件下发生液化、裂化及加氢反应，并在此反应过程中通过反应器侧壁上的沿高度方向依次设置的5个注入口注入120℃的冷氢，控制反应器内的总气速为0.07m/s及催化剂在反应器内的存量为反应器内液相质量的30wt％，待反应40min后，将从浆态床反应器排出的物料送入分离系统进行气、液、残渣三相分离，分别得到生物质气体、生物油及残渣；系统中的氢气循环使用，与新鲜的补充氢气一同进入上述的各个注氢点。
实施例24
本实施例提供的煤与生物质的一锅法液化工艺包括如下步骤：
生物质原料的预处理：
(1)取芦苇，将其烘干至含水量为1wt％，然后送入气流粉碎机进行粉碎处理，得到芦苇一次粉碎料，粒径D 50为300μm。
(2)将芦苇一次粉碎料送入压块机或压条机进行挤压成型，成型压力为5MPa，得到芦苇压缩料。
(3)将芦苇压缩料送入气流粉碎机，进行二次粉碎，得到芦苇二次粉碎料，粒径D 50为30μm，待用。
煤原料的预处理：
(1)取神东长焰煤，将其烘干脱水，然后送入球磨机进行粉碎处理，得到神东长焰煤一次粉碎料，粒径D 50为50μm。
(2)将神东长焰煤一次粉碎料送入压块机或压条机进行挤压成型，成型压力为 15MPa，得到神东长焰煤压缩料。
(3)将神东长焰煤压缩料送入球磨机，进行二次粉碎，得到神东长焰煤二次粉碎料，粒径D 50为45μm，待用。
生物质煤浆料的配制和液化反应：
将芦苇和煤的二次粉碎料与负载有W氧化物和Ni氧化物的生物质炭(其粒径为100μm-150μm)以及羟基氧化铁和硫磺按质量比为100：2：2：0.4的比例混匀得到混合物，将该混合物加入至废机油中形成生物质煤浆料；在所述生物质煤浆料中，所述芦苇的含量为30wt％，所述煤的含量为30wt％。
向所述生物质煤浆料中注入70℃、17MPa的氢气至高压氢气与生物质煤浆料的体积比为100：1，而后在换热器中将该生物质煤浆料升温至250℃，再向其中注入250℃、17MPa的氢气，并控制这两次注入的氢气总量与生物质煤浆料的体积比达到900：1以形成反应原料，再将该反应原料升温至430℃后送入浆态床反应器中，在反应压力为17MPa、反应温度为450℃的条件下发生液化、裂化及加氢反应，并在此反应过程中通过反应器侧壁上的沿高度方向依次设置的4个注入口注入120℃的冷氢，控制反应器内的总气速为0.06m/s及催化剂在反应器内的存量为反应器内液、固相质量的25wt％，待反应60min后，将从浆态床反应器排出的物料送入分离系统进行气、液、残渣三相分离，分别得到生物质气体、生物油及残渣；系统中的氢气循环使用，与新鲜的补充氢气一同进入上述各个注氢点。
对比例1
本实验例提供的煤与生物质的一锅法液化工艺包括如下步骤：
生物质原料的预处理：
(1)取芦苇，将其烘干至含水量为1.5wt％，然后送入气流粉碎机进行粉碎处理，得到芦苇一次粉碎料，粒径D 50为200μm。
(2)将芦苇一次粉碎料送入压块机或压条机进行挤压成型，成型压力为3MPa，得到芦苇压缩料。
(3)将芦苇压缩料送入气流粉碎机，进行二次粉碎，得到芦苇二次粉碎料，粒径D 50为40μm，待用。
煤原料的预处理：
(1)取神东长焰煤，将其烘干脱水，然后送入球磨机进行粉碎处理，得到神东长焰煤一次粉碎料，粒径D 50为80μm。
(2)将神东长焰煤一次粉碎料送入压块机或压条机进行挤压成型，成型压力为12MPa，得到神东长焰煤压缩料。
(3)将神东长焰煤压缩料送入球磨机，进行二次粉碎，得到神东长焰煤二次粉碎料，粒径D 50为80μm，待用。
生物质水煤浆的配制和液化反应：
将芦苇和煤的二次粉碎料与经硫化处理后的水溶性分散型加氢催化剂按质量比为100：4.4的比例混匀得到混合物，将该混合物加入至水中形成生物质水煤浆；在所述生物质水煤浆中，所述芦苇的含量为20wt％，所述煤的含量为45wt％。
向所述生物质水煤浆中注入70℃、20MPa的氢气至高压氢气与生物质水煤浆的体积比为100：1，而后在换热器中将该生物质水煤浆升温至250℃，再向其中注入250℃、20MPa的氢气，并控制这两次注入的氢气总量与生物质水煤浆的体积比达到900：1以形成反应原料，再将该反应原料升温至430℃后送入浆态床反应器中，在反应压力为20MPa、反应温度为450℃的条件下发生水解、裂化及加氢反应，并在此反应过程中通过反应器侧壁上的沿高度方向依次设置的4个注入口注入120℃的冷氢，控制反应器内的总气速为0.06m/s及催化剂在反应器内的存量为反应器内液、固相质量的25wt％，待反应60min后，将从浆态床反应器排出的物料送入分离系统进行气、液、残渣三相分离，分别得到生物质气体、生物油及残渣；系统中的氢气循环使用，与新鲜的补充氢气一同进入上述各个注氢点。
对比例2
本对比例提供的煤与生物质的一锅法液化工艺包括如下步骤：
生物质原料的预处理：
(1)取芦苇，将其烘干至含水量为1wt％，然后送入气流粉碎机进行粉碎处理，得到芦苇一次粉碎料，粒径D 50为300μm。
(2)将芦苇一次粉碎料送入压块机或压条机进行挤压成型，成型压力为5MPa，得到芦苇压缩料。
(3)将芦苇压缩料送入气流粉碎机，进行二次粉碎，得到芦苇二次粉碎料，粒径D 50为30μm，待用。
煤原料的预处理：
(1)取神东长焰煤，将其烘干脱水，然后送入球磨机进行粉碎处理，得到神东长焰煤一次粉碎料，粒径D 50为50μm。
(2)将神东长焰煤一次粉碎料送入压块机或压条机进行挤压成型，成型压力为15MPa，得到神东长焰煤压缩料。
(3)将神东长焰煤压缩料送入球磨机，进行二次粉碎，得到神东长焰煤二次粉碎料，粒径D 50为45μm，待用。
生物质煤浆料的配制和液化反应：
将芦苇和煤的二次粉碎料与油溶性分散型加氢催化剂按质量比为100：2：2：0.4的比例混匀得到混合物，将该混合物加入至废机油中形成生物质煤浆料；在所述生物质煤浆料中，所述芦苇的含量为30wt％，所述煤的含量为30wt％。
向所述生物质煤浆料中注入70℃、17MPa的氢气至高压氢气与生物质煤浆料的体积比为100：1，而后在换热器中将该生物质煤浆料升温至250℃，再向其中注入250℃、17MPa的氢气，并控制这两次注入的氢气总量与生物质煤浆料的体积比达到900：1以形成反应原料，再将该反应原料升温至430℃后送入浆态床反应器中，在反应压力为17MPa、反应温度为450℃的条件下发生液化、裂化及加氢反应，并在此反应过程中通过反应器侧壁上的沿高度方向依次设置的4个注入口注入120℃的冷氢，控制反应器内的总气速为0.06m/s及催化剂在反应器内的存量为反应器内液、固相质量的25wt％，待反应60min后，将从浆态床反应器排出的物料送入分离系统进行气、液、残渣三相分离，分别得到生物质气体、生物油及残渣；系统中的氢气循环使用，与新鲜的补充氢气一同进入上述各个注氢点。
对本发明上述实施例18-24和对比例所提供工艺的效果进行评价，结果分别如表3所示。
表3 工艺效果
Figure PCTCN2018122665-appb-000003
Figure PCTCN2018122665-appb-000004
由表3中可以明确的得出，选用催化剂不同，实施例18-24中的煤与生物质的转化率、生物质油收率明显优于对比例1和2，而残渣量明显低于对比例1和2。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (37)

  1. 一种生物质的一锅法液化工艺，其特征在于，包括如下步骤：
    配制含有催化剂、硫化剂和生物质的浆液，向所述浆液中通入氢气以发生反应，并控制反应压力为15-25MPa、反应温度为380-480℃，最终制得生物油；
    所述生物质为秸秆，所述浆液的配制步骤为，将秸秆依次进行干燥、初粉碎、压缩和二次粉碎，得到预处理生物质，而后将所述预处理生物质与所述催化剂和所述硫化剂混合得到混合物，将所述混合物加入至油品中研磨制浆，得到秸秆浓度为30～60wt％的所述浆液。
  2. 根据权利要求1所述的生物质的一锅法液化工艺，其特征在于，所述浆液的配制步骤中，将所述秸秆进行压缩的压力为0.5～3MPa、温度为30-60℃。
  3. 根据权利要求1或2所述的生物质的一锅法液化工艺，其特征在于，所述浆液的配制步骤中，
    所述秸秆的干燥温度为50-70℃、时间为3-5h，所述秸秆干燥后的含水率低于2wt％；初粉碎后中位粒度为100-300μm；经二次粉碎后中位粒度为30-50μm、二次粉碎后堆密度为400-500kg/m 3。
  4. 根据权利要求1-3任一项所述的生物质的一锅法液化工艺，其特征在于，在所述浆液中，所述秸秆的含量为55～60wt％。
  5. 根据权利要求1所述的生物质的一锅法液化工艺，其特征在于，所述生物质为植物油渣，所述浆液的配制步骤为，将植物油渣依次进行干燥、初粉碎、压缩和二次粉碎，得到预处理生物质，而后将所述预处理生物质与所述催化剂和所述硫化剂混合得到混合物，将所述混合物加入至油品中研磨制浆，得到植物油渣浓度为50-65wt％的所述浆液。
  6. 根据权利要求5所述的生物质的一锅法液化工艺，其特征在于，所述浆液的配制步骤中，将所述植物油渣进行压缩的压力为3-5MPa、温度为40-60℃。
  7. 根据权利要求5或6所述的生物质的一锅法液化工艺，其特征在于，所述浆液的配制步骤中，
    所述植物油渣的干燥温度为80-110℃、时间为2-6h，所述植物油渣干燥后的含水率低于2wt％；初粉碎后中位粒度为100-300μm；经二次粉碎后中位粒度为30-50μm、二 次粉碎后堆密度为1500-1600kg/m 3。
  8. 根据权利要求1-7任一项所述的生物质的一锅法液化工艺，其特征在于，所述浆液的配制步骤中，所述油品为废弃动植物油脂、废矿物油、矿物油或馏分油中的一种或多种。
  9. 根据权利要求1所述的生物质的一锅法液化工艺，其特征在于，包括以下步骤：
    配制含有催化剂、硫化剂和生物质的浆液，向所述浆液中通入氢气以发生反应，并控制反应压力为15-20MPa、反应温度为300-400℃，最终制得生物油；
    所述生物质为秸秆，所述浆液的配制步骤为，将秸秆依次进行干燥、初粉碎、压缩和二次粉碎，得到预处理生物质，而后将所述预处理生物质与所述催化剂和所述硫化剂混合得到混合物，将所述混合物加入至水中研磨制浆，得到秸秆浓度为35-50wt％的所述浆液。
  10. 根据权利要求9所述的生物质的一锅法液化工艺，其特征在于，所述浆液的配制步骤中，将所述秸秆进行压缩的压力为2～5MPa、温度为30～60℃。
  11. 根据权利要求9或10所述的生物质的一锅法液化工艺，其特征在于，所述浆液的配制步骤中，
    所述秸秆的干燥温度为70-110℃、时间为3-5h，所述秸秆干燥后的含水率低于2wt％；初粉碎后的中位粒度为100-300μm；经二次粉碎后的中位粒度为30-50μm、二次粉碎后堆密度为400-800kg/m 3。
  12. 根据权利要求1所述的生物质的一锅法液化工艺，其特征在于，包括以下步骤：
    配制含有催化剂、硫化剂和生物质的浆液，向所述浆液中通入氢气以发生反应，并控制反应压力为15-20MPa、反应温度为340-420℃，最终制得生物油；
    所述生物质为植物油渣，所述浆液的配制步骤为，将植物油渣依次进行干燥、初粉碎、压缩和二次粉碎，得到预处理生物质，而后将所述预处理生物质与所述催化剂和所述硫化剂混合得到混合物，将所述混合物加入至水中研磨制浆，得到植物油渣浓度为40-50wt％的所述浆液。
  13. 根据权利要求12所述的生物质的一锅法液化工艺，其特征在于，所述浆液的配制步骤中，将所述植物油渣进行压缩的压力为0.5-3MPa、温度为30-50℃。
  14. 根据权利要求12或13所述的生物质的一锅法液化工艺，其特征在于，所述浆液的配制步骤中，
    所述植物油渣的干燥温度为80-110℃、时间为2-6h，所述植物油渣干燥后的含水率低于2wt％；初粉碎后的中位粒度为50-300μm；经二次粉碎后的中位粒度为30-50μm、二次粉碎后堆密度为1400-1600kg/m 3。
  15. 根据权利要求1-14任一项所述的生物质的一锅法液化工艺，其特征在于，所述催化剂包括无定型羟基氧化铁、负载有活性组分的无定型氧化铝或负载有活性组分的生物质炭中的一种或多种，所述活性组分选自元素周期表第VIB、VIIB或VIII族金属的氧化物中的一种或多种。
  16. 根据权利要求15所述的生物质的一锅法液化工艺，其特征在于，
    所述活性组分选自Mo、W、Fe、Co、Ni、Mn或Pd的氧化物中的一种或多种。
  17. 根据权利要求1-14任一项所述的生物质的一锅法液化工艺，其特征在于，所述催化剂的用量为所述预处理生物质质量的1～10wt％；所述催化剂的粒径为5-500μm；所述硫化剂的用量为所述预处理生物质质量的0.1-0.4wt％。
  18. 根据权利要求1-8任一项所述的生物质的一锅法液化工艺，其特征在于，向所述浆液中通入氢气的具体方法为：
    向所述浆液中注入高压氢气，并控制所述高压氢气与所述浆液的体积比为(600～1500)：1，从而形成反应原料；
    将所述反应原料升温至380-480℃后送入浆态床反应器内以发生水解、裂化及加氢反应，同时向所述浆态床反应器内注入冷氢，控制所述浆态床反应器内的总气速为0.02～0.2m/s，优选为0.05～0.08m/s；
    其中，所述高压氢气的压力为15～27MPa，所述冷氢的温度为60～135℃。
  19. 根据权利要求18所述的生物质的一锅法液化工艺，其特征在于，将所述高压氢气分两次注入至所述浆液中，具体为：
    在向所述浆液中第一次注入所述高压氢气，直至所述高压氢气与所述浆液的体积比为50-200:1，而后将所述浆液升温至200～350℃，再向所述浆液中第二次注入所述高压氢气。
  20. 根据权利要求18或19所述的生物质的一锅法液化工艺，其特征在于，所述催化剂在所述浆态床反应器内的存量控制在所述浆态床反应器内液相质量的5～30wt％；
    所述反应的时间为30～120min。
  21. 根据权利要求9-11任一项所述的生物质的一锅法液化工艺，其特征在于，向所述浆液中通入氢气的具体方法为：
    向所述浆液中注入高压氢气，并控制所述高压氢气与所述浆液的体积比为(600～1500)：1，从而形成反应原料；
    将所述反应原料升温至300-400℃后送入浆态床反应器内以发生水解、裂化及加氢反应，同时向所述浆态床反应器内注入冷氢，控制所述浆态床反应器内的总气速为0.02～0.2m/s，优选为0.05～0.08m/s；
    其中，所述高压氢气的压力为15～22MPa，所述冷氢的温度为60～135℃。
  22. 根据权利要求12-14任一项所述的生物质的一锅法液化工艺，其特征在于，向所述浆液中通入氢气的具体方法为：
    向所述浆液中注入高压氢气，并控制所述高压氢气与所述浆液的体积比为(600～1500)：1，从而形成反应原料；
    将所述反应原料升温至340-420℃后送入浆态床反应器内以发生水解、裂化及加氢反应，同时向所述浆态床反应器内注入冷氢，控制所述浆态床反应器内的总气速为0.02～0.2m/s；
    其中，所述高压氢气的压力为15～22MPa，所述冷氢的温度为60～135℃。
  23. 根据权利要求21或22所述的生物质的一锅法液化工艺，其特征在于，将所述高压氢气分两次注入至所述浆液中，具体为：
    在向所述浆液中第一次注入所述高压氢气，直至所述高压氢气与所述浆液的体积比为50-200:1，而后将所述浆液升温至200～280℃，再向所述浆液中第二次注入所述高压氢气。
  24. 根据权利要求21-23任一项所述的生物质的一锅法液化工艺，其特征在于，所述催化剂在所述浆态床反应器内的存量控制在所述浆态床反应器内液相质量的5～30wt％；所述反应的时间为30～60min。
  25. 一种煤与生物质的一锅法液化工艺，其特征在于，包括如下步骤：
    生物质煤浆料的配制：
    收集生物质并控制含水率低于2wt％，然后粉碎至中位粒径为100～300μm；
    将粉碎后的生物质进行压缩成型，压缩压力为2～5MPa，压缩温度为30～60℃；
    将压缩成型后的生物质再次粉碎处理，粉碎至中位粒径为30～50μm，得生物质粉末；
    收集煤并控制含水率低于2wt％，然后粉碎至中位粒径为50～100μm，压缩温度为30～60℃；
    对粉碎后的煤进行压缩成型，压缩压力为5～15MPa；
    对压缩成型后的煤再次粉碎处理，得煤粉；
    将所述生物质粉末、所述煤粉、催化剂、硫化剂与流动介质混合，所述流动介质为油品或水，研磨制浆得到生物质煤浆料；
    液化反应：向所述生物质煤浆料中通入氢气以发生反应，并控制反应压力为15～25MPa，最终制得生物油；
    当所述流动介质为油品时，在生物质煤浆料的配制步骤中，进行所述混合时，为先将所述生物质粉末和所述煤粉进行除灰并与所述催化剂和硫化剂进行预混合后，再将所得预混料与所述油品混合，或者，为直接将所述生物质粉末、所述煤粉、所述催化剂与所述油品混合；煤再次粉碎至中位粒径为30-50μm；所述生物质粉末和所述煤粉共占所述生物质煤浆料的60-70wt％；液化反应温度为380-460℃；
    当所述流动介质为水时，在生物质煤浆料的配制步骤中，进行所述混合时，为先将所述生物质粉末和所述煤粉进行除灰并与所述催化剂和所述硫化剂进行预混合后，再将所得预混料与所述水混合，或者，为直接将所述生物质粉末、所述煤粉、所述催化剂、所述硫化剂与所述水混合；煤再次粉碎至中位粒径为30-100μm；所述生物质粉末和所述煤粉共占所述生物质煤浆料的55-65wt％；液化反应温度为300-460℃。
  26. 根据权利要求25所述的煤与生物质的一锅法液化工艺，其特征在于，所述生物质煤浆料中，当所述流动介质为油品时，生物质的浓度为20～30wt％，煤粉的浓度为30～45wt％；
    当所述流动介质为水时，生物质的浓度为15～30wt％，煤粉的浓度为35～50wt％。
  27. 根据权利要求25或26所述的煤与生物质的一锅法液化工艺，其特征在于，采用烘干脱水控制含水率，所述烘干脱水温度均为50～70℃，烘干脱水时间为3～5h。
  28. 根据权利要求25-27任一项所述的煤与生物质的一锅法液化工艺，其特征在于， 生物质煤浆料的配制步骤中控制所述生物质粉末的堆密度为300～500kg/m 3；当所述流动介质为油品时，控制所述煤粉的堆密度为1000～1200kg/m 3；当所述流动介质为水时，控制所述煤粉的堆密度为1200～1300kg/m 3。
  29. 根据权利要求25-28任一项所述的煤与生物质的一锅法液化工艺，其特征在于，所述研磨制浆的时间为2～8min。
  30. 根据权利要求25-29任一项所述的煤与生物质的一锅法液化工艺，其特征在于，所述煤为低阶煤；所述油品为潲水油、地沟油、酸败油、废润滑油、废机油、重油、渣油、洗油、蒽油、煤焦油、石油、或本工艺制得的生物油中的一种或多种。
  31. 根据权利要求25-30任一项所述的煤与生物质的一锅法液化工艺，其特征在于，在所述生物质煤浆料中，所述催化剂的用量为所述生物质与煤的用量总和的1～10wt％，优选为1～4wt％；所述催化剂的粒径为5～500μm。
  32. 根据权利要求25-31任一项所述的煤与生物质的一锅法液化工艺，其特征在于，所述通入氢气的具体方法为：
    向所述生物质煤浆料中注入高压氢气，并控制所述高压氢气与所述生物质煤浆料的体积比为(600～1500)：1，从而形成反应原料；
    将所述反应原料升温至320～450℃后送入浆态床反应器内以发生液化、裂化及加氢反应，同时向所述浆态床反应器内注入冷氢，控制所述浆态床反应器内的总气速为0.02～0.2m/s，优选为0.05～0.08m/s；
    其中，所述高压氢气的压力均为13～27MPa，所述冷氢的温度为60～135℃。
  33. 根据权利要求32所述的煤与生物质的一锅法液化工艺，其特征在于，将所述高压氢气分两次注入至所述生物质煤浆料中，具体为：
    向所述生物质煤浆料中第一次注入所述高压氢气，直至所述高压氢气与所述生物质煤浆料的体积比为50～200:1，而后将所述生物质煤浆料升温至200～350℃，而后再向所述生物质煤浆料中第二次注入所述高压氢气。
  34. 根据权利要求32或33所述的煤与生物质的一锅法液化工艺，其特征在于，所述催化剂在所述浆态床反应器内的存量控制在所述浆态床反应器内液相质量的5～30wt％。
  35. 根据权利要求25-34任一项所述的煤与生物质的一锅法液化工艺，其特征在于，当所述流动介质为油品时，所述反应的时间为30～90min；当所述流动介质为水时，所述反应的时间为30～60min。
  36. 根据权利要求25-35任一项所述的煤与生物质的一锅法液化工艺，其特征在于， 所述催化剂包括负载有第一活性组分的无定型氧化铝或负载有第一活性组分的生物质炭，所述第一活性组分选自元素周期表第VIB、VIIB或VIII族金属的氧化物中的一种或多种。
  37. 根据权利要求25-36任一项所述的煤与生物质的一锅法液化工艺，其特征在于，所述催化剂还包括无定型羟基氧化铁，和/或负载有第二活性组分的生物质炭，所述第二活性组分选自Mo、W、Fe、Co、Ni或Pd的氧化物中的一种或多种。
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