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WO2019128867A1 - 一种生物质的水解加氢工艺 - Google Patents

一种生物质的水解加氢工艺 Download PDF

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Publication number
WO2019128867A1
WO2019128867A1 PCT/CN2018/122667 CN2018122667W WO2019128867A1 WO 2019128867 A1 WO2019128867 A1 WO 2019128867A1 CN 2018122667 W CN2018122667 W CN 2018122667W WO 2019128867 A1 WO2019128867 A1 WO 2019128867A1
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Prior art keywords
reaction
biomass
slurry
pressure
temperature
Prior art date
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PCT/CN2018/122667
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English (en)
French (fr)
Inventor
林科
李林
郭立新
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Beijing SJ Environmental Protection and New Material Co Ltd
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Beijing SJ Environmental Protection and New Material Co Ltd
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Priority claimed from CN201711420301.XA external-priority patent/CN108264918B/zh
Priority claimed from CN201711419138.5A external-priority patent/CN108277036B/zh
Priority claimed from CN201711420277.XA external-priority patent/CN108264917B/zh
Priority claimed from CN201711419183.0A external-priority patent/CN108219817B/zh
Priority claimed from CN201711431460.XA external-priority patent/CN108192652B/zh
Priority claimed from CN201711431442.1A external-priority patent/CN108277038B/zh
Priority claimed from CN201711429943.6A external-priority patent/CN108179019B/zh
Priority claimed from CN201711431477.5A external-priority patent/CN108285808B/zh
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 WO2019128867A1 publication Critical patent/WO2019128867A1/zh
Anticipated expiration legal-status Critical
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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

Definitions

  • the invention relates to the field of bioenergy, in particular to a process for hydrolyzing hydrogenation of biomass.
  • Biomass refers to all organic substances formed directly or indirectly by photosynthesis of green plants, including plants, animals, microorganisms and their excretions and metabolites. It is renewable, low in pollution and widely distributed, therefore, from energy security. Starting from environmental protection, the development and utilization of biomass has become the strategic focus of the current development of renewable energy.
  • Biomass liquefaction technology is an important part of biomass resource utilization.
  • the liquefaction mechanism of biomass is as follows: biomass is first cleaved into oligomers, then dehydrated, dehydroxylated, dehydrogenated, deoxygenated and decarboxylated to form small molecules. The compound, the small molecule compound, is then reacted by condensation, cyclization, polymerization or the like to form a new compound.
  • biomass direct liquefaction technology refers to hydrolysis, supercritical liquefaction or introduction of hydrogen, inert gas, etc. at the appropriate temperature under the action of solvent or catalyst.
  • Biomass direct liquefaction technology mainly includes pyrolysis liquefaction, catalytic liquefaction and pressurized hydroliquefaction, especially for pressurized hydro-liquefaction products with high yield and good quality, which generally include 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 heavy oil as the solvent of the slurry has a large viscosity, so that the above slurry is not easy to flow, and it is easy to cause blockage of the conveying pipe, thereby making it difficult to achieve smooth transportation of the pump.
  • the prior art attempts to increase the concentration and dispersibility of biomass in the slurry by adding a dispersant to the slurry, the addition of the dispersant tends to affect 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.
  • the first technical solution provided by the present invention a process for hydrolyzing hydrogenation of biomass, comprising the following steps:
  • the biomass is straw
  • the slurry is prepared by sequentially drying, initial pulverizing, compressing and secondary pulverizing the straw, then mixing with the catalyst to obtain a mixture, and adding the mixture to the oil for grinding.
  • the slurry is obtained to obtain the slurry having a straw concentration of 30 to 60% by weight.
  • the straw raw material in the invention may be straw of cereals such as wheat, rice, corn, reed, sorghum, millet, etc., or legumes such as soybean, adzuki bean, mung bean, broad bean, pea, etc., and may also be cotton, linen,
  • the fiber crop straw such as ramie and 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 the 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 biomass 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 is contained in an amount of 0.1 to 10% by weight, preferably 2% by weight; the catalyst has a particle diameter of 5 ⁇ m to 500 ⁇ m;
  • the reaction raw material is sent to a slurry bed reactor to generate hydrolysis, cracking and hydrogenation reaction, while high pressure cold hydrogen is injected into the slurry bed reactor to control the total gas in the slurry bed reactor.
  • the speed is 0.02 ⁇ 0.2m / s, preferably 0.05 ⁇ 0.08m / s;
  • the pressure of the high-pressure hydrogen gas and the high-pressure cold hydrogen is 15-22 MPa, and the temperature of the high-pressure cold hydrogen is 50-135 °C.
  • the high pressure hydrogen gas is injected into the slurry twice, specifically:
  • the temperature of the high-pressure medium-temperature hydrogen gas is 360-420 ° C
  • the temperature of the high-pressure high-temperature hydrogen gas is 430-510 ° C.
  • the cold hydrogen is injected through 3 to 5 injection ports on the side wall of the slurry bed reactor.
  • the inventory of the catalyst in the slurry bed reactor is controlled to be 5 to 30% by weight of the liquid phase mass in the slurry bed reactor.
  • the reaction time is 30-120 min.
  • the catalyst is a vulcanized bioactive carbon loaded with an active component, and the active component is one or more of iron oxide, iron oxyhydroxide or iron hydroxide, and the active component and the biomass carbon
  • the total mass of the active component is 10 to 50% by weight
  • the preparation method of the biomass carbon loaded with active component comprises:
  • the specific method of supporting the active component on the biomass carbon carrier is:
  • the precipitate is an aqueous solution of at least one of ammonia carbonate or alkali metal carbonate, hydrogencarbonate or hydroxide, and the temperature of the precipitation process is controlled to be 30 ° C to 90 ° C, and the pH is 7 to 9.
  • the catalyst is a vulcanized amorphous iron oxyhydroxide.
  • a process for hydrolyzing hydrogenation of biomass comprising the following steps:
  • the biomass is vegetable oil residue
  • the slurry is prepared by sequentially drying, initial pulverizing, compressing and secondary pulverizing the vegetable oil residue, and then mixing with the catalyst to obtain a mixture, and adding the mixture to the oil.
  • the slurry is ground 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 to 5 MPa and a temperature of 40 to 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 the initial crushing 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 type of the oil, the method of grinding and pulping, the amount of the catalyst, the particle size, the specific method of introducing hydrogen into the slurry, the stock of the catalyst in the slurry bed reactor, and the reaction time are the same as those of the first technical solution.
  • the high pressure hydrogen gas is injected into the slurry twice, specifically:
  • the temperature of the high-pressure medium-temperature hydrogen gas is 360-440 ° C
  • the temperature of the high-pressure high-temperature hydrogen gas is 450-510 ° C.
  • a multi-stage 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, and then mixing with the first catalyst to obtain a mixture, and adding the mixture to the oil.
  • the slurry is ground to obtain the slurry having a straw concentration of 30 to 60% by weight.
  • the source of the straw in the preparation step of the slurry, the source of the straw, the contraction force of the straw, the temperature, the drying temperature of the straw, the time, the moisture content control, the particle size control in the pulverization, the bulk density of the straw, the viscosity of the slurry, the straw in the slurry
  • the content, the type of oil, the grinding and pulping method, etc. are the same as those of the first technical solution.
  • the first catalyst is contained in an amount of 0.1 to 10% by weight, preferably 2% by weight; the first catalyst has a particle diameter of 5 ⁇ m to 500 ⁇ m;
  • the second catalyst is added in an amount of 0.5 to 2% by weight of the first-stage hydrogenation product, and the second catalyst has a particle diameter of 5 ⁇ m to 500 ⁇ m;
  • the method further comprises the step of formulating the second catalyst into a catalyst slurry, specifically:
  • the catalyst slurry is prepared by mixing the second catalyst and the solvent oil in a mass ratio of (1 to 2): 10; the solvent oil is waste animal and vegetable oil, waste mineral oil, mineral oil, and fraction One or more of oil or bio-oil produced by the process.
  • the specific method for introducing hydrogen into the slurry in the step (1) is:
  • 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 and the high pressure cold hydrogen are both 15 to 27 MPa, and the temperature of the high pressure cold hydrogen is 50 to 135 ° C;
  • step (2) The method of introducing hydrogen into step (2) is:
  • the mixture of the primary hydrogenation product and the second catalyst is heated to 400 to 480 ° C, preferably 430 ° C, and then the mixture is fed to a second slurry bed reactor and passed through a high pressure high temperature hydrogen gas.
  • a second slurry bed reactor To generate a secondary hydrogenation reaction while simultaneously injecting high pressure cold hydrogen into the second slurry bed reactor, and controlling the total gas velocity in the second slurry bed reactor to be 0.06 to 0.1 m/s, and
  • the volume ratio of the high-pressure high-temperature hydrogen to the first-stage hydrogenation product is (1000-1500): 1;
  • the pressure of the high-pressure high-temperature hydrogen gas and the high-pressure cold hydrogen is 15-27 MPa
  • the temperature of the high-pressure high-temperature hydrogen gas is 430-480 ° C
  • the temperature of the high-pressure cold hydrogen is 50-135 ° C.
  • the high-pressure hydrogen gas is injected into the slurry twice, specifically:
  • the temperature of the high-pressure medium-temperature hydrogen gas is 260-350 ° C
  • the temperature of the second-injected high-pressure high-temperature hydrogen gas is 360-510 ° C.
  • the high pressure cold hydrogen is injected through the first slurry bed reactor or three to five injection ports on the side wall of the second slurry bed reactor.
  • the amount of the first catalyst in the first slurry bed reactor is controlled to be 5 to 30% by weight of the liquid phase mass in the first slurry bed reactor, and the second catalyst is in the second slurry
  • the inventory in the bed reactor is controlled in the range of 5 to 30% by weight of the liquid phase in the second slurry bed reactor.
  • the time of the first hydrogenation reaction is 30 to 60 minutes, and the time of the second hydrogenation reaction is 30 to 90 minutes.
  • the step of subjecting the secondary hydrogenation product to hydro-reforming under conditions of a pressure of 7 to 23 MPa and a temperature of 250 to 460 ° C is also included.
  • the first catalyst is a vulcanized biomass char loaded with a first active component, and the first active component is one or more of iron oxide, iron oxyhydroxide or iron hydroxide, The first active component is contained in an amount of 10 to 50% by weight based on the total mass of the active component and the biomass carbon; and the second catalyst is a vulcanized biochar which is loaded with the second active component, The second active component is one or more of oxides of Mo, Mn, W, Fe, Co, Ni or Pd, and the content of the active component is based on the total mass of the second active component and the biomass carbon. 1 to 5 wt%;
  • the preparation method of the biomass carbon loaded with the first active component comprises:
  • the first active component is supported on the first biomass carbon support to prepare the first catalyst.
  • a specific method of supporting the first active component on the first biomass carbon carrier is:
  • the first biomass carbon carrier and the first active component aqueous solution are mixed and formulated into a suspension, and the first active component is precipitated on the first biomass carbon carrier by adding a precipitating agent, and is washed and dried to obtain a solution.
  • the first catalyst wherein the precipitating agent is an aqueous solution of at least one of ammonia water or an alkali metal carbonate, hydrogencarbonate or hydroxide, and the temperature of the precipitation process is controlled to be 30 ° C to 90 ° C, and the pH is 7 ⁇ 9.
  • the preparation method of the biomass carbon loaded with the second active component comprises:
  • the biomass carbon is acidified or alkalized to obtain a second biomass carbon carrier
  • 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 second catalyst having a particle size of from 5 ⁇ m to 500 ⁇ m.
  • the acid concentration of the H+ substance in the acidified acid medium is 0.5 mol/L to 5 mol/L; the volume ratio of the biomass carbon to the acidic medium is 1:5 to 1:15, and the acidification temperature is 30 ⁇ . 80 ° C, acidification time is 1h ⁇ 10h; the amount of the substance of OH- in the alkalized alkaline medium is 0.5mol / L ⁇ 5mol / L; the volume ratio of the biomass carbon to the alkaline medium 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 first catalyst is vulcanized amorphous iron oxyhydroxide
  • the second catalyst is a vulcanized amorphous alumina loaded with a third active component
  • the third active component is selected from the periodic table of elements.
  • a multi-stage liquefaction process for biomass comprising the following steps:
  • the biomass is vegetable oil residue
  • the slurry is prepared by sequentially drying, initial pulverizing, compressing and secondary pulverizing the vegetable oil residue, and then mixing with the first catalyst to obtain a mixture, and adding the mixture to the oil. Grinding and pulping in the product to obtain the slurry having a vegetable oil residue concentration of 30 to 60% by weight;
  • the source of the vegetable oil residue, the compression and contraction force of the vegetable oil residue, the temperature, the drying temperature, the time, the particle size control during the crushing, the bulk density, the viscosity of the slurry, the oil type, the grinding and pulping are the same as the second technical solution.
  • the content of the first catalyst, the particle diameter, the dosage of the second catalyst, the particle size, the manner of dosing, and the introduction of hydrogen into the slurry in the step (1) The specific method, the method of introducing hydrogen into the step (2), the standards of the high-pressure high-temperature hydrogen and the high-pressure cold hydrogen are the same as the third technical scheme.
  • the high-pressure hydrogen gas is injected into the slurry twice, specifically:
  • the temperature of the high-pressure medium-temperature hydrogen gas is 230-350 ° C
  • the temperature of the second-injected high-pressure high-temperature hydrogen gas is 360-510 ° C.
  • the stock of the first catalyst in the first slurry bed reactor, the inventory of the second catalyst in the second slurry bed reactor, the primary and secondary hydrogenation reaction time, The conditions of the hydro-reforming, the composition of the first catalyst, the preparation method, the composition of the second catalyst, the preparation method of the biomass carbon loaded with the second active component, and the like are the same as those of the third technical solution.
  • the invention also provides a fifth technical solution,
  • a co-liquefaction process of 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, and the compression temperature is 30-60 ° C;
  • coal after compression molding is pulverized again, and pulverized to a median diameter of 30-50 ⁇ m to obtain coal powder;
  • the biomass powder and the coal powder are first subjected to ash removal and premixed with the catalyst, and then the obtained premix is The oil is mixed, 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 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 contained in an amount of 0.1 to 10% by weight, preferably 2% by weight; and the catalyst has a particle diameter of 5 to 500 ⁇ m.
  • the reaction raw material is sent into a slurry bed reactor to undergo liquefaction, cracking and hydrogenation reaction, while high pressure cold hydrogen is injected into the slurry bed reactor to control the total gas in the slurry bed reactor.
  • the speed is 0.02 ⁇ 0.2m / s, preferably 0.05 ⁇ 0.08m / s;
  • the pressure of the high pressure hydrogen and the high pressure cold hydrogen is 13-27 MPa, and the temperature of the high pressure cold hydrogen is 50-135 °C.
  • the high pressure hydrogen gas is injected into the biomass coal slurry twice, specifically:
  • the temperature of the high-pressure medium-temperature hydrogen gas is 300 to 400 ° C
  • the temperature of the high-pressure high-temperature hydrogen gas is 410 to 510 ° C.
  • the cold hydrogen is injected through 3 to 5 injection ports on the side wall of the slurry bed reactor.
  • the inventory of the catalyst in the slurry bed reactor is controlled to be 5 to 30% by weight of the liquid phase mass in the slurry bed reactor.
  • the reaction time is 30 to 90 min.
  • the preparation step of the biomass coal slurry further includes an operation of screening the biomass powder and the coal powder, and returning the solid material exceeding a defined particle size to the compression or the crushing step The operation is performed again; the defined particle size is from 80 ⁇ m to 100 ⁇ m.
  • the catalyst is a vulcanized biological carbon loaded with an active component, and the active component is one or more of iron oxide, iron oxyhydroxide or iron hydroxide;
  • the catalyst is a vulcanized amorphous iron oxyhydroxide.
  • 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, etc.
  • the compression and pulverization of the biomass material is omitted in the step of preparing the biomass coal slurry.
  • the process can also be a biomass material which is composed of one kind of biomass or a plurality of kinds of biomass.
  • the preparation method of the biomass carbon loaded with the active component in the invention comprises:
  • biomass charcoal as a biomass carbon carrier
  • the specific method of supporting the active component on the biomass carbon carrier is:
  • the precipitate is an aqueous solution of at least one of ammonia carbonate or alkali metal carbonate, hydrogencarbonate or hydroxide, and the temperature of the precipitation process is controlled to be 30 ° C to 90 ° C, and the pH is 7 to 9.
  • the catalyst is a vulcanized amorphous iron oxyhydroxide.
  • a co-hydrolysis hydrogenation process of 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;
  • the biomass powder and the pulverized coal are degreased and premixed with the catalyst, and then the premixed is obtained.
  • the material 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 biomass density of the biomass powder is controlled to be 300 to 500 kg/m 3
  • the bulk density of the coal powder is controlled to be 1200 to 1300 kg/m 3 .
  • drying temperature, time, the time of the grinding and pulping, the content of the catalyst in the slurry, the particle size, the type of coal, the specific method of introducing hydrogen, the source of biomass, the type of catalyst, and the preparation are the same as the fifth technical solution.
  • the high pressure hydrogen gas is injected into the biomass coal slurry twice, specifically:
  • the temperature of the high-pressure medium-temperature hydrogen gas is 300 to 400 ° C
  • the temperature of the high-pressure high-temperature hydrogen gas is 410 to 510 ° C.
  • the inventory 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 min.
  • a multi-stage 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, and the compression temperature is 30-60 ° C;
  • coal after compression molding is pulverized again, and pulverized to a median diameter of 30 to 50 ⁇ m to obtain coal powder;
  • biomass powder, the pulverized coal, the catalyst and the oil are proportion-mixed and ground to obtain a biomass coal slurry, and the biomass powder and the pulverized coal together comprise the biomass coal 60 to 70% by weight of the slurry;
  • First-stage hydrogenation reaction hydrogen is introduced into the biomass coal slurry to generate a first-stage hydrogenation reaction, and the reaction pressure is 15-25 MPa, and the reaction temperature is 280-350 ° C to obtain a first-stage hydrogenation product;
  • Secondary hydrogenation reaction adding a second catalyst to the first-stage hydrogenation product and introducing hydrogen gas to generate a secondary hydrogenation reaction, controlling the reaction pressure to be 15-25 MPa, and the reaction temperature being 400-480 ° C, to obtain a secondary a hydrogenation product, the second hydrogenated product is finally separated to obtain a bio-oil;
  • the biomass powder and the coal powder are first subjected to ash removal and premixed with the catalyst, and then the obtained premix is The oil is mixed, or the biomass powder, the pulverized coal, the catalyst, and the oil are directly mixed.
  • the biomass coal slurry the concentration of biomass, the concentration of coal powder, the drying time, the temperature, the compression mode, the biomass density of the compressed biomass powder, the pulverized coal, the pulverization method, the grinding and pulping method, and the time
  • the slurry viscosity, coal and oil varieties are equal to the fifth technical solution.
  • the preparation step of the biomass kerosene paddle further includes an operation of screening the biomass powder and the pulverized coal, and returning the solid material exceeding a defined particle size to the compression or the pulverization step The operation is performed again; the defined particle size is from 80 ⁇ m to 100 ⁇ m.
  • the content of the first catalyst is 0.1 to 10% by weight, preferably 2% by weight; the particle diameter of the first catalyst is 5 ⁇ m to 500 ⁇ m;
  • the second catalyst is added in an amount of 0.5 to 2% by weight of the first-stage hydrogenation product, and the second catalyst has a particle diameter of 5 ⁇ m to 500 ⁇ m;
  • the method further comprises the step of formulating the second catalyst into a catalyst slurry, specifically:
  • the catalyst slurry is prepared by mixing the second catalyst with a solvent oil (water) in a mass ratio of (1 to 2):10.
  • the specific method for introducing hydrogen into the first-stage hydrogenation reaction step is:
  • 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 and the high pressure cold hydrogen is 13 to 27 MPa, and the temperature of the high pressure cold hydrogen is 50 to 135 ° C;
  • the method of introducing hydrogen into the second-stage reaction step is:
  • the mixture of the primary hydrogenation product and the second catalyst is heated to 380 to 480 ° C, preferably 430 ° C, and then the mixture is fed to a second slurry bed reactor and passed through a high pressure high temperature hydrogen gas.
  • a second slurry bed reactor To generate a secondary hydrogenation reaction while simultaneously injecting high pressure cold hydrogen into the second slurry bed reactor, and controlling the total gas velocity in the second slurry bed reactor to be 0.06 to 0.1 m/s, and
  • the volume ratio of hydrogen to the primary hydrogenation product is (1000 to 1500): 1;
  • the pressure of the high-pressure high-temperature hydrogen gas and the high-pressure cold hydrogen is 13-27 MPa
  • the temperature of the high-pressure high-temperature hydrogen gas is 430-480 ° C
  • the temperature of the high-pressure cold hydrogen is 50-135 ° C.
  • the high pressure hydrogen gas is injected into the biomass coal slurry twice, specifically:
  • the temperature of the high-pressure medium-temperature hydrogen gas is 180 to 350 ° C
  • the temperature of the second injection high-pressure high-temperature hydrogen gas is 360 to 510 ° C.
  • the high pressure cold hydrogen is injected through the first slurry bed reactor or three to five injection ports on the side wall of the second slurry bed reactor.
  • the amount of the first catalyst in the first slurry bed reactor is controlled to be 5 to 30% by weight of the liquid phase mass in the first slurry bed reactor, and the second catalyst is in the second slurry
  • the inventory in the bed reactor is controlled in the range of 5 to 30% by weight of the liquid phase in the second slurry bed reactor.
  • the time of the first hydrogenation reaction is 30 to 60 minutes, and the time of the second hydrogenation reaction is 30 to 90 minutes.
  • the step of subjecting the secondary hydrogenation product to hydro-reforming under conditions of a pressure of 7 to 23 MPa and a temperature of 250 to 460 ° C is also included.
  • the first catalyst is a vulcanized biomass char loaded with a first active component, and the first active component is one or more of iron oxide, iron oxyhydroxide or iron hydroxide;
  • the second catalyst is a vulcanized biochar carrying a second active component, and the second active component is one or more of oxides of Mo, W, Fe, Co, Ni or Pd;
  • the first catalyst is vulcanized amorphous iron oxyhydroxide
  • the second catalyst is a vulcanized amorphous alumina loaded with a third active component
  • the third active component is selected from the periodic table of elements.
  • the biomass raw material in the present invention may be straw of solid 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, industrially. Wood, paper waste, etc.; it can also be liquid feces, etc.; it can be a biomass or a biomass material composed of a variety of biomass.
  • the preparation method of the biomass carbon loaded with the first active component comprises:
  • the first active component is supported on the first biomass carbon support to prepare the first catalyst.
  • a specific method of supporting the first active component on the first biomass carbon carrier is:
  • the first biomass carbon carrier and the first active component aqueous solution are mixed and formulated into a suspension, and the first active component is precipitated on the first biomass carbon carrier by adding a precipitating agent, and is washed and dried to obtain a solution.
  • the first catalyst wherein the precipitating agent is an aqueous solution of at least one of ammonia water or an alkali metal carbonate, hydrogencarbonate or hydroxide, and the temperature of the precipitation process is controlled to be 30 ° C to 90 ° C, and the pH is 7 ⁇ 9.
  • the preparation method of the biomass carbon loaded with the second active component comprises:
  • 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 second catalyst having a particle size of from 5 ⁇ m 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.
  • a multi-stage liquefaction process for coal and biomass comprising the following steps:
  • the pulverized biomass is compression-molded, and the compression pressure is 2 to 5 MPa;
  • 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;
  • First-stage hydrogenation reaction introducing hydrogen into the biomass coal slurry to generate a first-stage hydrogenation reaction, controlling the reaction pressure to 15-20 MPa, and reacting at a temperature of 220-300 ° C to obtain a first-stage hydrogenation product;
  • Secondary hydrogenation reaction adding a second catalyst to the first-stage hydrogenation product and introducing hydrogen gas to generate a second-stage hydrogenation reaction, controlling the reaction pressure to be 15-20 MPa, and the reaction temperature is 380-420 ° C, and obtaining the second stage a hydrogenation product, the second hydrogenated product is finally separated to obtain a bio-oil;
  • the biomass powder and the coal powder are first subjected to ash removal and premixed with the catalyst, and then the obtained premix is The water is mixed or, alternatively, the biomass powder, the pulverized coal, the catalyst, and the water are directly mixed.
  • the biomass coal slurry, the concentration of biomass, the concentration of coal powder, the drying time, the temperature, the compression mode, the biomass density of the compressed biomass powder, the pulverized coal, the pulverization method, the grinding and pulping method, and the time The viscosity of the slurry, the type of coal and biomass are the same as the sixth technical solution.
  • the composition and preparation method of the second catalyst are the same as those of the seventh technical solution.
  • the hydrolyzed hydrogenation process of biomass provided by the present invention, wherein the slurry is prepared by sequentially drying, initial pulverizing, compressing and secondary pulverizing the biomass, and then mixing with the catalyst to obtain a mixture, and adding the mixture to the oil.
  • the slurry is obtained by grinding and pulping.
  • the first process of the invention is that the biomass is firstly compressed and then secondarily pulverized.
  • the biomass is subjected to compression treatment, so that the loose biomass undergoes re-alignment such as collapse and closure.
  • the stage of mechanical deformation greatly reduces the volume of biomass, thereby reducing the porosity of the biomass, increasing its density and specific gravity, making it advantageous for dispersion in the flowing medium, and improving its presence in the flowing medium.
  • the content of the reaction material increases the concentration of the reaction material, and the content of the straw in the oil slurry can be as high as 30-60 wt%, which is much higher than 5-16 wt% in the prior art; the content of the vegetable oil residue in the slurry can be Up to 50-65wt%, and due to the increase of biomass concentration in the slurry, it will inevitably increase the amount of biomass transported by the pump per unit time, thereby improving the whole organism.
  • the efficiency of the liquefaction process reduces the industrial cost and energy consumption; in addition, the increase in the specific gravity of the biomass also facilitates the suspension and dispersion of the biomass in the slurry, thereby reducing the viscosity of the biomass slurry and achieving biomass pulping.
  • the smooth flow of the slurry in the pipeline avoids the blockage of the pipeline, realizes the smooth operation and transportation of the pump, and also makes the high-viscosity waste oil which cannot be used as a biomass liquefaction solvent in the prior art, such as waste engine oil and waste oil. , rancid oil, etc., can also be used.
  • the invention prepares a bio-oil by preparing a slurry containing a catalyst and a biomass, and then introducing hydrogen into the slurry to generate a primary or secondary reaction, and finally controlling the reaction pressure and the reaction temperature, and the process of the invention is in the presence of hydrogen. Under the action of the catalyst, the biomass is cracked and hydrogenated to realize the conversion from biomass to bio-oil, 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 process of the invention under the action of hydrogen and the first catalyst and the second catalyst, causes the biomass to undergo cracking hydrogenation reaction, thereby realizing the conversion from biomass to bio-oil, in the process of the invention, the biomass conversion rate can be Up to 98-99%.
  • the hydrolyzation hydrogenation process of biomass provided by the present 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 the straw and the oil in the process of the invention is 500-1400 mPa. s (50 ° C), thereby achieving smooth flow of the slurry after biomass slurrying, avoiding blockage of the pipeline, achieving smooth operation and transportation of the pump; by controlling the compression temperature at 40-60 ° C, Further compressing the vegetable oil residue at this temperature can significantly enhance the rheology of the vegetable oil residue and reduce the viscosity of the biomass slurry.
  • the viscosity of the slurry formed by the vegetable oil residue and the oil in the process of the present 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 inventive first realization of the mixing and liquefaction of coal, biomass and oil provides a common 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.
  • Biomass coal water slurry Biomass coal water slurry.
  • the compression treatment can cause the pore structure inside the coal and biomass material to collapse and close, and plastic rheology and plastic deformation occur, thereby greatly increasing the density of the coal and biomass raw materials, so that it can be well dispersed in the solvent oil;
  • 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 dispersant;
  • the 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 to 60 ° C is used as the temperature at the time of compression.
  • 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 kerosene 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 meet the subsequent processing technology.
  • 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 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
  • the reaction is carried out by introducing hydrogen into the biomass kerosene slurry, and the reaction pressure is 15-25 MPa, and the reaction temperature is 380-480 ° C, thereby finally producing a bio-oil;
  • the process of the invention makes the coal and the biomass at a high pressure Liquefaction under high temperature conditions, and further cracking and hydrogenation reaction under the action of hydrogen and catalyst, thereby realizing the conversion of coal and biomass to bio-oil.
  • the conversion ratio of coal to biomass can reach 90-95%
  • the yield of bio-oil can reach 40-75%
  • the residue amount is not higher than 3%.
  • the reaction is carried out by introducing hydrogen into the biomass coal water slurry, and controlling the reaction pressure to be 15 to 25 MPa and the reaction temperature to be 300 to 420 ° C to finally obtain a bio-oil; the process of the present invention is in the presence of an appropriate amount of water.
  • the high-temperature and high-temperature hydrolysis of coal and biomass is carried out, and under the action of hydrogen and catalyst, the hydrolyzed product is further cracked and hydrogenated to realize the conversion from coal and biomass to bio-oil.
  • the conversion ratio of coal to biomass can reach 85-95%
  • the yield of bio-oil can reach 60-80%
  • the amount of residue is less than 5%.
  • the multi-stage liquefaction process of coal and biomass provided by the invention liquefies coal and biomass under high temperature and high pressure conditions, and the liquefied products successively occur under the action of hydrogen and the first catalyst and the second catalyst. Cracking, hydrogenation and deep cracking, hydrogenation reactions to achieve the conversion of coal and biomass to bio-oil and the refining of bio-oil.
  • the biomass and coal conversion rate can reach 95 to 99%, the bio-oil yield can reach 70-80%, and the residue amount is less than 2.5%.
  • the multi-stage liquefaction process of coal and biomass provided by the invention generates hydrolysis of coal and biomass by high pressure and high temperature, and primary cracking of hydrolyzed products in the presence of hydrogen and the first catalyst and the second catalyst. Hydrogenation reaction and deep cracking, hydrogenation reaction, thereby realizing the conversion of coal and biomass to bio-oil and the purification of bio-oil.
  • the conversion rate of biomass and coal can reach 97 to 99%, the yield of bio-oil can reach 70-80%, and the amount of residue is less than 3%.
  • amorphous alumina loaded with a metal oxide of Group VIB, VIIB or VIII is used as the second catalyst, and hydrogen gas is introduced to refine the bio-oil, which is better obtained by vulcanization with a noble metal.
  • the hydrogenation performance further avoids coke formation, and the amorphous alumina has an acidity, which makes the cracking more sufficient.
  • the co-liquefaction process of coal and biomass provided by the invention can ensure uniform particle size of solid particles used for preparing biomass oil coal slurry, so that the stability of the obtained biomass coal slurry is more stable. Well, it is not easy to settle during transportation, avoiding blockage of the transportation pipeline and damage to the liquefaction equipment.
  • the solid biomass is pretreated by drying, pulverizing and ash removal, and then mixed with the catalyst to better utilize the surface energy of the coal and biomass powder to cause the catalyst to adhere to the surface, so that the catalyst can be timely Hydrogen transfer is provided for coal and biomass liquefaction products, thereby ensuring that coke polycondensation does not occur during the entire process, thereby reducing the amount of residue.
  • the hydrolyzed hydrogenation process of biomass provided by the present invention, by using a slurry bed reactor, the reaction raw material is first sent from the bottom of the reactor to the slurry bed reactor to react, and then the reactor is injected into the reactor. Hydrogen, so in the reactor can rely on the different specific gravity of gas, liquid, solid materials and the change in specific gravity caused by the production of light oil after the reaction, to achieve differential control of the flow velocity of each phase, so that biomass raw materials Hydrolysis, cracking, and hydrogenation reactions occur from bottom to top in the reactor. In this process, even if the biomass and catalyst solid particles rise with gas and light oil, they return to the upper cold hydrogen.
  • the hydrolyzation hydrogenation process of biomass provided by the present invention in the first-stage reaction, by injecting high-pressure hydrogen into the slurry twice, that is, injecting high-pressure hydrogen gas before and after heating the slurry, the injection of the previous high-pressure hydrogen gas may be Increase the disturbance of the slurry in the heat exchanger to avoid deposition of solid biomass and catalyst.
  • high pressure hydrogen is injected into the slurry three times, that is, high pressure hydrogen is injected once before and after the slurry is heated, and then before the mixture of the first hydrogenation product and the second catalyst enters the second slurry bed reactor.
  • the high-pressure hydrogen gas is injected again, and the injection of the first high-pressure hydrogen gas can increase the disturbance of the slurry in the heat exchanger, thereby avoiding the deposition of biomass and catalyst.
  • the gas velocity can be supplied to various liquids, solids, and catalysts, and the difference in phase and density of the mixture can be achieved by the difference in phase and density of the mixture, and can be based on the layers in the reactor.
  • the density difference is adjusted by the hydrogen injection port on the outer wall of the reactor to ensure sufficient hydrolysis, cracking and hydrogenation reactions.
  • the hydrolyzed hydrogenation process of biomass provided by the invention the catalyst added in the slurry is subjected to vulcanization treatment, and the catalyst after vulcanization has better hydrogenation performance, can further avoid coke formation, and further hydrolyze hydrogenation reaction. full.
  • a process for hydrolyzing hydrogenation of biomass comprising the following steps:
  • the rice straw and the reed straw 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 rice straw and the reed straw are sent to a briquetting machine for compression extrusion at a temperature of 30 ° C and a pressure of 3 MPa, followed by secondary pulverization, and the median particle size after secondary pulverization is 30 ⁇ m.
  • the bulk density after the secondary pulverization was 500 kg/m 3 , which was used.
  • the specific method of supporting iron oxide on the above biomass carbon carrier is:
  • the biological carbon carrier and the aqueous solution of iron oxide are mixed and formulated into a suspension, and an aqueous solution of sodium carbonate and ammonia water as a precipitating agent is added, and the iron oxide is precipitated on the biomass carbon carrier, and the catalyst is obtained by washing, drying and vulcanization.
  • the temperature of the precipitation process was 90 ° C, and the pH was 7, and the iron oxide content was 50% by weight based on the total mass of the iron oxide and the biomass carbon carrier.
  • the pretreated biomass and the catalyst are mixed to obtain a mixture, and the mixture is added to a mixed oil of a hydrophobic oil and a residual oil to be stirred and slurried to form a slurry.
  • the total content of the rice straw and the reed straw in the slurry is 60 wt. %, the viscosity of the slurry is 500mPa. s (50 ° C), the content of the catalyst in the above slurry was 10% by weight, and the particle diameter of the catalyst to be charged was 5 ⁇ m.
  • Hydrogen is introduced into the biomass slurry to react, the reaction pressure is controlled to 20 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, thereby forming a reaction raw material; feeding the above-mentioned reaction raw material into the slurry bed reactor to cause hydrolysis, Cracking and hydrogenation reaction, simultaneously injecting high-pressure cold hydrogen into the slurry-bed reactor to control the total gas velocity in the slurry-bed reactor to be 0.2 m/s; wherein the pressures of high-pressure hydrogen and high-pressure cold hydrogen are both 22 MPa. , the temperature of the high pressure cold hydrogen is 135 ° C;
  • the high pressure cold hydrogen is injected through three injection ports on the side wall of the slurry bed reactor.
  • the inventory of the catalyst in the slurry bed reactor accounted for 30% by weight of the liquid phase mass in the slurry bed reactor, and the reaction time was 30 min.
  • a process for hydrolyzing hydrogenation of biomass comprising the following steps:
  • the linseed oil residue and the peanut oil residue are sent to a dryer and dried at 110 ° C for 2 hours to a water content of less than 2 wt%, and then sent to an ultrafine pulverizer for preliminary pulverization, and the median diameter after initial pulverization is 300 ⁇ m, and then The initially pulverized linseed oil slag and peanut oil slag are sent to a briquetting machine for compression extrusion at a temperature of 60 ° C and a pressure of 3 MPa, followed by secondary pulverization, and the median particle size after secondary pulverization is 50 ⁇ m. After the second pulverization, the bulk density was 1500 kg/m 3 and was used.
  • the biological carbon carrier and the aqueous solution of iron oxyhydroxide are mixed and formulated into a suspension, and an aqueous solution of sodium hydrogencarbonate and potassium hydroxide as a precipitating agent is added, and the iron oxyhydroxide is precipitated on the biomass carbon carrier, washed, dried,
  • the catalyst was prepared by vulcanization, the temperature of the precipitation process was 30 ° C, and the pH was 9, and the content of iron oxyhydroxide was 10 wt% based on the total mass of the iron oxyhydroxide and the biomass carbon support.
  • the pretreated biomass and the catalyst are mixed to obtain a mixture, and the mixture is added to a mixed oil of waste lubricating oil and waste engine oil to be dispersed and slurried to form a slurry, and the total content of linseed oil residue and peanut oil residue in the slurry is detected. 50wt%, the viscosity of the slurry is 700mPa. s (50 ° C), the content of the catalyst in the above slurry was 0.1% by weight, and the particle diameter of the catalyst to be charged was 500 ⁇ m.
  • Hydrogen is introduced into the biomass slurry to react, and the reaction pressure is 15 MPa and the reaction temperature is 420 ° 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; feeding the above-mentioned reaction raw material into the slurry bed reactor to cause hydrolysis, Cracking and hydrogenation reaction, simultaneously injecting high-pressure cold hydrogen into the slurry-bed reactor to control the total gas velocity in the slurry-bed reactor to be 0.02 m/s; wherein the pressures of high-pressure hydrogen and high-pressure cold hydrogen are both 15 MPa. , the temperature of the high pressure cold hydrogen is 50 ° C;
  • the high pressure cold hydrogen is injected through five injection ports on the side wall of the slurry bed reactor.
  • the inventory of the catalyst in the slurry bed reactor accounted for 5 wt% of the liquid phase mass in the slurry bed reactor, and the reaction time was 120 min.
  • a multi-stage 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 200 ⁇ m, and then the initial pulverization is carried out.
  • the cotton straw is sent to a briquetting machine for compression extrusion molding at a temperature of 50 ° C and a pressure of 2 MPa, followed by secondary pulverization, and the median diameter after secondary pulverization is 40 ⁇ m, and the cotton after secondary pulverization
  • the bulk density of the straw is 450kg/m 3 , which is reserved.
  • the specific method of supporting iron hydroxide and iron oxide on the first biomass carbon carrier is as follows:
  • the first biomass carbon carrier, an aqueous solution of iron hydroxide and iron oxide is mixed to prepare a suspension, and an aqueous solution of ammonia water and potassium hydroxide as a precipitating agent is added to precipitate iron hydroxide and iron oxide in the first biomass carbon carrier.
  • the first catalyst is prepared by washing, drying and vulcanization, the temperature of the precipitation process is 60 ° C, the pH is 8, and the iron hydroxide is determined by the total mass of the iron hydroxide, the iron oxide and the first biomass carbon carrier.
  • the total content of iron oxide and iron oxide is 30% by weight; the particle diameter of the first catalyst is 5 to 500 ⁇ m.
  • the second biomass carbon carrier is prepared, wherein the acid concentration of the H + substance in the acidified acid medium is 3 mol/L, and the volume ratio of the biomass carbon to the acidic medium is 1: 10, the acidification temperature is 50 ° C, the acidification time is 6 h;
  • the pretreated biomass and the first catalyst are mixed to obtain a mixture, and the mixture is added to a mixed oil of heavy oil and washing oil to be emulsified and pulped to form a slurry.
  • the total content of the cotton straw in the slurry is 55 wt%.
  • the viscosity of the slurry is 600mPa. s (50 ° C), in the above slurry, the content of the first catalyst was 2% by weight.
  • reaction pressure is 20 MPa
  • reaction temperature is 420 ° C
  • secondary hydrogenation product is obtained, and the secondary hydrogenation is added.
  • the hydrogen product is subjected to hydrogenation reforming at a pressure of 23 MPa and a temperature of 250 ° C to collect the oil phase to obtain a bio-oil; wherein the second catalyst is added in an amount of 1 wt% of the mass of the first-stage hydrogenation product;
  • the specific method of introducing hydrogen into the slurry is: injecting high-pressure hydrogen into the slurry, and controlling the volume ratio of the high-pressure hydrogen to the slurry to be 700:1, thereby forming a first-stage reaction raw material; Into the first slurry bed reactor to generate a first-stage hydrogenation reaction, while injecting high-pressure cold hydrogen into the first slurry-bed reactor to control the total gas velocity in the first slurry-bed reactor to be 0.1 m/s
  • the pressure of high pressure hydrogen and high pressure cold hydrogen is 22 MPa
  • the temperature of the high pressure cold hydrogen is 95 ° C;
  • the specific method of introducing hydrogen gas is: raising the mixture of the primary hydrogenation product and the second catalyst to 420 ° C, and then feeding the mixture into the second slurry bed reactor and passing the high pressure.
  • the high-temperature hydrogen gas is subjected to the second-stage hydrogenation reaction, and at the same time, the high-pressure cold hydrogen is injected into the second slurry-bed reactor, and the total gas velocity in the second slurry-bed reactor is controlled to be 0.08 m/s, and the high-pressure high-temperature hydrogen gas is
  • the volume ratio of the first-stage hydrogenation product is 1200:1; wherein the pressures of the high-pressure high-temperature hydrogen gas and the high-pressure cold hydrogen are both 22 MPa, the temperature of the high-pressure high-temperature hydrogen gas is 450 ° C, and the temperature of the high-pressure cold hydrogen is 85 °C.
  • the high pressure cold hydrogen is injected through four injection ports on the sidewalls of the first slurry bed reactor and the second slurry bed reactor.
  • the first catalyst in the first slurry bed reactor accounts for 10% by weight of the liquid phase mass in the first slurry bed reactor, and the second catalyst in the second slurry bed reactor accounts for the second slurry bed. 20 wt% of the liquid phase mass in the reactor; the time of the first hydrogenation reaction is 40 min, and the time of the second hydrogenation reaction is 45 min.
  • a multi-stage liquefaction process for biomass comprising the following steps:
  • the olive oil residue is sent to a dryer and dried at 85 ° 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.
  • the median diameter after the initial pulverization is 150 ⁇ m, and then the initial The pulverized olive oil slag is sent to a plodder and subjected to compression extrusion at a temperature of 45 ° C and a pressure of 3.5 MPa, followed by secondary pulverization treatment, and the median diameter after secondary pulverization is 35 ⁇ m.
  • the bulk density after the secondary pulverization was 1,535 kg/m 3 , and was used.
  • the pretreated biomass is mixed with the vulcanized amorphous iron oxyhydroxide (having a particle diameter of 50 to 500 ⁇ m) as a first catalyst to obtain a mixture, and the mixture is added to an rancid oil to be sheared and formed.
  • the slurry after testing, the total content of the olive oil residue in the slurry is 62% by weight, and the viscosity of the slurry is 600 mPa. s (50 ° C), the content of amorphous iron oxyhydroxide in the above slurry was 2% by weight.
  • the amount of the amorphous alumina supported as the second catalyst with W oxide and Ni oxide is 0.5% by weight of the mass of the primary hydrogenation product, and the particle size of the second catalyst to be added is 50 -400 ⁇ m;
  • the specific method of introducing hydrogen gas is: injecting high-pressure hydrogen into the slurry twice, specifically: after injecting high-pressure medium-temperature hydrogen into the slurry for the first time, and heat-treating the slurry to 250 ° C.
  • the temperature of the high-pressure medium-temperature hydrogen is 350 ° C, the temperature of the high-pressure high-temperature hydrogen is 360 ° C;
  • the total volume of the high-pressure medium-temperature hydrogen and the high-pressure high-temperature hydrogen introduced into the slurry a volume ratio of 800:1 to form a primary reaction feedstock;
  • the primary reaction feedstock is fed to a first slurry bed reactor to effect a primary hydrogenation reaction while simultaneously to the first slurry bed reactor
  • Injecting high-pressure cold hydrogen into the reactor controlling the total gas velocity in the first slurry-bed reactor to be 0.05 m/s; wherein, the pressures of the high-pressure hydrogen and the high-pressure cold hydrogen are both 22 MPa, and the temperature of the high-pressure cold hydrogen is 65 ° C;
  • the specific method of introducing hydrogen gas is: heating the mixture of the primary hydrogenation product and the second catalyst to 430 ° C, and then feeding the mixture into the second slurry bed reactor and passing the high pressure.
  • the high-temperature hydrogen gas is subjected to the second-stage hydrogenation reaction, and at the same time, the high-pressure cold hydrogen is injected into the second slurry-bed reactor, and the total gas velocity in the second slurry-bed reactor is controlled to be 0.07 m/s, and the high-pressure high-temperature hydrogen gas is
  • the volume ratio of the first-stage hydrogenation product is 1450:1; wherein the pressures of the high-pressure high-temperature hydrogen gas and the high-pressure cold hydrogen are both 25 MPa, the temperature of the high-pressure high-temperature hydrogen gas is 470 ° C, and the temperature of the high-pressure cold hydrogen is 120 °C.
  • the high pressure cold hydrogen is injected through five injection ports on the sidewalls of the first slurry bed reactor and the second slurry bed reactor.
  • the first catalyst in the first slurry bed reactor accounts for 10% by weight of the liquid phase mass in the first slurry bed reactor, and the second catalyst in the second slurry bed reactor accounts for the second slurry bed. 15 wt% of the liquid phase mass in the reactor; the time of the first hydrogenation reaction is 50 min, and the time of the second hydrogenation reaction is 50 min.
  • a process for hydrolyzing hydrogenation of biomass comprising the following steps:
  • the pea straw, the sorghum straw and the rice straw are sent to a dryer and dried at 50 ° C for 3 hours to a water content of less than 2 wt%, and then sent to an ultrafine pulverizer for preliminary pulverization, and the median diameter after the initial pulverization is 250 ⁇ m. Then, the initially pulverized pea straw, sorghum straw and rice straw are fed into a plodder at a temperature of 55 ° C and a pressure of 1.5 MPa for compression extrusion molding, followed by secondary pulverization, and the median after secondary pulverization. The particle size was 45 ⁇ m, and the bulk density after secondary pulverization was 440 kg/m 3 , which was used.
  • Hydrogen is introduced into the biomass slurry to react, and the reaction pressure is 17 MPa and the reaction temperature is 420 ° C to prepare a bio-oil;
  • the specific method for introducing hydrogen into the slurry is: injecting high-pressure hydrogen into the slurry twice, specifically: after injecting high-pressure medium-temperature hydrogen into the slurry for the first time, and heat-treating the slurry to 420 ° C, and then to the slurry.
  • the second injection of high-pressure high-temperature hydrogen wherein, the temperature of the high-pressure medium-temperature hydrogen is 420 ° C, the temperature of the high-pressure high-temperature hydrogen is 430 ° C; the volume ratio of the total volume of the high-pressure medium-temperature hydrogen and the high-pressure high-temperature hydrogen to the slurry is 900: 1, thereby forming a reaction feedstock; the reaction feedstock fed to the hydrogenation reaction of the hydrolysis slurry bed reactor occurs while injecting hydrogen into the cold high pressure above the slurry bed reactor, control of the total gas in the slurry bed reactor The speed is 0.08 m / s; wherein, the pressure of high pressure hydrogen and high pressure cold hydrogen is 20 MPa, the temperature of the high pressure cold hydrogen is 95 ° C;
  • the high pressure cold hydrogen is injected through five injection ports on the side wall of the slurry bed reactor.
  • the inventory of the catalyst in the slurry bed reactor accounted for 25 wt% of the liquid phase mass in the slurry bed reactor, and the reaction time was 50 min.
  • a process for hydrolyzing hydrogenation of biomass comprising the following steps:
  • the soybean oil residue is sent to a dryer and dried at 95 ° C for 2.5 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 300 ⁇ m, and then the initial pulverization is performed.
  • the soybean oil residue is sent to a plodder for compression extrusion at a temperature of 58 ° C and a pressure of 3.1 MPa, followed by secondary pulverization, and the median particle size after secondary pulverization is 48 ⁇ m, after secondary pulverization
  • the bulk density is 1512 kg/m 3 and is ready for use.
  • the specific method for introducing hydrogen into the slurry is: injecting high-pressure hydrogen into the slurry twice, specifically: after injecting high-pressure medium-temperature hydrogen into the slurry for the first time, heat-treating the slurry to 390 ° C, and then to the slurry.
  • the second injection of high-pressure high-temperature hydrogen wherein, the temperature of the high-pressure medium-temperature hydrogen is 400 ° C, the temperature of the high-pressure high-temperature hydrogen is 490 ° C; the volume ratio of the total volume of the high-pressure medium-temperature hydrogen and the high-pressure high-temperature hydrogen to the slurry is 800: 1, thereby forming a reaction raw material; feeding the above-mentioned reaction raw material into a slurry bed reactor to generate a hydrolyzation hydrogenation reaction, simultaneously injecting high-pressure cold hydrogen into the slurry-bed reactor to control the total gas in the slurry-bed reactor The speed is 0.07 m / s; wherein, the pressure of high pressure hydrogen and high pressure cold hydrogen is 22 MPa, the temperature of the high pressure cold hydrogen is 105 ° C;
  • the high pressure cold hydrogen is injected through five injection ports on the side wall of the slurry bed reactor.
  • the inventory of the catalyst in the slurry bed reactor accounted for 23% by weight of the liquid phase mass in the slurry bed reactor, and the reaction time was 100 min.
  • a multi-stage liquefaction process for biomass comprising the following steps:
  • the hemp stalk and the broad bean stalk are sent to a dryer and dried at 65 ° C for 3 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 260 ⁇ m, and then the initial The pulverized hemp stalk and the broad bean stalk are sent to a plodder for compression extrusion at a temperature of 50 ° C and a pressure of 0.5 MPa, followed by secondary pulverization, and the median diameter of the biomass after secondary pulverization It is 30 ⁇ m, and the bulk density after secondary pulverization is 410 kg/m 3 , which is reserved.
  • the iron oxide is supported on the first biomass carbon carrier and vulcanized to obtain a first catalyst.
  • the specific method of supporting iron oxide on the above first biomass carbon carrier is:
  • the first biomass carbon carrier and the aqueous solution of iron oxide are mixed and formulated into a suspension, and an aqueous solution of sodium hydroxide and ammonia water as a precipitating agent is added, and the iron oxide is precipitated on the first biomass carbon carrier, washed, dried, and vulcanized.
  • the first catalyst is prepared, the temperature of the precipitation process is 80 ° C, the pH is 7.5, and the content of iron oxide is 50 wt% based on the total mass of the iron oxide and the first biomass carbon carrier; the particle diameter of the first catalyst is 10-450 ⁇ m.
  • the second biomass carbon carrier is prepared, and the amount of the OH- substance in the alkalized alkaline medium is 0.5 mol/L, and the biomass carbon and the alkaline medium are used.
  • the volume ratio is 1:15, the alkalization temperature is 30 ° C, and the acidification time is 10 h;
  • the pretreated biomass and the first catalyst are mixed to obtain a mixture, and the mixture is added to the trench oil to be dispersed and pulped to form a slurry.
  • the total content of the cannabis straw and the broad bean straw in the slurry is determined to be 40% by weight.
  • the viscosity is 1200mPa. s (50 ° C), the content of the first catalyst in the above slurry was 0.2% by weight.
  • the dosage of the second catalyst is 0.8 wt% of the mass of the first-stage hydrogenation product; in the step (1), the specific method of introducing hydrogen gas is: injecting high-pressure hydrogen into the slurry, and controlling the high-pressure hydrogen and the slurry.
  • the volume ratio is 600:1 to form a first-stage reaction raw material; the first-stage reaction raw material is sent to the first slurry-bed reactor to generate a primary hydrogenation reaction, and at the same time, a high pressure is injected into the first slurry-bed reactor.
  • Cold hydrogen, controlling the total gas velocity in the first slurry bed reactor is 0.2 m / s; wherein, the pressure of high pressure hydrogen and high pressure cold hydrogen are 27 MPa, the temperature of high pressure cold hydrogen is 50 ° C;
  • the specific method of introducing hydrogen gas is: heating the mixture of the primary hydrogenation product and the second catalyst to 400 ° C, and then feeding the mixture to the second slurry bed reactor. And introducing high-pressure high-temperature hydrogen gas to generate a second-stage hydrogenation reaction, simultaneously injecting high-pressure cold hydrogen into the second slurry-bed reactor, and controlling the total gas velocity in the second slurry-bed reactor to be 0.06 m/s, and the volume ratio of the high-pressure high-temperature hydrogen to the first-stage hydrogenation product is 1500:1; wherein the high-pressure high-temperature hydrogen and the high-pressure cold hydrogen have a pressure of 27 MPa, and the high-pressure high-temperature hydrogen has a temperature of 430 °C, the temperature of the high pressure cold hydrogen is 50 °C.
  • the high pressure cold hydrogen is injected through three injection ports on the sidewalls of the first slurry bed reactor and the second slurry bed reactor.
  • the first catalyst in the first slurry bed reactor accounts for 5% by weight of the liquid phase mass in the first slurry bed reactor, and the second catalyst in the second slurry bed reactor accounts for the second slurry bed. 30 wt% of the liquid phase mass in the reactor; the time of the first hydrogenation reaction is 30 min, and the time of the second hydrogenation reaction is 90 min.
  • a multi-stage liquefaction process for biomass comprising the following steps:
  • the peanut oil residue is sent to a dryer and dried at 80 ° C for 2 h to a water content of less than 2 wt %, and then sent to an ultrafine pulverizer for preliminary pulverization.
  • the median diameter after initial pulverization is 160 ⁇ m, and then the initial pulverization is performed.
  • Peanut 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 treatment.
  • the median diameter of the biomass after secondary pulverization is 45 ⁇ m, twice.
  • the pulverized bulk density was 1510 kg/m 3 and was used.
  • the specific method for supporting the iron oxyhydroxide on the first biomass carbon carrier is as follows:
  • the first biomass carbon carrier and the aqueous solution of iron oxyhydroxide are mixed and formulated into a suspension, and an aqueous solution of sodium hydroxide and ammonia water as a precipitating agent is added, and the iron oxyhydroxide is precipitated on the first biomass carbon carrier, washed and dried.
  • vulcanization treatment to obtain a first catalyst the temperature of the precipitation process is 40 ° C, the pH value is 8.5, and the content of iron oxyhydroxide is 50 wt% based on the total mass of the iron oxyhydroxide and the first biomass carbon carrier; the first catalyst
  • the particle size is 110-250 ⁇ m.
  • the biomass carbon is alkalized to obtain a second biomass carbon carrier, wherein the alkalinized alkaline medium has a concentration of OH - 5 mol / L, dry distillation biomass carbon and alkaline medium
  • the volume ratio is 1:5, the alkalization temperature is 80 ° C, and the acidification time is 1 h;
  • the pretreated biomass and the first catalyst are mixed to obtain a mixture, and the mixture is added to the trench oil to be emulsified and pulped to form a slurry.
  • the total content of the peanut oil residue in the slurry is 65 wt%, and the viscosity of the slurry is 690mPa.
  • s (50 ° C) the content of the first catalyst in the above slurry was 4% by weight.
  • reaction has a reaction pressure of 25 MPa and a reaction temperature of 450 ° C to obtain a secondary hydrogenation product, and the secondary hydrogenation product is separated to collect an oil phase to obtain a bio-oil;
  • the dosage of the second catalyst is 1.4 wt% of the mass of the first-stage hydrogenation product
  • the specific method of introducing hydrogen gas is: injecting high-pressure hydrogen into the slurry, and controlling the volume ratio of the high-pressure hydrogen gas to the slurry to be 800:1, thereby forming a first-stage reaction raw material; a first-stage hydrogenation reaction occurs in a slurry-bed reactor, and high-pressure cold hydrogen is injected into the first slurry-bed reactor to control the total gas velocity in the first slurry-bed reactor to be 0.1 m/s;
  • the pressure of high pressure hydrogen and high pressure cold hydrogen is 26 MPa, and the temperature of high pressure cold hydrogen is 70 ° C;
  • the specific method of introducing hydrogen gas is: raising the mixture of the primary hydrogenation product and the second catalyst to 450 ° C, and then feeding the mixture to the second slurry bed reactor. And introducing high-pressure high-temperature hydrogen gas to generate a second-stage hydrogenation reaction, simultaneously injecting high-pressure cold hydrogen into the second slurry-bed reactor, and controlling the total gas velocity in the second slurry-bed reactor to be 0.09 m/s, and the volume ratio of the high-pressure high-temperature hydrogen to the first-stage hydrogenation product is 1100:1; wherein the high-pressure high-temperature hydrogen and the high-pressure cold hydrogen have a pressure of 27 MPa, and the high-pressure high-temperature hydrogen has a temperature of 460 °C, the temperature of the high pressure cold hydrogen is 60 °C.
  • the high pressure cold hydrogen is injected through three injection ports on the sidewalls of the first slurry bed reactor and the second slurry bed reactor.
  • the first catalyst in the first slurry bed reactor accounts for 23% by weight of the liquid phase mass in the first slurry bed reactor, and the second catalyst in the second slurry bed reactor accounts for the second slurry bed. 30 wt% of the liquid phase mass in the reactor; the time of the first hydrogenation reaction is 50 min, and the time of the second hydrogenation reaction is 85 min.
  • the biomass conversion obtained by the method of the present invention is 95-99%
  • the oil phase yield is 71-86%
  • the residue amount is less than 0.1 wt%
  • the carbon content in the obtained oil phase is 73-90 wt%
  • a hydrogen content of 5-17 wt% is a hydrogen content of 0.1-10 wt%.
  • the two-stage reaction can further reduce the oxygen content in the oil phase.
  • Coal to biomass conversion (quality of liquefied reaction product - mass of catalyst - quality 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).
  • a co-liquefaction process of coal and biomass comprising the following steps:
  • the lignite was taken, dried and dehydrated, and pulverized to a median diameter of 50 ⁇ m, and then extruded at 30 ° C to a molding pressure of 15 MPa to obtain a brown coal compressed material.
  • the lignite compressed material was pulverized to obtain a lignite pulverized material having a particle diameter of 30 ⁇ m.
  • the above-mentioned lignite pulverized material is added to the mixture of liquid slag and waste engine oil together with the amorphous iron oxyhydroxide after vulcanization in the reactor to form a biomass kerosene slurry, and hydrogen gas is introduced into the biomass kerosene slurry to occur.
  • the reaction was controlled to a reaction pressure of 16 MPa and a reaction temperature of 480 ° C to finally obtain a bio-oil.
  • a co-hydrolysis hydrogenation process of coal and biomass comprising the following steps:
  • the straw is taken, dried and dehydrated, pulverized to a median particle size of 100 ⁇ m, and then sent to a briquetting machine or a plodder for extrusion molding, and the molding pressure is 2 MPa to obtain a straw compressed material.
  • the straw compressed material is sent to a hammer mill to be pulverized to obtain a straw pulverized material having a median diameter of 30 ⁇ m, which is ready for use.
  • 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 at a molding pressure of 5 MPa to obtain a brown coal compressed material.
  • the lignite compressed material is sent to a ball mill and pulverized to obtain a lignite pulverized material having a median diameter of 100 ⁇ m, which is ready for use.
  • the straw pulverized material and the lignite pulverized material are subjected to ash removal, and then mixed with the oxidized iron oxide-loaded biomass carbon to obtain a mixture, and the mixture is added to water to form the biomass coal water slurry.
  • the biomass coal water slurry is subjected to hydrogen gas to react, and the reaction pressure is controlled to 15 MPa, the reaction temperature is 300 ° C, and the reaction is carried out for 30 minutes to finally obtain a bio-oil.
  • the biomass carbon loaded with iron oxide is prepared by the following method:
  • biomass charcoal as a biomass carbon carrier
  • the specific method of supporting the sulfurized iron oxide on the biomass carbon carrier is:
  • the biomass carbon carrier and the sulfurized iron oxide aqueous solution are mixed and formulated into a suspension, and the sulfided iron oxide is precipitated on the biomass carbon carrier by adding a precipitating agent, and the catalyst is obtained by washing and drying.
  • the precipitating agent is aqueous ammonia and sodium carbonate solution, and the temperature of the precipitation process is controlled to 30 ° C and the pH is 7.
  • the iron oxide content is 10% by weight based on the total mass of the iron oxide and the biomass carbon.
  • a multi-stage liquefaction process for coal and biomass comprising the following steps:
  • the reed is taken, dried and dehydrated, and then sent to a jet mill for pulverization treatment 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 be subjected to secondary pulverization to obtain a secondary pulverized material of reed, and the particle diameter D 50 is 50 ⁇ m, which is ready for use.
  • the reed compressed material and the Shendong long flame coal compressed material may be separately mixed with a portion of the waste engine oil and then sent to the ball mill for the second pulverization.
  • the secondary pulverized material of the reed and the coal is mixed with the carbon oxyhydroxide-loaded biomass carbon after the sulfidation treatment in the reactor to obtain a mixture, and the mixture is added to the waste engine oil to form the biomass.
  • Kerosene slurry as a preferred mode, the above-mentioned biomass kerosene slurry can continue to be treated by a colloid mill, and the slurryability of the biomass kerosene slurry can be continuously improved.
  • Hydrogen is introduced into the biomass kerosene slurry to generate a primary hydrogenation reaction to obtain a primary hydrogenation product; and a primary hydrogenation product is added to the reactor to be vulcanized and loaded with Pd oxide and Ni oxide.
  • the biomass carbon is passed through hydrogen to generate a secondary hydrogenation reaction to obtain a secondary hydrogenation product, and the secondary hydrogenation product is separated to finally obtain a bio-oil.
  • the pressure for controlling the two reactions was 17 MPa
  • the temperature of the first hydrogenation reaction was 310 ° C
  • the reaction time was 45 min
  • the temperature of the second hydrogenation reaction was 460 ° C
  • the reaction time was 70 min.
  • the content of the reed is 25 wt%
  • the content of the coal is 45 wt%
  • the content of the first catalyst is 0.1 wt%
  • the particle diameter of the first catalyst is 500 ⁇ m
  • the second catalyst is added in an amount of 0.5% by weight of the first-stage hydrogenated product, the second catalyst has a particle diameter of 500 ⁇ m
  • the second catalyst is added to the first-stage hydrogenated product.
  • the method further comprises the step of formulating the second catalyst into a catalyst slurry, which is specifically: mixing the second catalyst with the waste engine oil at a mass ratio of 1:10 to prepare the catalyst slurry. .
  • a multi-stage liquefaction process for coal and biomass comprising the following steps:
  • the mixture is mixed with the carbonic acid-loaded biomass carbon in the reactor to obtain a mixture, and the mixture is added to the water to form the biomass coal water slurry.
  • Hydrogen is introduced into the biomass coal water slurry to generate a primary hydrogenation reaction to obtain a first-stage hydrogenation product; and then a Mo-oxide and a Co oxide supported in the reactor are vulcanized to the primary hydrogenation product.
  • the biomass carbon is passed through hydrogen to generate a secondary hydrogenation reaction to obtain a secondary hydrogenation product, which is separated to finally obtain a bio-oil.
  • the pressure for controlling the two reactions is 18 MPa
  • the temperature of the first hydrogenation reaction is 240 ° C
  • the reaction time is 50 min
  • the temperature of the second hydrogenation reaction is 380 ° C
  • the reaction time is 30 min.
  • the content of the leaves and melons is 20% by weight
  • the content of the coal is 40% by weight
  • the content of the first catalyst is 2% by weight
  • the second catalyst is added in an amount of 0.8% by weight of the first-stage hydrogenated product, the second catalyst has a particle diameter of 400 ⁇ m
  • the second catalyst is added to the first stage
  • the method further comprises the step of formulating the second catalyst into a catalyst slurry, which is specifically: mixing the second catalyst with water at a mass ratio of 2:10 to prepare the catalyst slurry. .
  • a co-liquefaction process of coal and biomass comprising the following steps:
  • the algae is taken, dried and dehydrated, and then sent to a jet mill for pulverization treatment to obtain an algal primary pulverized material having a particle diameter D 50 of 200 ⁇ m.
  • the algae primary pulverized material is sent to a briquetting machine or a beading machine for extrusion molding at 45 ° C, and the molding pressure is 2 MPa to obtain an algae compressed material.
  • the algae compressed material was sent to a jet mill to be subjected to secondary pulverization to obtain an algal secondary pulverized material having a particle diameter D 50 of 40 ⁇ m, which was used.
  • the lignite is taken, dried and dehydrated, and then sent to a ball mill for pulverization treatment to obtain a lignite primary pulverized material having a particle diameter D 50 of 80 ⁇ m.
  • the lignite primary pulverized material is sent to a briquetting machine or a plodder for extrusion molding at 60 ° C, and the molding pressure is 15 MPa to obtain a brown coal compressed material.
  • the brown coal compressed material is sent to a ball mill for secondary pulverization to obtain a brown coal secondary pulverized material having a particle diameter D 50 of 30 ⁇ m, which is ready for use.
  • the above-mentioned algae and lignite secondary pulverized material are screened, and the >100 ⁇ m algae is separated from the lignite, and then put into the compression section or the second pulverization step to be treated again with the subsequent feed to obtain a more uniform particle size. Thereby obtaining a more stable biomass kerosene slurry.
  • the secondary pulverized material of the algae and lignite is subjected to ash removal and mixed with the amorphous iron oxyhydroxide after vulcanization in the reactor to obtain a mixture, and the mixture is added to the bio-oil prepared by the process, thereby forming a
  • the biomass kerosene slurry is introduced into the biomass kerosene slurry to generate a reaction, and the reaction pressure is controlled to 20 MPa and the reaction temperature is 390 ° C to obtain a bio-oil.
  • sulfur and amorphous iron oxyhydroxide were mixed at a mass ratio of 0.4:1 to obtain a catalyst.
  • the content of the algae is 20% by weight
  • the content of the coal is 40% by weight
  • the content of the catalyst is 4% by weight
  • the particle diameter of the catalyst is 300 ⁇ m.
  • the specific method for introducing hydrogen gas is: injecting high-pressure hydrogen into the biomass kerosene slurry, and controlling a volume ratio of the high-pressure hydrogen gas to the biomass kerosene slurry to be 600:1, thereby forming a reaction raw material;
  • the reaction raw material is sent to the slurry bed reactor to generate liquefaction, cracking and hydrogenation reaction, and high pressure cold hydrogen is injected into the slurry bed reactor to control the total gas velocity in the slurry bed reactor.
  • 0.2 m/s wherein the pressures of the high pressure hydrogen gas and the high pressure cold hydrogen are both 13 MPa, and the temperature of the high pressure cold hydrogen is 135 °C.
  • a co-hydrolysis hydrogenation process of coal and biomass comprising the following steps:
  • 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 slag, and the particle diameter D 50 is 150 ⁇ m.
  • soybean slag oil slag primary pulverized material is sent to a briquetting machine or a plodder for extrusion molding, and the molding pressure is 4 MPa, and the soybean oil slag compressed material is obtained.
  • 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 secondary pulverized material of Shendong Changyan coal and soybean oil slag is added to water together with the amorphous iron oxyhydroxide after vulcanization treatment in the reactor to form the biomass coal water slurry.
  • the above The biomass coal water slurry can continue to be treated by a colloid mill, and the slurryability of the biomass coal water slurry can be continuously improved.
  • Hydrogen was introduced into the biomass coal water slurry to react, and the reaction pressure was 22 MPa, the reaction temperature was 410 ° C, and the reaction time was 60 min, and finally a bio-oil was obtained.
  • sulfur and amorphous iron oxyhydroxide are mixed at a mass ratio of 0.8:1 to obtain a catalyst.
  • the soybean oil slag content is 25 wt%
  • the coal content is 40 wt%
  • the catalyst content is 6 wt%
  • the catalyst has a particle diameter of 200 ⁇ m.
  • the specific method for introducing hydrogen gas is: after injecting high-pressure medium-temperature hydrogen gas with a pressure of 18 MPa and a temperature of 350 ° C for the first time into the biomass coal water slurry, and heat-heating the biomass coal water slurry Up to 200 ° C, and then injecting a high pressure and high temperature hydrogen gas having a pressure of 18 MPa and a temperature of 510 ° C into the biomass coal water slurry for a second time, and controlling the volume of the twice injected high pressure hydrogen gas and the biomass coal water slurry
  • the ratio is 700:1 to form a reaction raw material; the reaction raw material is sent to a slurry bed reactor to undergo hydrolysis, cracking and hydrogenation reaction, and a pressure of 18 MPa and a temperature are injected into the slurry bed reactor.
  • the cold hydrogen was injected via 5 injection ports on the side wall of the slurry bed reactor to control the total gas velocity in the slurry bed reactor to be 0.08 m/s.
  • a multi-stage liquefaction process for coal and biomass comprising the following steps:
  • the pulverized material After the pulverized material is degreased, it is mixed with the amorphous iron oxyhydroxide which has been vulcanized in the reactor to obtain a mixture, and the mixture is added to the mixed coal tar and petroleum to form the biomass kerosene slurry. Hydrogen is introduced into the biomass kerosene slurry to generate a first-stage hydrogenation reaction to obtain a first-stage hydrogenation product; then, the first-stage hydrogenation product is added to the first-stage hydrogenation product, and the W-oxide and Ni oxide are oxidized in the reactor.
  • the amorphous alumina of the material is passed through hydrogen to generate a secondary hydrogenation reaction to obtain a secondary hydrogenation product, and the secondary hydrogenation product is finally separated to obtain a bio-oil; the pressure is 7 MPa and the temperature is 460.
  • the pressure for controlling the two reactions is 23 MPa
  • the temperature for the first hydrogenation reaction is 290 ° C
  • the temperature for the secondary hydrogenation reaction is 400 ° C
  • the time for the first hydrogenation reaction is 40 min
  • the secondary hydrogenation reaction is carried out.
  • the first catalyst was prepared by mixing sulfur and amorphous iron oxyhydroxide in a mass ratio of 0.6:1 for 35 minutes.
  • the content of the palm oil slag is 10% by weight
  • the content of the rice straw is 15% by weight
  • the content of the coal is 40% by weight
  • the content of the first catalyst is 8% by weight.
  • the first catalyst has a particle diameter of 100 ⁇ m; the second catalyst is added in an amount of 1.8 wt% of the first-stage hydrogenated product, and the second catalyst has a particle diameter of 100 ⁇ m; Before the second catalyst is added to the first-stage hydrogenation product, the method further comprises the step of formulating the second catalyst into a catalyst slurry, which is specifically: mass ratio of the second catalyst to the solvent oil is 1: The catalyst slurry is prepared by mixing in proportion to 10; the solvent oil is animal oil and bio-oil prepared by the process.
  • the specific method for introducing hydrogen into the first-stage hydrogenation reaction in this embodiment is: after injecting high-pressure medium-temperature hydrogen gas having a pressure of 23 MPa and a temperature of 260 ° C for the first time into the biomass kerosene slurry, the raw The heat exchange of the material kerosene slurry is heated to 280 ° C, and then the second high pressure high temperature hydrogen gas having a pressure of 23 MPa and a temperature of 430 ° C is injected into the biomass kerosene slurry, and the two injected high pressure hydrogen gas and the biomass are controlled.
  • the volume ratio of the kerosene slurry is 800:1, thereby forming a first-stage reaction raw material; the first-stage reaction raw material is sent into the first slurry-bed reactor to generate a primary hydrogenation reaction, and simultaneously to the first slurry state
  • the bed reactor is filled with high pressure cold hydrogen having a pressure of 23 MPa and a temperature of 80 ° C, and the high pressure cold hydrogen is injected through four injection ports on the side wall of the first slurry bed reactor to control the first slurry state.
  • the total gas velocity in the bed reactor was 0.05 m/s.
  • the hydrogen is introduced into the second hydrogenation reaction by heating the mixture of the primary hydrogenation product and the second catalyst to 440 ° C, and then feeding the mixture to the second slurry state.
  • a high-pressure high-temperature hydrogen gas having a pressure of 23 MPa and a temperature of 440 ° C is introduced into the bed reactor to generate a secondary hydrogenation reaction, and a high pressure of 23 MPa and a temperature of 80 ° C is injected into the second slurry bed reactor.
  • Cold hydrogen the high pressure cold hydrogen is injected through four injection ports on the side wall of the second slurry bed reactor, and controls the total gas velocity in the second slurry bed reactor to be 0.07 m/s, and hydrogen gas
  • the volume ratio to the primary hydrogenation product was 1350:1.
  • the inventory of the first catalyst in the first slurry bed reactor is controlled at 5% by weight of the liquid phase mass in the first slurry bed reactor, and the second catalyst is in the second slurry bed
  • the inventory in the reactor was controlled at 30 wt% of the liquid phase mass in the second slurry bed reactor.
  • a multi-stage liquefaction process for coal and biomass comprising the following steps:
  • the reed is taken, dried and dehydrated, and then sent to a jet mill for pulverization treatment 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 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 50 ⁇ m, which is ready for use.
  • the brown coal is taken, dried and dehydrated, and then sent to a ball mill for pulverization treatment to obtain a lignite primary pulverized material having a particle diameter D 50 of 100 ⁇ m.
  • the lignite primary pulverized material is sent to a briquetting machine or a plodder for extrusion molding, and the molding pressure is 12 MPa to obtain a brown coal compressed material.
  • the brown coal compressed material is sent to a ball mill for secondary pulverization to obtain a brown coal secondary pulverized material having a particle diameter D 50 of 100 ⁇ m, which is ready for use.
  • the aluminum oxide is shaped and hydrogen is introduced to generate a secondary hydrogenation reaction to obtain a secondary hydrogenation product, and the secondary hydrogenation product is finally separated to obtain a bio-oil; and the conditions include a pressure of 23 MPa and a temperature of 250 ° C.
  • the step of hydro-reforming the secondary hydrogenation product is carried out.
  • the pressure for controlling the two reactions is 20 MPa
  • the temperature of the first hydrogenation reaction is 280 ° C
  • the temperature of the second hydrogenation reaction is 400 ° C
  • the time of the first hydrogenation reaction is 60 min
  • the second hydrogenation reaction The first catalyst was prepared by mixing sulfur and amorphous iron oxyhydroxide in a mass ratio of 1:1 for 30 min.
  • the content of the first catalyst is 10 wt%
  • the particle diameter of the first catalyst is 5 ⁇ m
  • the dosage of the second catalyst is the mass of the first-stage hydrogenation product.
  • the second catalyst has a particle diameter of 5 ⁇ m; and before the addition of the second catalyst to the primary hydrogenation product, further comprising the step of formulating the second catalyst into a catalyst slurry, Specifically, the catalyst slurry is prepared by mixing the second catalyst with water at a mass ratio of 2:10.
  • the specific method for introducing hydrogen into the first-stage hydrogenation reaction in the present embodiment is: after injecting high-pressure medium-temperature hydrogen gas having a pressure of 27 MPa and a temperature of 180 ° C for the first time into the biomass coal water slurry, The heat transfer of the biomass coal water slurry is heated to 350 ° C, and then a second high pressure high temperature hydrogen gas with a pressure of 27 MPa and a temperature of 360 ° C is injected into the biomass coal water slurry, and the two injected high pressure hydrogen gas is controlled.
  • the volume ratio of the biomass coal water slurry is 1000:1, thereby forming a first-stage reaction raw material; the first-stage reaction raw material is sent into the first slurry-bed reactor to generate a primary hydrogenation reaction, and at the same time
  • a high pressure cold hydrogen having an injection pressure of 27 MPa and a temperature of 50 ° C is injected, and the high pressure cold hydrogen is injected through three injection ports on the side wall of the first slurry bed reactor, and the control station
  • the total gas velocity in the first slurry bed reactor was 0.02 m/s.
  • the specific method of introducing hydrogen into the secondary hydrogenation reaction in this embodiment is: heating the mixture of the primary hydrogenation product and the second catalyst to 480 ° C, and then feeding the mixture to the second
  • a high-pressure high-temperature hydrogen gas having a pressure of 27 MPa and a temperature of 430 ° C is introduced into the slurry bed reactor to generate a secondary hydrogenation reaction, and a pressure of 27 MPa and a temperature of 50 ° C are injected into the second slurry bed reactor.
  • High pressure cold hydrogen which is injected through three injection ports on the side wall of the second slurry bed reactor, and controls the total gas velocity in the second slurry bed reactor to be 0.06 m/s, And the volume ratio of hydrogen to the primary hydrogenation product is 1500:1.
  • the inventory of the first catalyst in the first slurry bed reactor is controlled at 30 wt% of the liquid phase mass in the first slurry bed reactor, and the second catalyst is in the second slurry bed
  • the inventory in the reactor was controlled at 5% by weight of the liquid phase mass in the second slurry bed reactor.
  • a co-liquefaction process of coal and biomass comprising the following steps:
  • the lignite is taken, dried and dehydrated, and pulverized to a median particle size of 50 ⁇ m, and then sent to a briquetting machine or a plodder for extrusion molding at a molding pressure of 15 MPa to obtain a brown coal compressed material.
  • the lignite compressed material was sent to a hammer mill to be pulverized to obtain a lignite pulverized material having a particle diameter of 30 ⁇ m.
  • the above-mentioned lignite pulverized material is added to the mixture of liquid slag and waste engine oil together with the amorphous iron oxyhydroxide after vulcanization in the reactor to form a biomass kerosene slurry, and hydrogen gas is introduced into the biomass kerosene slurry to occur.
  • the reaction was carried out, and the reaction pressure was controlled to 4 MPa, and the reaction temperature was 430 ° C to finally obtain a bio-oil.
  • a co-liquefaction process of coal and biomass comprising the following steps:
  • the lignite is taken, dried and dehydrated, and pulverized to a median particle size of 50 ⁇ m, and then sent to a briquetting machine or a plodder for extrusion molding at a molding pressure of 15 MPa to obtain a brown coal compressed material.
  • the lignite compressed material was sent to a hammer mill to be pulverized to obtain a lignite pulverized material having a particle diameter of 30 ⁇ m.
  • the lignite pulverized material is added to a mixture of liquid slag and waste engine oil together with the oil-soluble dispersive hydrogenation catalyst which has been vulcanized in the reactor to form a biomass kerosene slurry, and hydrogen gas is introduced into the biomass kerosene slurry.
  • the reaction was carried out, and the reaction pressure was controlled to 16 MPa, and the reaction temperature was 480 ° C to finally obtain a bio-oil.
  • the co-conversion rate and the bio-oil yield of the biomass obtained by the process of the present invention are higher than those of the comparative examples 1-2, and the amount of residue is significantly reduced, thereby knowing
  • the method of the invention can significantly improve the biomass conversion rate and the yield of bio-oil, and reduce the amount of residue.
  • the secondary reaction can significantly reduce the residue content and the oxygen content in the oil phase.

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Abstract

一种生物质或煤与生物质的水解加氢工艺，其浆液的配制步骤为，将生物质依次进行干燥、初粉碎、压缩和二次粉碎，而后与催化剂混合得到混合物，将混合物加入至油品/水中研磨制浆即得生物质/煤浆液。该工艺将生物质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，使松散的生物质先后经历重新排位、机械变性和塑形流变等阶段，使得生物质的体积大幅度降低，由此可减少生物质的孔隙率，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，提高了泵在单位时间内对生物质的输送量，保证了泵的平稳运转和输送，同时提高了生物质的转化率。

Description

一种生物质的水解加氢工艺 技术领域
本发明涉及生物能源领域，具体涉及一种生物质的水解加氢工艺。
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。生物质是指一切直接或间接利用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、低污染性和广泛分布性，因此，从能源安全和环境保护出发，生物质的开发利用已成为当前发展可再生能源的战略重点。
生物质液化技术是生物质资源利用中的重要组成部分，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。目前主要可分为间接液化和直接液化两大类，其中，生物质直接液化技术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、催化液化和加压加氢液化等，尤其以加压加氢液化产品收率高、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水解加氢工艺。
为解决上述技术问题，本发明采用如下技术方案：
本发明提供的第一种技术方案：一种生物质的水解加氢工艺，包括如下步骤：
配制含有催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380-420℃，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，而后与所述催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％；初粉碎后的中位粒度为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。
在所述浆液中，所述浆液的粘度为500-1400mPa﹒s(50℃)。
在所述浆液中，所述生物质的含量为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。
在所述浆液中，所述催化剂的含量为0.1～10wt％，优选为2wt％；所述催化剂的粒径为5μm-500μm；
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(600～1000)：1，从而形成反应原料；
将所述反应原料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高压冷氢，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，所述高压氢气和高压冷氢的压力均为15-22MPa，所述高压冷氢的温度为50～135℃。
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高压中温氢气后，并将所述浆液换热升温至380-420℃，而后再向所述浆液中第二次注入高压高温氢气；
其中，所述高压中温氢气的温度为360-420℃，所述高压高温氢气的温度为430～510℃。
所述冷氢经由所述浆态床反应器侧壁上的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。
所述催化剂为经硫化处理的负载有活性组分的生物质炭，所述活性组分为氧化铁、羟基氧化铁或氢氧化铁中的一种或多种，以活性组分和生物质炭的总质量计，活性组分的含量为10～50wt％；
所述负载有活性组分的生物质炭的制备方法包括：
(1)取生物质炭为生物质炭载体；
(2)将活性组分负载于所述生物质炭载体上，制得所述催化剂。
将活性组分负载于所述生物质炭载体上的具体方法为：
将所述生物质炭载体、所述活性组分水溶液混合配制成悬浮液，加入沉淀剂将活性组分沉淀于生物质炭载体上，经洗涤、干燥制得所述催化剂；其中，所述沉淀剂为氨水或碱金属的碳酸盐、碳酸氢盐、氢氧化物中至少一种的水溶液，沉淀过程温度控制为30℃～90℃，pH值为7～9。
或所述催化剂为经硫化处理的无定型羟基氧化铁。
本发明还提供第二种技术方案：
一种生物质的水解加氢工艺，包括如下步骤：
配制含有催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380-440℃，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，而后与所述催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。
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％；初粉碎后的中位粒度为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。
在所述浆液中，所述浆液的粘度为300-700mPa﹒s(50℃)。
其中，所述油品的种类，研磨制浆方式，催化剂的用量、粒径，向所述浆液中通入氢气的具体方法，所述催化剂在所述浆态床反应器内的存量，反应时间，冷氢注入方式，催化剂的组成，所述负载有活性组分的生物质炭的制备方法均与第一种技术方案相同。
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高压中温氢气后，并将所述浆液换热升温至380-440℃，而后再向所述浆液中第二次注入高压高温氢气；
其中，所述高压中温氢气的温度为360-440℃，所述高压高温氢气的温度为450～510℃。
本发明还提供第三种技术方案：
一种生物质的多级液化工艺，包括如下步骤：
(1)配制含有第一催化剂和生物质的浆液，向所述浆液中通入氢气以发生一级加氢反应，控制反应压力为15～25MPa、反应温度为280～350℃，得到一级加氢产物；
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，而后与所述第一催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)向所述一级加氢产物中加入第二催化剂并通入氢气以发生二级加氢反应，控制反应压力为15～25MPa、反应温度为400～480℃，得到二级加氢产物，所述二级加氢产物经分离后收集油相，得到生物油。
其中，所述浆液的配制步骤中，秸秆的来源，秸秆的圧缩圧力、温度，秸秆的干燥温度、时间，含水率控制，粉碎中粒径控制，秸秆的堆密度，浆液粘度，浆液中秸秆的含量，油品的种类，研磨制浆方式等均与第一种技术方案相同。
在所述浆液中，所述第一催化剂的含量为0.1～10wt％，优选为2wt％；所述第一催化剂的粒径为5μm-500μm；
所述第二催化剂的投加量为所述一级加氢产物质量的0.5～2wt％，所述第二催化剂的粒径为5μm-500μm；
在将所述第二催化剂加入至所述一级加氢产物中之前，还包括将所述第二催化剂配制成催化剂油浆的步骤，具体为：
将所述第二催化剂与溶剂油按质量比为(1～2)：10的比例混合即制得所述催化剂油浆；所述溶剂油为废弃动植物油脂、废矿物油、矿物油、馏分油或本工艺制得的生物油中的一种或几种。
步骤(1)中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(600～1000)：1，从而形成一级反应原料；
将所述一级反应原料送入第一浆态床反应器内以发生一级加氢反应，同时向所述第一浆态床反应器内注入高压冷氢，控制所述第一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，所述高压氢气和高压冷氢的压力均为15～27MPa，所述高压冷氢的温度为50～135℃；
步骤(2)中通入氢气的方法为：
将所述一级加氢产物与所述第二催化剂的混合物升温至400～480℃，优选为430℃，而后将所述混合物送入至第二浆态床反应器内并通入高压高温氢气以发生二级加氢反应，同时向所述第二浆态床反应器内注入高压冷氢，并控制所述第二浆态床反应器内的总气速为0.06～0.1m/s，且所述高压高温氢气与所述一级加氢产物的体积比为(1000～1500)：1；
其中，所述高压高温氢气和高压冷氢的压力均为15～27MPa，所述高压高温氢气的温度为430～480℃，所述高压冷氢的温度为50～135℃。
步骤(1)中，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高压中温氢气后，并将所述浆液换热升温至280～350℃，而后再向所述浆液中第二次注入高压高温氢气；
其中，所述高压中温氢气的温度为260～350℃，所述第二次注入的高压高温氢气的温度为360～510℃。
所述高压冷氢经由所述第一浆态床反应器或所述第二浆态床反应器侧壁上的3～5个注入口注入。
所述第一催化剂在所述第一浆态床反应器内的存量控制在所述第一浆态床反应器内液相质量的5～30wt％，所述第二催化剂在所述第二浆态床反应器内的存量控制在所述第二浆态床反应器内液相质量的5～30wt％。
所述一级加氢反应的时间为30～60min，所述二级加氢反应的时间为30～90min。
还包括在压力为7～23MPa、温度为250～460℃的条件下对所述二级加氢产物进行加氢重整的步骤。
所述第一催化剂为经硫化处理的负载有第一活性组分的生物质炭，所述第一活性组分为氧化铁、羟基氧化铁或氢氧化铁中的一种或多种，以第一活性组分和生物质炭的总质量计，第一活性组分的含量为10～50wt％；所述第二催化剂为经硫化处理的负载有第二活性组分的生物质炭，所述第二活性组分为Mo、Mn、W、Fe、Co、Ni或Pd的氧化物中的一种或多种，以第二活性组分和生物质炭的总质量计，活性组分的含量为1～5wt％；
所述负载有第一活性组分的生物质炭的制备方法包括：
(1)取生物质炭为第一生物质炭载体；
(2)将第一活性组分负载于所述第一生物质炭载体上，制得所述第一催化剂。
将第一活性组分负载于所述第一生物质炭载体上的具体方法为：
将所述第一生物质炭载体、所述第一活性组分水溶液混合配制成悬浮液，加入沉淀剂将第一活性组分沉淀于第一生物质炭载体上，经洗涤、干燥制得所述第一催化剂；其中，所述沉淀剂为氨水或碱金属的碳酸盐、碳酸氢盐、氢氧化物中至少一种的水溶液，沉淀过程温度控制为30℃～90℃，pH值为7～9。
所述负载有第二活性组分的生物质炭的制备方法包括：
S1、生物质炭经酸化或碱化处理后，制得第二生物质炭载体；
S2、将第二活性组分和所述第二生物质炭载体混合研磨，制得第二催化剂。
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的第二催化剂。
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。
或第一催化剂为经硫化处理的无定型羟基氧化铁，所述第二催化剂为经硫化处理的负载有第三活性组分的无定型氧化铝，所述第三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。
本发明还提供第四种技术方案：
一种生物质的多级液化工艺，包括如下步骤：
(1)配制含有第一催化剂和生物质的浆液，向所述浆液中通入氢气以发生一级加氢反应，控制反应压力为15～25MPa、反应温度为250～350℃，得到一级加氢产物；
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，而后与所述第一催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30～60wt％的所述浆液；
(2)向所述一级加氢产物中加入第二催化剂并通入氢气以发生二级加氢反应，控制反应压力为15～25MPa、反应温度为380～480℃，得到二级加氢产物，所述二级加氢产物经分离后收集油相，得到生物油。
其中，所述浆液的配制步骤中，植物油渣的来源，植物油渣的压缩圧缩圧力、温度，干燥温度、时间，粉碎中粒径控制，堆密度，浆液的粘度，油品种类，研磨制浆方式等均与第二种技术方案相同。
其中，在所述浆液中，所述第一催化剂的含量、粒径，所述第二催化剂的投加量、粒径、投加方式，步骤(1)中向所述浆液中通入氢气的具体方法，步骤(2)中通入氢气的方法，高压高温氢气和高压冷氢的标准均与第三种技术方案相同。
进一步地，步骤(1)中，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高压中温氢气后，并将所述浆液换热升温至250～350℃， 而后再向所述浆液中第二次注入高压高温氢气；
其中，所述高压中温氢气的温度为230～350℃，所述第二次注入的高压高温氢气的温度为360～510℃。
其中，所述第一催化剂在所述第一浆态床反应器内的存量，所述第二催化剂在所述第二浆态床反应器内的存量，一级、二级加氢反应时间，加氢重整的条件，所述第一催化剂的组成、制备方法，所述第二催化剂的组成、负载有第二活性组分的生物质炭的制备方法等均与第三种技术方案相同。
本发明还提供第五种技术方案，
一种煤与生物质的共同液化工艺，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；
对粉碎后的煤进行压缩成型，压缩压力为5～15MPa，压缩温度为30～60℃；
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380～480℃，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。
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。
在所述生物质煤浆料中，所述催化剂的含量为0.1～10wt％，优选为2wt％；所述催化剂的粒径为5μm～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(600～1000)：1，从而形成反应原料；
将所述反应原料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高压冷氢，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，所述高压氢气和高压冷氢的压力均为13～27MPa，所述高压冷氢的温度为50～135℃。
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：
在向所述生物质煤浆料中第一次注入高压中温氢气后，并将所述生物质煤浆料换热升温至300～400℃，而后再向所述生物质煤浆料中第二次注入高压高温氢气；
其中，所述高压中温氢气的温度为300～400℃，所述高压高温氢气的温度为410～510℃。
所述冷氢经由所述浆态床反应器侧壁上的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。
所述生物质煤浆料的配制步骤中，还包括对所述生物质粉末和所述煤粉进行筛选的操作，并将超过限定粒度的所述固料送回所述压缩或所述粉碎环节中再次进行操作；所述限定粒度为80μm～100μm。
所述催化剂为经硫化处理的负载有活性组分的生物质炭，所述活性组分为氧化铁、羟基氧化铁或氢氧化铁中的一种或多种；
或所述催化剂为经硫化处理的无定型羟基氧化铁。
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，当采用液态生物质时，则在生物质煤浆料配制的步骤中省去对生物质原料的压缩和粉碎过程；还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。
本发明中负载有活性组分的生物质炭的制备方法包括：
(1)选取生物质炭为生物质炭载体；
(2)将活性组分负载于所述生物质炭载体上，制得所述催化剂。
将活性组分负载于所述生物质炭载体上的具体方法为：
将所述生物质炭载体、所述活性组分水溶液混合配制成悬浮液，加入沉淀剂将活性组分沉淀于生物质炭载体上，经洗涤、干燥制得所述催化剂；其中，所述沉淀剂为氨水或碱金属的碳酸盐、碳酸氢盐、氢氧化物中至少一种的水溶液，沉淀过程温度控制为30℃～90℃，pH值为7～9。
或所述催化剂为经硫化处理的无定型羟基氧化铁。
本发明还提供第六种技术方案：
一种煤与生物质的共同水解加氢工艺，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、催化剂与水混合、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55～65wt％；
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300～420℃，最终制得生物油；
在所述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。
所述生物质煤浆料中，生物质的浓度为15～30wt％，煤粉的浓度为35～50wt％。
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1200～1300kg/m 3。
其中，所述烘干温度、时间，所述研磨制浆的时间，浆料中催化剂的含量、粒径，煤的种类，所述通入氢气的具体方法，生物质来源，催化剂的种类、制备方法均与第五种技术方案相同。
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：
在向所述生物质煤浆料中第一次注入高压中温氢气后，并将所述生物质煤浆料换热升温至300～400℃，而后再向所述生物质煤浆料中第二次注入高压高温氢气；
其中，所述高压中温氢气的温度为300～400℃，所述高压高温氢气的温度为410～510℃。
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。
本发明还提供第七种技术方案：
一种煤与生物质的多级液化工艺，包括如下步骤：
生物质煤油桨的配制：
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；
对粉碎后的煤进行压缩成型，压缩压力为5～15MPa，压缩温度为30～60℃；
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、催化剂与油品按比例进行配比混合、研磨制桨得到生物质煤浆料，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％；
一级加氢反应：向所述生物质煤浆料中通入氢气以发生一级加氢反应，并控制反应 压力为15～25MPa、反应温度为280～350℃，得到一级加氢产物；
二级加氢反应：向所述一级加氢产物中加入第二催化剂并通入氢气以发生二级加氢反应，控制反应压力为15～25MPa、反应温度为400～480℃，得到二级加氢产物，所述二级加氢产物经分离后最终得到生物油；
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。
其中，所述生物质煤浆料中，生物质的浓度，煤粉的浓度，烘干时间、温度，压缩方式，压缩后生物质粉末、煤粉的堆密度，粉碎方式，研磨制浆方式、时间，浆料粘度，煤、油品种类均等与第五种技术方案相同。
所述生物质煤油桨的配制步骤中，还包括对所述生物质粉末和所述煤粉进行筛选的操作，并将超过限定粒度的所述固料送回所述压缩或所述粉碎环节中再次进行操作；所述限定粒度为80μm～100μm。
在所述生物质煤浆料中，所述第一催化剂的含量为0.1～10wt％，优选为2wt％；所述第一催化剂的粒径为5μm～500μm；
所述第二催化剂的投加量为所述一级加氢产物质量的0.5～2wt％，所述第二催化剂的粒径为5μm～500μm；
在将所述第二催化剂加入至所述一级加氢产物中之前，还包括将所述第二催化剂配制成催化剂油浆的步骤，具体为：
将所述第二催化剂与溶剂油(水)按质量比为(1～2)：10的比例混合即制得所述催化剂油浆。
所述一级加氢反应步骤中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(600～1000)：1，从而形成一级反应原料；
将所述一级反应原料送入第一浆态床反应器内以发生一级加氢反应，同时向所述第一浆态床反应器内注入高压冷氢，控制所述第一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，所述高压氢气和高压冷氢的压力均为13～27MPa，所述高压冷氢的温度为50～135℃；
所述二级反应步骤中通入氢气的方法为：
将所述一级加氢产物与所述第二催化剂的混合物升温至380～480℃，优选为430℃，而后将所述混合物送入至第二浆态床反应器内并通入高压高温氢气以发生二级加氢反应，同时向所述第二浆态床反应器内注入高压冷氢，并控制所述第二浆态床反应器内的总气速为0.06～0.1m/s，且氢气与所述一级加氢产物的体积比为(1000～1500)：1；
其中，所述高压高温氢气和高压冷氢的压力均为13～27MPa，所述高压高温氢气的温度为430～480℃，所述高压冷氢的温度为50～135℃。
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：
在向所述生物质煤浆料中第一次注入高压中温氢气后，并将所述生物质煤浆料换热升温至200～350℃，而后再向所述生物质煤浆料中第二次注入高压高温氢气；
其中，所述高压中温氢气的温度为180～350℃，所述第二次注入的高压高温氢气的温度为360～510℃。
所述高压冷氢经由所述第一浆态床反应器或所述第二浆态床反应器侧壁上的3～5个注入口注入。
所述第一催化剂在所述第一浆态床反应器内的存量控制在所述第一浆态床反应器内液相质量的5～30wt％，所述第二催化剂在所述第二浆态床反应器内的存量控制在所述第二浆态床反应器内液相质量的5～30wt％。
所述一级加氢反应的时间为30～60min，所述二级加氢反应的时间为30～90min。
还包括在压力为7～23MPa、温度为250～460℃的条件下对所述二级加氢产物进行加氢重整的步骤。
所述第一催化剂为经硫化处理的负载有第一活性组分的生物质炭，所述第一活性组分为氧化铁、羟基氧化铁或氢氧化铁中的一种或多种；所述第二催化剂为经硫化处理的负载有第二活性组分的生物质炭，所述第二活性组分为Mo、W、Fe、Co、Ni或Pd的氧化物中的一种或多种；
或第一催化剂为经硫化处理的无定型羟基氧化铁，所述第二催化剂为经硫化处理的负载有第三活性组分的无定型氧化铝，所述第三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。
本发明中的生物质原料可以是固态的麦子、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；也可以是液态的粪便等；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。
所述负载有第一活性组分的生物质炭的制备方法包括：
(1)选取生物质炭为第一生物质炭载体；
(2)将第一活性组分负载于所述第一生物质炭载体上，制得所述第一催化剂。
将第一活性组分负载于所述第一生物质炭载体上的具体方法为：
将所述第一生物质炭载体、所述第一活性组分水溶液混合配制成悬浮液，加入沉淀剂将第一活性组分沉淀于第一生物质炭载体上，经洗涤、干燥制得所述第一催化剂；其中，所述沉淀剂为氨水或碱金属的碳酸盐、碳酸氢盐、氢氧化物中至少一种的水溶液，沉淀过程温度控制为30℃～90℃，pH值为7～9。
所述负载有第二活性组分的生物质炭的制备方法包括：
(1)生物质炭经酸化或碱化处理后，制得第二生物质炭载体；
(2)将第二活性组分和所述第二生物质炭载体混合研磨，制得第二催化剂。
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的第二催化剂。
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。
本发明还提供第八种技术方案：
一种煤与生物质的多级液化工艺，包括以下步骤：
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；
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；
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、催化剂与水混合、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％；
一级加氢反应：向所述生物质煤浆料中通入氢气以发生一级加氢反应，并控制反应压力为15～20MPa、反应温度为220～300℃，得到一级加氢产物；
二级加氢反应：向所述一级加氢产物中加入第二催化剂并通入氢气以发生二级加氢反应，控制反应压力为15～20MPa、反应温度为380～420℃，得到二级加氢产物，所述二级加氢产物经分离后最终得到生物油；
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。
其中，所述生物质煤浆料中，生物质的浓度，煤粉的浓度，烘干时间、温度，压缩方式，压缩后生物质粉末、煤粉的堆密度，粉碎方式，研磨制浆方式、时间，浆料粘度，煤、生物质的种类均等与第六种技术方案相同。
其中，所述生物质煤浆料中，第一、第二催化剂的含量、粒径，第二催化剂的加入方式，一级加氢反应步骤中通入氢气的具体方法，所述二级反应步骤中通入氢气的方法，高压冷氢的注入方式，第一、第二催化剂在第一、第二浆态床中的存量，第一、第二加氢反应时间，加氢重整条件，第一、第二催化剂的组成和制备方法等均与第七种技术方案相同。
本发明的上述技术方案具有如下优点：
1、本发明提供的生物质的水解加氢工艺，浆液的配制步骤为，将生物质依次进行干燥、初粉碎、压缩和二次粉碎，而后与催化剂混合得到混合物，将混合物加入至油品中研磨制浆即得浆液，本发明首创性的将生物质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，使松散的生物质先后经历坍塌、闭合等重新排位、机械变形的阶段，使得生物质的体积大幅度降低，由此可减少生物质的孔隙率，增大其密度和比重，使之有利于分散在流动介质中，并可提高其在流动介质中的含量，增加了反应物料的浓度，本发明秸秆在油品浆液中的含量可高达30～60wt％，远远高于现有技术中的5～16wt％；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，生物质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和生物质的浆液，再向上述浆液中通入氢气以发生一级或二级反应，并控制反应压力和反应温度，最终制得生物油，本发明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，从而实现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％。本发明的工艺在临氢及第一催化剂、第二催化剂的作用下，使得生物质发生裂化加氢反应，从而实现由生物质向生物油的转化，在本发明工艺中，生物质转化率可高达98-99％。
2、本发明提供的生物质的水解加氢工艺，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；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。
3、本发明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共同液化工艺。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℃)的生物质煤油浆；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。
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油浆的成浆性好，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。
通过向所述生物质煤油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380～480℃，最终制得生物油；本发明的工艺使得煤与生物质在高压高温条件下液化，并在临氢及催化剂的作用下，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90～95％，生物油的收率可达40～75％，且残渣量不高于3％。
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300～420℃，最终制得生物油；本发明的工艺在适量水的存在下使得煤与生物质发生高压高温水解，并在临氢及催化剂的作用下，使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，煤与生物质转化率可达85～95％，生物油的收率可达60～80％，且残渣量不足5％。
本发明提供的煤与生物质的多级液化工艺，通过在高温高压条件下使得煤与生物质发生液化，并在临氢及以第一催化剂、第二催化剂的作用下，液化产物依次发生初级裂化、加氢反应和深度裂化、加氢反应，从而实现由煤与生物质向生物油的转化以及生物油的精制。在本发明所述的工艺中，生物质和煤转化率可达95～99％，生物油的收率可达70～80％，且残渣量不足2.5％。
本发明提供的煤与生物质的多级液化工艺，通过在高压高温下使得煤与生物质发生水解，并在临氢及以第一催化剂、第二催化剂的作用下，水解产物依次发生初级裂化、加氢反应和深度裂化、加氢反应，从而实现由煤与生物质向生物油的转化以及生物油的精制。在本发明所述的工艺中，生物质与煤的转化率可达97～99％，生物油的收率可达70～80％，且残渣量不足3％。
在二级反应中，采用负载有第VIB、VIIB或VIII族金属氧化物的无定型氧化铝作为第二催化剂，并通入氢气，对生物油进行精制，能够利用贵金属硫化后获得的更好的 加氢性能，进一步避免生焦，并且无定型氧化铝具有酸性，可以使得裂解更加充分。
4、本发明提供的煤与生物质的共同液化工艺，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，使所得生物质煤油浆稳定性更好，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。通过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，以更好地利用煤与生物质粉体的表面能使得催化剂附着在其表面，这样催化剂便可及时地为煤与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的水解加氢工艺，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，由此可确保水解加氢等反应的充分进行，从而有利于提高生物质转化率和生物油收率。
4、本发明提供的生物质的水解加氢工艺，一级反应中，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。二级反应中，通过将高压氢气分三次注入至浆液中，即在对浆液升温前后各注入一次高压氢气，然后在一级加氢产物与第二催化剂的混合物进入第二浆态床反应器前再注入一次高压氢气，第一次高压氢气的注入可增大换热器内浆液的扰动，从而避免生物质和催化剂的沉积。分三次注入高压氢气，可以实现气体速度对各种液体、固体、催化剂的速度供给，并依靠混合物的相态、密度差异实现反应器内上升、停留的差异，同时可以根据反应器内各层间的密度差，通过反应器外壁的氢气注入口补充调整气量，保证水解、裂化、加氢反应的充分进行。
5、本发明提供的生物质的水解加氢工艺，在浆液中添加的催化剂经过了硫化处理，硫化处理后的催化剂有较好的加氢性能，能够进一步避免生焦，使得水解加氢反应更充分。
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
一种生物质的水解加氢工艺，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，而后将初粉碎后的水稻秸秆和芦苇秸秆送入压块机中在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，经二次粉碎后的中位粒度为30μm，经二次粉碎后的堆密度为500kg/m 3，备用。
催化剂的制备
(1)取生物质炭为生物质炭载体；
(2)将氧化铁负载于上述生物质炭载体上，硫化处理，制得催化剂。
将氧化铁负载于上述生物质炭载体上的具体方法为：
将上述生物质炭载体、氧化铁的水溶液混合配制成悬浮液，加入作为沉淀剂的碳酸钠和氨水的水溶液，将氧化铁沉淀于生物质炭载体上，经洗涤、干燥、硫化处理制得催化剂，沉淀过程的温度为90℃，pH值为7，以氧化铁和生物质炭载体的总质量计，氧化铁的含量为50wt％。
生物质浆液的配制
将预处理得到的生物质和催化剂混合得到混合物，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，该浆液中水稻秸秆和芦苇秸秆的总含量为60wt％，该浆液的粘度为500mPa﹒s(50℃)，在上述浆液中，催化剂的含量为10wt％， 所投加的催化剂的粒径为5μm。
水解加氢反应：
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高压冷氢，控制浆态床反应器内的总气速为0.2m/s；其中，高压氢气和高压冷氢的压力均为22MPa，高压冷氢的温度为135℃；
所述高压冷氢经由浆态床反应器侧壁上的3个注入口注入。催化剂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％，反应时间为30min。
实施例2
一种生物质的水解加氢工艺，包括如下步骤：
生物质的预处理
将亚麻油渣和花生油渣送入干燥机中在110℃下干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300μm，而后将初粉碎后的亚麻油渣和花生油渣送入压块机中在60℃的温度、3MPa的压力下进行压缩挤压成型，之后进行二次粉碎，经二次粉碎后的中位粒度为50μm，经二次粉碎后的堆密度为1500kg/m 3，备用。
催化剂的制备
(1)取生物质炭为生物质炭载体；
(2)将羟基氧化铁负载于上述生物质炭载体上，硫化处理，制得催化剂。
将羟基氧化铁负载于上述生物质炭载体上的具体方法为：
将上述生物质炭载体、羟基氧化铁的水溶液混合配制成悬浮液，加入作为沉淀剂的碳酸氢钠和氢氧化钾的水溶液，将羟基氧化铁沉淀于生物质炭载体上，经洗涤、干燥、硫化处理制得催化剂，沉淀过程的温度为30℃，pH值为9，以羟基氧化铁和生物质炭载体的总质量计，羟基氧化铁的含量为10wt％。
生物质浆液的配制
将预处理得到的生物质和催化剂混合得到混合物，将上述混合物加入至废润滑油和废机油的混合油中分散制浆，形成浆液，经检测，该浆液中亚麻油渣和花生油渣的总含量为50wt％，该浆液的粘度为700mPa﹒s(50℃)，在上述浆液中，催化剂的含量为0.1wt％，所投加的催化剂的粒径为500μm。
水解加氢反应：
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420℃，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高压冷氢，控制浆态床反应器内的总气速为0.02m/s；其中，高压氢气和高压冷氢的压力均为15MPa，高压冷氢的温度为50℃；
所述高压冷氢经由浆态床反应器侧壁上的5个注入口注入。催化剂在浆态床反应器内的存量占浆态床反应器内液相质量的5wt％，反应时间为120min。
实施例3
一种生物质的多级液化工艺，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200μm，而后将初粉碎后的棉花秸秆送入压块机中在50℃的温度、2MPa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450kg/m 3，备用。
第一催化剂的制备
(1)取生物质炭为第一生物质炭载体；
(2)将氢氧化铁和氧化铁负载于上述第一生物质炭载体上，硫化处理，制得第一催化剂。
将氢氧化铁和氧化铁负载于上述第一生物质炭载体上的具体方法为：
将第一生物质炭载体，氢氧化铁和氧化铁的水溶液混合配制成悬浮液，加入作为沉淀剂的氨水和氢氧化钾的水溶液，将氢氧化铁和氧化铁沉淀于第一生物质炭载体上，经洗涤、干燥、硫化处理制得第一催化剂，沉淀过程的温度为60℃，pH值为8，以氢氧化铁、氧化铁和第一生物质炭载体的总质量计，氢氧化铁和氧化铁的总含量为30wt％；第一催化剂的粒径为5-500μm。
第二催化剂的制备
S1、生物质炭经酸化处理后，制得第二生物质炭载体，所述酸化处理的酸性介质中H +的物质的量浓度为3mol/L，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6h；
S2、将Pd氧化物、Ni氧化物和第二生物质炭载体混合，将上述混合物经过振动研磨和球磨至粒径为100-400μm，硫化处理，制得第二催化剂；以Pd氧化物、Ni氧化物和第二生物质炭载体的总质量计，Pd氧化物和Ni氧化物的总含量为5wt％。
生物质浆液的配制
将预处理得到的生物质和第一催化剂混合得到混合物，将上述混合物加入至重油和洗油的混合油中乳化制浆，形成浆液，经检测，该浆液中棉花秸秆的总含量为55wt％，该浆液的粘度为600mPa﹒s(50℃)，在上述浆液中，第一催化剂的含量为2wt％。
液化反应：
(1)向生物质浆液中通入氢气以发生一级加氢反应，反应压力为20MPa、反应温度为300℃，得到一级加氢产物；
(2)向所述一级加氢产物中加入第二催化剂并通入氢气以发生二级加氢反应，反应压力为20MPa、反应温度为420℃，得到二级加氢产物，将二级加氢产物在压力为23MPa、温度为250℃的条件下进行加氢重整收集油相，得到生物油；其中，第二催化剂的投加量为所述一级加氢产物质量的1wt％；
步骤(1)中，通入氢气的具体方法为：向所述浆液中注入高压氢气，并控制高压氢气与浆液的体积比为700：1，从而形成一级反应原料；将一级反应原料送入第一浆态床反应器内以发生一级加氢反应，同时向第一浆态床反应器内注入高压冷氢，控制第一浆态床反应器内的总气速为0.1m/s；其中，高压氢气和高压冷氢的压力均为22MPa，所述高压冷氢的温度为95℃；
步骤(2)中，通入氢气的具体方法为：将一级加氢产物与第二催化剂的混合物升温至420℃，而后将该混合物送入至第二浆态床反应器内并通入高压高温氢气以发生二级加氢反应，同时向第二浆态床反应器内注入高压冷氢，并控制第二浆态床反应器内的总气速为0.08m/s，且高压高温氢气与一级加氢产物的体积比为1200：1；其中，所述高压高温氢气和高压冷氢的压力均为22MPa，所述高压高温氢气的温度为450℃，所述高压冷氢的温度为85℃。
所述高压冷氢经由第一浆态床反应器和第二浆态床反应器侧壁上的4个注入口注入。第一催化剂在第一浆态床反应器内的存量占第一浆态床反应器内液相质量的10wt％，第二催化剂在第二浆态床反应器内的存量占第二浆态床反应器内液相质量的20wt％；一级加氢反应的时间为40min，二级加氢反应的时间为45min。
实施例4
一种生物质的多级液化工艺，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85℃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150μm，而后将初粉碎后的橄榄油渣送入压条机中在45℃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35μm，经二次粉碎后的堆密度为1535kg/m 3，备用。
生物质浆液的配制
将预处理得到的生物质与作为第一催化剂的经硫化处理的无定型羟基氧化铁(其粒径为50-500μm)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，该浆液中橄榄油渣的总含量为62wt％，该浆液的粘度为600mPa﹒s(50℃)，在上述浆液中，无定型羟基氧化铁的含量为2wt％。
液化反应：
(1)向生物质浆液中通入氢气以发生一级加氢反应，反应压力为16MPa、反应温度为320℃，得到一级加氢产物；
(2)将作为第二催化剂的负载有W氧化物和Ni氧化物的无定型氧化铝与酸败油按质量比为2：10的比例混合制得催化剂油浆，向所述一级加氢产物中加入该催化剂油 浆并通入氢气以发生二级加氢反应，反应压力为16MPa、反应温度为430℃，得到二级加氢产物，所述二级加氢产物经分离后收集油相，得到生物油；
其中，作为第二催化剂负载有W氧化物和Ni氧化物的无定型氧化铝的投加量为所述一级加氢产物质量的0.5wt％，所投加的第二催化剂的粒径为50-400μm；
步骤(1)中，通入氢气的具体方法为：将高压氢气分两次注入至浆液中，具体为：在向浆液中第一次注入高压中温氢气后，并将浆液换热升温至250℃，而后再向浆液中第二次注入高压高温氢气；其中，高压中温氢气的温度为350℃，高压高温氢气的温度为360℃；通入的高压中温氢气和高压高温氢气的总体积与浆液的体积比为800：1，从而形成一级反应原料；将所述一级反应原料送入第一浆态床反应器内以发生一级加氢反应，同时向所述第一浆态床反应器内注入高压冷氢，控制第一浆态床反应器内的总气速为0.05m/s；其中，高压氢气和高压冷氢的压力均为22MPa，所述高压冷氢的温度为65℃；
步骤(2)中，通入氢气的具体方法为：将一级加氢产物与第二催化剂的混合物升温至430℃，而后将该混合物送入至第二浆态床反应器内并通入高压高温氢气以发生二级加氢反应，同时向第二浆态床反应器内注入高压冷氢，并控制第二浆态床反应器内的总气速为0.07m/s，且高压高温氢气与一级加氢产物的体积比为1450：1；其中，所述高压高温氢气和高压冷氢的压力均为25MPa，所述高压高温氢气的温度为470℃，所述高压冷氢的温度为120℃。
所述高压冷氢经由第一浆态床反应器和第二浆态床反应器侧壁上的5个注入口注入。第一催化剂在第一浆态床反应器内的存量占第一浆态床反应器内液相质量的10wt％，第二催化剂在第二浆态床反应器内的存量占第二浆态床反应器内液相质量的15wt％；一级加氢反应的时间为50min，二级加氢反应的时间为50min。
实施例5
一种生物质的水解加氢工艺，包括如下步骤：
生物质的预处理
将豌豆秸秆、高粱秸秆和水稻秸秆送入干燥机中在50℃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，初粉碎后的中位粒径为250μm，而后将初粉碎后的豌豆秸秆、高粱秸秆和水稻秸秆送入压条机中在55℃的温度、1.5MPa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度为45μm，经二次粉 碎后的堆密度为440kg/m 3，备用。
生物质浆液的配制
将预处理得到的生物质与作为催化剂的经硫化处理的无定型羟基氧化铁混合得到混合物，将上述混合物加入至潲水油和渣油的混合油中均质制浆，形成浆液，经检测，该浆液中豌豆秸秆、高粱秸秆和水稻秸秆的总含量为40wt％，该浆液的粘度为820mPa﹒s(50℃)，无定型羟基氧化铁的含量为8wt％，所投加的无定型羟基氧化铁的粒径为300μm。
水解加氢反应：
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420℃，制得生物油；
通入氢气的具体方法为：向所述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中温氢气后，并将浆液换热升温至420℃，而后再向浆液中第二次注入高压高温氢气；其中，高压中温氢气的温度为420℃，高压高温氢气的温度为430℃；通入的高压中温氢气和高压高温氢气的总体积与浆液的体积比为900：1，从而形成反应原料；将上述反应原料送入浆态床反应器内以发生水解加氢 反应，同时向上述浆态床反应器内注入高压冷氢，控制浆态床反应器内的总气速为0.08m/s；其中，高压氢气和高压冷氢的压力均为20MPa，所述高压冷氢的温度为95℃；
所述高压冷氢经由浆态床反应器侧壁上的5个注入口注入。催化剂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％，反应时间为50min。
实施例6
一种生物质的水解加氢工艺，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2.5h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300μm，而后将初粉碎后的大豆油渣送入压条机中在58℃的温度、3.1MPa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度为48μm，经二次粉碎后的堆密度为1512kg/m 3，备用。
生物质浆液的配制
将预处理得到的生物质与作为催化剂的经硫化处理的无定型羟基氧化铁混合得到混合物，将上述混合物加入至蒽油和循环馏分油的混合油中搅拌制浆，形成浆液；经检测，该浆液中大豆油渣的含量为65wt％，该浆液的粘度为691mPa﹒s(50℃)，无定型羟基氧化铁的含量为0.3wt％，所投加的无定型羟基氧化铁的粒径为20μm。
水解加氢反应：
向生物质浆液中通入氢气以发生反应，控制反应压力为19MPa、反应温度为390℃，制得生物油；
通入氢气的具体方法为：向所述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中温氢气后，并将浆液换热升温至390℃，而后再向浆液中第二次注入高压高温氢气；其中，高压中温氢气的温度为400℃，高压高温氢气的温度为490℃；通入的高压中温氢气和高压高温氢气的总体积与浆液的体积比为800：1，从而形成反应原料；将上述反应原料送入浆态床反应器内以发生水解加氢反应，同时向上述浆态床反应器内注入高压冷氢，控制浆态床反应器内的总气速为0.07m/s；其中，高压氢气和高压冷氢的压力均为22MPa，所述高压冷氢的温度为105℃；
所述高压冷氢经由浆态床反应器侧壁上的5个注入口注入。催化剂在浆态床反应器内的存量占浆态床反应器内液相质量的23wt％，反应时间为100min。
实施例7
一种生物质的多级液化工艺，包括如下步骤：
生物质的预处理
将大麻秸秆和蚕豆秸秆送入干燥机中在65℃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，初粉碎后的中位粒径为260μm，而后将初粉碎后的大麻秸秆和蚕豆秸秆送入压条机中在50℃的温度、0.5MPa的压力下进行压缩挤压成型，之后进行二次粉碎处理，经二次粉碎后的生物质的中位粒径为30μm，经二次粉碎后的堆密度为410kg/m 3，备用。
第一催化剂的制备
(1)选取生物质炭为第一生物质炭载体；
(2)将氧化铁负载于上述第一生物质炭载体上，硫化处理，制得第一催化剂。
将氧化铁负载于上述第一生物质炭载体上的具体方法为：
将第一生物质炭载体、氧化铁的水溶液混合配制成悬浮液，加入作为沉淀剂的氢氧化钠和氨水的水溶液，将氧化铁沉淀于第一生物质炭载体上，经洗涤、干燥、硫化处理制得第一催化剂，沉淀过程的温度为80℃，pH值为7.5，以氧化铁和第一生物质炭载体的总质量计，氧化铁的含量为50wt％；第一催化剂的粒径为10-450μm。
第二催化剂的制备
S1、生物质炭经碱化处理后，制得第二生物质炭载体，所述碱化处理的碱性介质中OH-的物质的量浓度为0.5mol/L，生物质炭与碱性介质体积比为1:15，碱化温度为30℃，酸化时间为10h；
S2、将Pd氧化物、Mo氧化物和第二生物质炭载体混合，将上述混合物经过振动研磨和球磨至粒径为100-500μm，硫化处理，制得第二催化剂；以Pd氧化物、Mo氧化物和第二生物质炭载体的总质量计，Pd氧化物、Mo氧化物的总含量为4wt％。
生物质浆液的配制
将预处理得到的生物质和第一催化剂混合得到混合物，将上述混合物加入至地沟油中分散制浆，形成浆液，经检测，该浆液中大麻秸秆和蚕豆秸秆的总含量为40wt％，该浆液的粘度为1200mPa﹒s(50℃)，在上述浆液中，第一催化剂的含量为0.2wt％。
液化反应：
(1)向生物质浆液中通入氢气以发生一级加氢反应，反应压力为25MPa、反应温度为350℃，得到一级加氢产物；
(2)向所述一级加氢产物中加入第二催化剂并通入氢气以发生二级加氢反应，反应压力为25MPa、反应温度为400℃，得到二级加氢产物，所述二级加氢产物经分离后收集油相，得到生物油；
其中，第二催化剂的投加量为所述一级加氢产物质量的0.8wt％；步骤(1)中，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，从而形成一级反应原料；将一级反应原料送入第一浆态床反应器内以发生一级加氢反应，同时向第一浆态床反应器内注入高压冷氢，控制第一浆态床反应器内的总气速为0.2m/s；其中，高压氢气和高压冷氢的压力均为27MPa，高压冷氢的温度为50℃；
步骤(2)中，通入氢气的具体方法为：将所述一级加氢产物与所述第二催化剂的混合物升温至400℃，而后将所述混合物送入至第二浆态床反应器内并通入高压高温氢气以发生二级加氢反应，同时向所述第二浆态床反应器内注入高压冷氢，并控制所述第二浆态床反应器内的总气速为0.06m/s，且高压高温氢气与所述一级加氢产物的体积比为1500：1；其中，所述高压高温氢气和高压冷氢的压力均为27MPa，所述高压高温氢气的温度为430℃，所述高压冷氢的温度为50℃。
所述高压冷氢经由第一浆态床反应器和第二浆态床反应器侧壁上的3个注入口注入。第一催化剂在第一浆态床反应器内的存量占第一浆态床反应器内液相质量的5wt％，第二催化剂在第二浆态床反应器内的存量占第二浆态床反应器内液相质量的30wt％；一级加氢反应的时间为30min，二级加氢反应的时间为90min。
实施例8
一种生物质的多级液化工艺，包括如下步骤：
生物质的预处理
将花生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160μm，而后将初粉碎后的花生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，之后进行二次粉碎处理，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1510kg/m 3，备用。
第一催化剂的制备
(1)选取生物质炭为第一生物质炭载体；
(2)将羟基氧化铁负载于上述第一生物质炭载体上，硫化处理，制得第一催化剂。
将羟基氧化铁负载于上述第一生物质炭载体上的具体方法为：
将第一生物质炭载体、羟基氧化铁的水溶液混合配制成悬浮液，加入作为沉淀剂的氢氧化钠和氨水的水溶液，将羟基氧化铁沉淀于第一生物质炭载体上，经洗涤、干燥、硫化处理制得第一催化剂，沉淀过程的温度为40℃，pH值为8.5，以羟基氧化铁和第一生物质炭载体的总质量计，羟基氧化铁的含量为50wt％；第一催化剂的粒径为110-250μm。
第二催化剂的制备
S1、生物质炭经碱化处理后，制得第二生物质炭载体，所述碱化处理的碱性介质中OH -的物质的量浓度为5mol/L，干馏生物质炭与碱性介质体积比为1:5，碱化温度为80℃，酸化时间为1h；
S2、将Pd氧化物、Mo氧化物和第二生物质炭载体混合，将上述混合物经过振动研磨和球磨至粒径为30-250μm，硫化处理，制得第二催化剂；以Pd氧化物、Mo氧化物和第二生物质炭载体的总质量计，Pd氧化物、Mo氧化物的总含量为1.5wt％。
生物质浆液的配制
将预处理得到的生物质和第一催化剂混合得到混合物，将上述混合物加入至地沟油中乳化制浆，形成浆液，经检测，该浆液中花生油渣的总含量为65wt％，该浆液的粘度为690mPa﹒s(50℃)，在上述浆液中，第一催化剂的含量为4wt％。
液化反应：
(1)向生物质浆液中通入氢气以发生一级加氢反应，反应压力为25MPa、反应温度为300℃，得到一级加氢产物；
(2)将第二催化剂与地沟油按质量比为1.5：10的比例混合制得催化剂油浆，向所述一级加氢产物中加入该催化剂油浆并通入氢气以发生二级加氢反应，反应压力为25MPa、反应温度为450℃，得到二级加氢产物，所述二级加氢产物经分离后收集油相，得到生物油；
其中，第二催化剂的投加量为所述一级加氢产物质量的1.4wt％；
步骤(1)中，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800：1，从而形成一级反应原料；将一级反应原料送入第一浆态床反应器内以发生一级加氢反应，同时向第一浆态床反应器内注入高压冷氢，控制第一浆态床反应器内的总气速为0.1m/s；其中，高压氢气和高压冷氢的压力均为26MPa，高压冷氢的温度为70℃；
步骤(2)中，通入氢气的具体方法为：将所述一级加氢产物与所述第二催化剂的混合物升温至450℃，而后将所述混合物送入至第二浆态床反应器内并通入高压高温氢气以发生二级加氢反应，同时向所述第二浆态床反应器内注入高压冷氢，并控制所述第二浆态床反应器内的总气速为0.09m/s，且高压高温氢气与所述一级加氢产物的体积比为1100：1；其中，所述高压高温氢气和高压冷氢的压力均为27MPa，所述高压高温氢 气的温度为460℃，所述高压冷氢的温度为60℃。
所述高压冷氢经由第一浆态床反应器和第二浆态床反应器侧壁上的3个注入口注入。第一催化剂在第一浆态床反应器内的存量占第一浆态床反应器内液相质量的23wt％，第二催化剂在第二浆态床反应器内的存量占第二浆态床反应器内液相质量的30wt％；一级加氢反应的时间为50min，二级加氢反应的时间为85min。
试验例1
对采用本发明的实施例1-8方法制备的产物的分布进行对比，如下表1所示。
表1 实施例1-8产物分布对比
Figure PCTCN2018122667-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71-86％，残渣量小于0.1wt％，且得到的油相中碳含量为73-90wt％、氢含量为5-17wt％，氧含量为0.1-10wt％。且两级反应能够进一步降低油相中氧含量。
以下是本发明提供的煤与生物质的共同液化工艺的实施例，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＝液化反应产物经分离后的得到的油相的质量/(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9
一种煤与生物质的共同液化工艺，包括如下步骤：
取褐煤，将其烘干脱水，并粉碎至中位粒径为50μm，然后在30℃下进行挤压成型，成型压力为15MPa，得到褐煤压缩料。将褐煤压缩料进行粉碎，得到粒径为30μm的褐煤粉碎料。将上述褐煤粉碎料与在反应器内经硫化处理后的无定型羟基氧化铁共同加入至液态粪便和废机油的混合物中以形成生物质煤油浆，向所述生物质煤油浆中通入氢气以发生反应，并控制反应压力为16MPa、反应温度为480℃，最终制得生物油。
实施例10
一种煤与生物质的共同水解加氢工艺，包括如下步骤：
秸秆的预处理：
(1)取秸秆，将其烘干脱水，粉碎至中位粒径为100μm，然后送入压块机或压条机进行挤压成型，成型压力为2MPa，得到秸秆压缩料。
(2)将秸秆压缩料送入锤片粉碎机，进行粉碎，得到中位粒径为30μm的秸秆粉碎料，待用。
煤原料的预处理：
(1)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。
(2)将褐煤压缩料送入球磨机，进行粉碎，得到中位粒径为100μm的褐煤粉碎料，待用。
生物质水煤浆的配制和水解加氢反应：
将上述秸秆粉碎料和褐煤粉碎料进行除灰后与经硫化处理后的负载有氧化铁的生物质炭混合得到混合物，将所述混合物加入至水中，从而形成所述生物质水煤浆，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15MPa、反应温度为300℃，反应30min，最终制得生物油。
在本实施例中，所述负载有氧化铁的生物质炭是由如下方法制备得到：
(1)选取生物质炭为生物质炭载体；
(2)将经硫化处理的氧化铁负载于所述生物质炭载体上，制得所述催化剂。
将经硫化处理的氧化铁负载于所述生物质炭载体上的具体方法为：
将所述生物质炭载体、所述经硫化处理的氧化铁水溶液混合配制成悬浮液，加入沉 淀剂将经硫化处理的氧化铁沉淀于生物质炭载体上，经洗涤、干燥制得所述催化剂；其中，所述沉淀剂为氨水和碳酸钠溶液，沉淀过程温度控制为30℃，pH值为7。
以氧化铁和生物质炭的总质量计，氧化铁的含量为10wt％。
实施例11
一种煤与生物质的多级液化工艺，包括如下步骤：
生物质原料的预处理：
(1)取芦苇，将其烘干脱水，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50μm，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40μm，待用。
当然，作为本实施例的一种替代方式，也可以将上述芦苇压缩料和神东长焰煤压缩料分别与部分废机油混合后共同送入球磨机进行第二次粉碎。
生物质煤油浆的配制和加氢反应：
芦苇和煤的二次粉碎料经除灰后与在反应器内经硫化处理后的负载有羟基氧化铁的生物质炭混合得到混合物，将所述混合物加入至废机油中，从而形成所述生物质煤油浆；作为一种优选方式，上述生物质煤油浆可以继续通过胶体磨处理，能够继续提高所述生物质煤油浆的成浆性。
向所述生物质煤油浆中通入氢气以发生一级加氢反应，得到一级加氢产物；向一级加氢产物中加入在反应器内硫化的负载有Pd氧化物和Ni氧化物的生物质炭并通入氢气以发生二级加氢反应，得到二级加氢产物，所述二级加氢产物经分离后最终得到生物油。
其中，控制两次反应的压力均为17MPa、一级加氢反应的温度为310℃、反应时间 为45min，二级加氢反应的温度为460℃，反应时间为70min。在所述生物质煤油浆中，所述芦苇的含量为25wt％，所述煤的含量为45wt％，所述第一催化剂的含量为0.1wt％，所述第一催化剂的粒径为500μm；所述第二催化剂的投加量为所述一级加氢产物质量的0.5wt％，所述第二催化剂的粒径为500μm；在将所述第二催化剂加入至所述一级加氢产物中之前，还包括将所述第二催化剂配制成催化剂油浆的步骤，其具体为：将所述第二催化剂与废机油按质量比为1：10的比例混合即制得所述催化剂油浆。
实施例12
一种煤与生物质的多级液化工艺，包括如下步骤：
生物质原料的预处理：
(1)取树叶和瓜果，将其烘干脱水，然后送入气流粉碎机进行粉碎处理，得到树叶和瓜果一次粉碎料，粒径D 50为240μm。
(2)将树叶和瓜果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2MPa，得到树叶和瓜果压缩料。
(3)将树叶和瓜果压缩料送入气流粉碎机，进行二次粉碎，得到树叶和瓜果二次粉碎料，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100μm。
(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30μm，待用。
生物质水煤浆的配制和水解加氢反应：
树叶和瓜果二次粉碎料除灰后与在反应器内经硫化处理后的负载有氢氧化铁的生物质炭混合得到混合物，将所述混合物加入至水中，从而形成所述生物质水煤浆；
向所述生物质水煤浆中通入氢气以发生一次加氢反应，得到一级加氢产物；然后向一级加氢产物中加入在反应器内硫化的负载有Mo氧化物和Co氧化物的生物质炭并通入氢气以发生二级加氢反应，得到二级加氢产物，所述二级加氢产物经分离后最终得到生物油。
其中，控制两次反应的压力均为18MPa，一级加氢反应的温度为240℃、反应时间 为50min，二级加氢反应的温度为380℃、反应时间为30min。在所述生物质水煤浆中，所述树叶和瓜果的含量为20wt％，所述煤的含量为40wt％，所述第一催化剂的含量为2wt％，所述第一催化剂的粒径为400μm；所述第二催化剂的投加量为所述一级加氢产物质量的0.8wt％，所述第二催化剂的粒径为400μm；在将所述第二催化剂加入至所述一级加氢产物中之前，还包括将所述第二催化剂配制成催化剂浆液的步骤，其具体为：将所述第二催化剂与水按质量比为2：10的比例混合即制得所述催化剂浆液。
实施例13
一种煤与生物质的共同液化工艺，包括如下步骤：
生物质原料的预处理：
(1)取藻类，将其烘干脱水，然后送入气流粉碎机进行粉碎处理，得到藻类一次粉碎料，粒径D 50为200μm。
(2)将藻类一次粉碎料送入压块机或压条机在45℃下进行挤压成型，成型压力为2MPa，得到藻类压缩料。
(3)将藻类压缩料送入气流粉碎机，进行二次粉碎，得到藻类二次粉碎料，粒径D 50为40μm，待用。
煤原料的预处理：
(1)取褐煤，将其烘干脱水，然后送入球磨机进行粉碎处理，得到褐煤一次粉碎料，粒径D 50为80μm。
(2)将褐煤一次粉碎料送入压块机或压条机在60℃下进行挤压成型，成型压力为15MPa，得到褐煤压缩料。
(3)将褐煤压缩料送入球磨机，进行二次粉碎，得到褐煤二次粉碎料，粒径D 50为30μm，待用。
将上述藻类与褐煤的二次粉碎料进行筛选，将＞100μm的藻类与褐煤分离出来，然后投入压缩环节或第二次粉碎环节中随后续进料一起再次处理，以获得更加均一的粒径，从而获得更加稳定的生物质煤油浆。
生物质煤油浆的配制和液化反应：
藻类与褐煤经过筛选的二次粉碎料经除灰后与在反应器内经硫化处理后的无定型羟基氧化铁混合得到混合物，将所述混合物加入至本工艺制得的生物油中，从而形成所述生物质煤油浆，向所述生物质煤油浆中通入氢气以发生反应，并控制反应压力为20MPa、反应温度为390℃，最终制得生物油。其中，硫磺和无定型羟基氧化铁以质量 比为0.4：1混合配制得到催化剂。在所述生物质煤油浆中，所述藻类的含量为20wt％，所述煤的含量为40wt％，所述催化剂的含量为4wt％，所述催化剂的粒径为300μm。
所述通入氢气的具体方法为：向所述生物质煤油浆中注入高压氢气，并控制所述高压氢气与所述生物质煤油浆的体积比为600：1，从而形成反应原料；将所述反应原料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高压冷氢，控制所述浆态床反应器内的总气速为0.2m/s；其中，所述高压氢气和高压冷氢的压力均为13MPa，所述高压冷氢的温度为135℃。
实施例14
一种煤与生物质的共同水解加氢工艺，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150μm。
(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4MPa，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90μm。
(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60μm，待用。
神东长焰煤和大豆油油渣的二次粉碎料与在反应器内经硫化处理后的无定型羟基氧化铁共同加入水中，从而形成所述生物质水煤浆，作为进一步的优选方式，上述生物质水煤浆可以继续通过胶体磨处理，能够继续提高所述生物质水煤浆的成浆性。
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22MPa、反应温度为410℃，反应的时间为60min，最终制得生物油。其中，硫磺和无定型羟基氧化铁以质量比为0.8：1混合配制得到催化剂。在所述生物质水煤浆中，所述大豆油油渣的含量 为25wt％，所述煤的含量为40wt％，所述催化剂的含量为6wt％，所述催化剂的粒径为200μm。
所述通入氢气的具体方法为：在向所述生物质水煤浆中第一次注入压力为18MPa、温度为350℃的高压中温氢气后，并将所述生物质水煤浆换热升温至200℃，而后再向所述生物质水煤浆中第二次注入压力为18MPa、温度为510℃的高压高温氢气，并控制两次注入的高压氢气与所述生物质水煤浆的体积比为700：1，从而形成反应原料；将所述反应原料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压力为18MPa、温度为100℃的高压冷氢，所述冷氢经由所述浆态床反应器侧壁上的5个注入口注入，控制所述浆态床反应器内的总气速为0.08m/s。
实施例15
一种煤与生物质的多级液化工艺，包括如下步骤：
生物质与煤原料的处理：
取水稻秸秆、棕榈油油渣以及褐煤，将其烘干脱水，粉碎至中位粒径为100μm，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，得到水稻秸秆、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35μm的水稻秸秆和棕榈油油渣以及褐煤的粉碎料，待用。
生物质煤油浆的配制和液化加氢反应：
将上述粉碎料除灰后与在反应器内经硫化处理后的无定型羟基氧化铁混合得到混合物，将所述混合物加入至混合后的煤焦油和石油中，从而形成所述生物质煤油浆，向所述生物质煤油浆中通入氢气以发生一级加氢反应，得到一级加氢产物；然后向所述一级加氢产物中加入在反应器内硫化的负载有W氧化物和Ni氧化物的无定型氧化铝并通入氢气以发生二级加氢反应，得到二级加氢产物，所述二级加氢产物经分离后最终得到生物油；还包括在压力为7MPa、温度为460℃的条件下对所述二级加氢产物进行加氢重整的步骤。
其中，控制两次反应的压力均为23MPa、一级加氢反应的温度为290℃、二级加氢反应的温度为400℃，一级加氢反应的时间为40min，二级加氢反应的时间为35min，将硫磺和无定型羟基氧化铁以质量比为0.6：1混合配制得到第一催化剂。在所述生物质煤油浆中，所述棕榈油油渣的含量为10wt％，所述水稻秸秆的含量为15wt％，所述煤的含量为40wt％，所述第一催化剂的含量为8wt％，所述第一催化剂的粒径为100μm；所 述第二催化剂的投加量为所述一级加氢产物质量的1.8wt％，所述第二催化剂的粒径为100μm；在将所述第二催化剂加入至所述一级加氢产物中之前，还包括将所述第二催化剂配制成催化剂油浆的步骤，其具体为：将所述第二催化剂与溶剂油按质量比为1：10的比例混合即制得所述催化剂油浆；所述溶剂油为动物油和本工艺制得的生物油。
本实施例中的一级加氢反应中通入氢气的具体方法为：在向所述生物质煤油浆中第一次注入压力为23MPa、温度为260℃的高压中温氢气后，将所述生物质煤油浆换热升温至280℃，而后再向所述生物质煤油浆中第二次注入压力为23MPa、温度为430℃的高压高温氢气，并控制两次注入的高压氢气与所述生物质煤油浆的体积比为800：1，从而形成一级反应原料；将所述一级反应原料送入第一浆态床反应器内以发生一级加氢反应，同时向所述第一浆态床反应器内注入压力为23MPa、温度为80℃的高压冷氢，所述高压冷氢经由所述第一浆态床反应器侧壁上的4个注入口注入，控制所述第一浆态床反应器内的总气速为0.05m/s。
本实施例中二级加氢反应中通入氢气的方法为：将所述一级加氢产物与所述第二催化剂的混合物升温至440℃，而后将所述混合物送入至第二浆态床反应器内并通入压力为23MPa，温度为440℃的高压高温氢气以发生二级加氢反应，同时向所述第二浆态床反应器内注入压力为23MPa、温度为80℃的高压冷氢，所述高压冷氢经由所述第二浆态床反应器侧壁上的4个注入口注入，并控制第二浆态床反应器内的总气速为0.07m/s，且氢气与所述一级加氢产物的体积比为1350：1。所述第一催化剂在所述第一浆态床反应器内的存量控制在所述第一浆态床反应器内液相质量的5wt％，所述第二催化剂在所述第二浆态床反应器内的存量控制在所述第二浆态床反应器内液相质量的30wt％。
实施例16
一种煤与生物质的多级液化工艺，包括如下步骤：
生物质原料的预处理：
(1)取芦苇，将其烘干脱水，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50μm，待用。
煤原料的预处理：
(1)取褐煤，将其烘干脱水，然后送入球磨机进行粉碎处理，得到褐煤一次粉碎料，粒径D 50为100μm。
(2)将褐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，得到褐煤压缩料。
(3)将褐煤压缩料送入球磨机，进行二次粉碎，得到褐煤二次粉碎料，粒径D 50为100μm，待用。
生物质水煤浆的配制和水解加氢工艺：
将芦苇与褐煤的二次粉碎料与在反应器内经硫化处理后的无定型羟基氧化铁混合得到混合物，将所述混合物加入至水中，从而形成所述生物质水煤浆；向所述生物质水煤浆中通入氢气以发生一级加氢反应，得到一级加氢产物；然后向所述一级加氢产物中加入在反应器内硫化的负载有Pd氧化物和Co氧化物的无定型氧化铝并通入氢气以发生二级加氢反应，得到二级加氢产物，所述二级加氢产物经分离后最终得到生物油；还包括在压力为23MPa、温度为250℃的条件下对所述二级加氢产物进行加氢重整的步骤。
其中，控制两次反应的压力均为20MPa，一级加氢反应的温度为280℃、二级加氢反应的温度为400℃，一级加氢反应的时间为60min，二级加氢反应的时间为30min，将硫磺和无定型羟基氧化铁以质量比为1：1混合配制得到第一催化剂。在所述生物质水煤浆中，所述第一催化剂的含量为10wt％，所述第一催化剂的粒径为5μm；所述第二催化剂的投加量为所述一级加氢产物质量的2wt％，所述第二催化剂的粒径为5μm；在将所述第二催化剂加入至所述一级加氢产物中之前，还包括将所述第二催化剂配制成催化剂浆液的步骤，其具体为：将所述第二催化剂与水按质量比为2：10的比例混合即制得所述催化剂浆液。
本实施例中的一级加氢反应中通入氢气的具体方法为：在向所述生物质水煤浆中第一次注入压力为27MPa、温度为180℃的高压中温氢气后，并将所述生物质水煤浆换热升温至350℃，而后再向所述生物质水煤浆中第二次注入压力为27MPa、温度为360℃的高压高温氢气，并控制两次注入的高压氢气与所述生物质水煤浆的体积比为1000：1，从而形成一级反应原料；将所述一级反应原料送入第一浆态床反应器内以发生一级加氢反应，同时向所述第一浆态床反应器内注入压力为27MPa、温度为50℃的高压冷氢，所述高压冷氢经由所述第一浆态床反应器侧壁上的3个注入口注入，控制所述第一浆态床反应器内的总气速为0.02m/s。
本实施例中的二级加氢反应中通入氢气的具体方法为：将所述一级加氢产物和所述第二催化剂的混合物升温至480℃，而后将所述混合物送入至第二浆态床反应器内并通入压力为27MPa，温度为430℃的高压高温氢气以发生二级加氢反应，同时向所述第二浆态床反应器内注入压力为27MPa、温度为50℃的高压冷氢，所述高压冷氢经由所述第二浆态床反应器侧壁上的3个注入口注入，并控制第二浆态床反应器内的总气速为0.06m/s，且氢气与所述一级加氢产物的体积比为1500：1。所述第一催化剂在所述第一浆态床反应器内的存量控制在所述第一浆态床反应器内液相质量的30wt％，所述第二催化剂在所述第二浆态床反应器内的存量控制在所述第二浆态床反应器内液相质量的5wt％。
对比例1
一种煤与生物质的共同液化工艺，包括如下步骤：
取褐煤，将其烘干脱水，并粉碎至中位粒径为50μm，然后送入压块机或压条机进行挤压成型，成型压力为15MPa，得到褐煤压缩料。将褐煤压缩料送入锤片粉碎机，进行粉碎，得到粒径为30μm的褐煤粉碎料。将上述褐煤粉碎料与在反应器内经硫化处理后的无定型羟基氧化铁共同加入至液态粪便和废机油的混合物中以形成生物质煤油浆，向所述生物质煤油浆中通入氢气以发生反应，并控制反应压力为4MPa、反应温度为430℃，最终制得生物油。
对比例2
一种煤与生物质的共同液化工艺，包括如下步骤：
取褐煤，将其烘干脱水，并粉碎至中位粒径为50μm，然后送入压块机或压条机进行挤压成型，成型压力为15MPa，得到褐煤压缩料。将褐煤压缩料送入锤片粉碎机，进行粉碎，得到粒径为30μm的褐煤粉碎料。将上述褐煤粉碎料与在反应器内经硫化处理后的油溶性分散型加氢催化剂共同加入至液态粪便和废机油的混合物中以形成生物质煤油浆，向所述生物质煤油浆中通入氢气以发生反应，并控制反应压力为16MPa、反应温度为480℃，最终制得生物油。
对本发明实施例和对比例的工艺效果进行对比，其结果如下表2所示。
表2 各实施例和对比例的工艺效果比较
Figure PCTCN2018122667-appb-000002
Figure PCTCN2018122667-appb-000003
从表2可以看出，相对于对比例1-2，采用本发明的工艺得到的生物质与煤的共同转化率和生物油的收率均较高，而残渣量则明显减少，从而得知本发明的方法可以明显提高生物质转化率和生物油的收率，降低残渣量。二级反应能够显著降低残渣含量和油相中氧含量。
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 (27)

  1. 一种生物质的水解加氢工艺，其特征在于，包括如下步骤：
    配制含有催化剂和生物质的浆液，向所述浆液中通入氢气以发生反应，并控制反应压力和反应温度，最终制得生物油；
    所述浆液的配制步骤为，将生物质依次进行干燥、初粉碎、压缩和二次粉碎，而后与所述催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，得到所述浆液；
    所述反应为一级反应，当所述生物质为秸秆时，控制反应压力为15-20MPa、反应温度为380-420℃；所得浆液的浓度为30～60wt％；
    当所述生物质为植物油渣时，控制反应压力为15-20MPa、反应温度为380-440℃；所得浆液的浓度为50-65wt％。
  2. 根据权利要求1所述的生物质的水解加氢工艺，其特征在于，所述反应为二级反应，包括以下步骤：
    (1)配制含有第一催化剂和生物质的浆液，向所述浆液中通入氢气以发生一级加氢反应，控制反应压力和反应温度，得到一级加氢产物；
    (2)向所述一级加氢产物中加入第二催化剂并通入氢气以发生二级加氢反应，控制反应压力和反应温度，得到二级加氢产物，所述二级加氢产物经分离后收集油相，得到生物油；
    当所述生物质为秸秆时，一级加氢反应控制反应压力为15～25MPa、反应温度为280～350℃；二级加氢反应控制反应压力为15～25MPa、反应温度为400～480℃；
    当所述生物质为植物油渣时，一级加氢反应控制反应压力为15～25MPa、反应温度为250～350℃；二级加氢反应控制反应压力为15～25MPa、反应温度为380～480℃。
  3. 根据权利要求1或2所述的生物质的水解加氢工艺，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℃；将所述植物油渣进行压缩的压力为3～5MPa、温度为40-60℃。
  4. 根据权利要求1-3任一项所述的生物质的水解加氢工艺，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％；初粉碎后的中位粒度为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。
  5. 根据权利要求1-4任一项所述的生物质的水解加氢工艺，其特征在于，在所述浆液中，所述秸秆的含量为55～60wt％。
  6. 根据权利要求1-5任一项所述的生物质的水解加氢工艺，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。
  7. 根据权利要求1-6任一项所述的生物质的水解加氢工艺，其特征在于，在所述浆液中，所述反应为一级反应时，所述催化剂的含量为0.1～10wt％；所述催化剂的粒径为5μm-500μm；
    当所述反应为二级反应时，所述第一催化剂的含量为0.1～10wt％；所述第一催化剂的粒径为5μm-500μm；
    所述第二催化剂的投加量为所述一级加氢产物质量的0.5～2wt％，所述第二催化剂的粒径为5μm-500μm；
    在将所述第二催化剂加入至所述一级加氢产物中之前，还包括将所述第二催化剂配制成催化剂油浆的步骤，具体为：
    将所述第二催化剂与溶剂油按质量比为(1～2)：10的比例混合即制得所述催化剂油浆；所述溶剂油为废弃动植物油脂、废矿物油、矿物油、馏分油或本工艺制得的生物油中的一种或几种。
  8. 根据权利要求1-7任一项所述的生物质的水解加氢工艺，其特征在于，
    当所述反应为一级反应时，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(600～1000)：1，从而形成反应原料；
    将所述反应原料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高压冷氢，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，所述高压氢气和高压冷氢的压力均为15～22MPa，所述高压冷氢的温度为50～135℃；
    当所述反应为二级反应时，步骤(1)中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(600～1000)：1，从而形成一级反应原料；
    将所述一级反应原料送入第一浆态床反应器内以发生一级加氢反应，同时向所述第一浆态床反应器内注入高压冷氢，控制所述第一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，所述高压氢气和高压冷氢的压力均为15～27MPa，所述高压冷氢的温度为50～135℃；
    步骤(2)中通入氢气的方法为：
    将所述一级加氢产物与所述第二催化剂的混合物升温至400～480℃，优选为430℃，而后将所述混合物送入至第二浆态床反应器内并通入高压高温氢气以发生二级加氢反应，同时向所述第二浆态床反应器内注入高压冷氢，并控制所述第二浆态床反应器内的总气速为0.06～0.1m/s，且所述高压高温氢气与所述一级加氢产物的体积比为(1000～1500)：1；
    其中，所述高压高温氢气和高压冷氢的压力均为15～27MPa，所述高压高温氢气的温度为430～480℃，所述高压冷氢的温度为50～135℃。
  9. 根据权利要求8所述的生物质的水解加氢工艺，其特征在于，当所述反应为一级反应时，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高压中温氢气后，并将所述浆液换热升温至380-420℃，而后再向所述浆液中第二次注入高压高温氢气；
    其中，所述高压中温氢气的温度为360-420℃，所述高压高温氢气的温度为430～510℃。
  10. 根据权利要求8或9所述的生物质的水解加氢工艺，其特征在于，当所述反应为一级反应时，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％；
    当所述反应为二级反应时，所述第一催化剂在所述第一浆态床反应器内的存量控制在所述第一浆态床反应器内液相质量的5～30wt％，所述第二催化剂在所述第二浆态床反应器内的存量控制在所述第二浆态床反应器内液相质量的5～30wt％。
  11. 根据权利要求1-10任一项所述的生物质的水解加氢工艺，其特征在于，当所述反应为一级反应时，所述反应的时间为30-120min；当所述反应为二级反应时，所述一级加氢反应的时间为30～60min，所述二级加氢反应的时间为30～90min。
  12. 根据权利要求1-11任一项所述的生物质的水解加氢工艺，其特征在于，当所述反应为一级反应时，所述催化剂为经硫化处理的负载有活性组分的生物质炭，所述活性组分为氧化铁、羟基氧化铁或氢氧化铁中的一种或多种；
    或所述催化剂为经硫化处理的无定型羟基氧化铁；
    当所述反应为二级反应时，所述第一催化剂为经硫化处理的负载有第一活性组分的生物质炭，所述第一活性组分为氧化铁、羟基氧化铁或氢氧化铁中的一种或多种；所述第二催化剂为经硫化处理的负载有第二活性组分的生物质炭，所述第二活性组分为Mo、Mn、W、Fe、Co、Ni或Pd的氧化物中的一种或多种；
    或第一催化剂为经硫化处理的无定型羟基氧化铁，所述第二催化剂为经硫化处理的负载有第三活性组分的无定型氧化铝，所述第三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。
  13. 根据权利要求2-11任一项所述的生物质的水解加氢工艺，其特征在于，当所述反应为二级反应时，还包括在压力为7～23MPa、温度为250～460℃的条件下对所述二级加氢产物进行加氢重整的步骤。
  14. 根据权利要求1所述的生物质的水解加氢工艺，其特征在于，所述浆液中还包括煤，具体包括如下步骤：
    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；
    对粉碎后的煤进行压缩成型，压缩压力为5～15MPa，压缩温度为30～60℃；
    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、催化剂与流动介质混合、研磨制浆得到生物质煤浆液，所述流动介质为油品或水；
    液化反应：向所述生物质煤浆料中通入氢气以发生反应，并控制反应压力和反应温度，最终制得生物油；
    在所述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进行预混合后，再将所得预混料与所述流动介质混合，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；
    所述反应为一级反应，当所述流动介质为油品时，煤粉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％；并控制反应压力为15～25MPa、反应温度为380～480℃；
    当所述流动介质为水时，煤粉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％；并控制反应压力为15～25MPa、反应温度为300～420℃。
  15. 根据权利要求14所述的生物质的水解加氢工艺，其特征在于，所述反应为二级反应，当所述流动介质为油品时，所述反应包括以下步骤：
    一级加氢反应：向所述生物质煤浆料中通入氢气以发生一级加氢反应，并控制反应压力为15～25MPa、反应温度为280～350℃，得到一级加氢产物；
    二级加氢反应：向所述一级加氢产物中加入第二催化剂并通入氢气以发生二级加氢反应，控制反应压力为15～25MPa、反应温度为400～480℃，得到二级加氢产物，所述二级加氢产物经分离后最终得到生物油；
    当所述流动介质为水时，所述反应包括以下步骤：
    一级加氢反应：向所述生物质煤浆料中通入氢气以发生一级加氢反应，并控制反应压力为15～20MPa、反应温度为220～300℃，得到一级加氢产物；
    二级加氢反应：向所述一级加氢产物中加入第二催化剂并通入氢气以发生二级加氢反应，控制反应压力为15～20MPa、反应温度为380～420℃，得到二级加氢产物，所述二级加氢产物经分离后最终得到生物油。
  16. 根据权利要求14或15所述的生物质的水解加氢工艺，其特征在于，当所述流动介质为油品时，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％；
    当所述介质为水时，所述生物质煤浆料中，生物质的浓度为15～30wt％，煤粉的浓度为35～50wt％。
  17. 根据权利要求14-16任一项所述的生物质的水解加氢工艺，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。
  18. 根据权利要求14-17任一项所述的生物质的水解加氢工艺，其特征在于，当所述流动介质为油品时，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
    当所述流动介质为水时，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1200～1300kg/m 3。
  19. 根据权利要求14-18任一项所述的生物质的水解加氢工艺，其特征在于，所述研磨制浆的时间为2～8min。
  20. 根据权利要求14-19任一项所述的生物质的水解加氢工艺，其特征在于，所述煤为低阶煤；当所述流动介质为油品时，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。
  21. 根据权利要求14-20任一项所述的煤与生物质的水解加氢工艺，其特征在于，当所述反应为一级反应时，在所述生物质煤浆料中，所述催化剂的含量为0.1～10wt％，优选为2wt％；所述催化剂的粒径为5μm～500μm；
    当所述反应为二级反应时，在所述生物质煤浆料中，所述第一催化剂的含量为0.1～10wt％，优选为2wt％；所述第一催化剂的粒径为5μm～500μm；
    所述第二催化剂的投加量为所述一级加氢产物质量的0.5～2wt％，所述第二催化剂的粒径为5μm～500μm；
    在将所述第二催化剂加入至所述一级加氢产物中之前，还包括将所述第二催化剂配制成催化剂浆液的步骤，具体为：
    将所述第二催化剂与水按质量比为(1～2)：10的比例混合即制得所述催化剂浆液。
  22. 根据权利要求14-21任一项所述的生物质的水解加氢工艺，其特征在于，当所述反应为一级反应时，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(600～1000)：1，从而形成反应原料；
    将所述反应原料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高压冷氢，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，所述高压氢气和高压冷氢的压力均为13～27MPa，所述高压冷氢的温度为50～135℃；
    当所述反应为二级反应时，所述一级加氢反应步骤中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(600～1000)：1，从而形成一级反应原料；
    将所述一级反应原料送入第一浆态床反应器内以发生一级加氢反应，同时向所述第一浆态床反应器内注入高压冷氢，控制所述第一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，所述高压氢气和高压冷氢的压力均为13～27MPa，所述高压冷氢的温度为50～135℃；
    所述二级反应步骤中通入氢气的方法为：
    将所述一级加氢产物与所述第二催化剂的混合物升温至380～480℃，优选为430℃，而后将所述混合物送入至第二浆态床反应器内并通入高压高温氢气以发生二级加氢反应，同时向所述第二浆态床反应器内注入高压冷氢，并控制所述第二浆态床反应器内的总气速为0.06～0.1m/s，且氢气与所述一级加氢产物的体积比为(1000～1500)：1；
    其中，所述高压高温氢气和高压冷氢的压力均为13～27MPa，所述高压高温氢气的温度为430～480℃，所述高压冷氢的温度为50～135℃。
  23. 根据权利要求22所述的生物质的水解加氢工艺，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：
    当所述反应为一级反应，所述流动介质为油品时，在向所述生物质煤浆料中第一次注入高压中温氢气后，并将所述生物质煤浆料换热升温至300～400℃，而后再向所述生物质煤浆料中第二次注入高压高温氢气；
    其中，所述高压中温氢气的温度为300～400℃，所述高压高温氢气的温度为410～510℃；
    当所述反应为一级反应，所述流动介质为水时，在向所述生物质煤浆料中第一次注 入高压中温氢气后，并将所述生物质煤浆料换热升温至300～400℃，而后再向所述生物质煤浆料中第二次注入高压高温氢气；
    其中，所述高压中温氢气的温度为300～400℃，所述高压高温氢气的温度为410～510℃；
    当所述反应为二级反应，所述流动介质为油品时，在向所述生物质煤浆料中第一次注入高压中温氢气后，并将所述生物质煤浆料换热升温至200～350℃，而后再向所述生物质煤浆料中第二次注入高压高温氢气；
    其中，所述高压中温氢气的温度为180～350℃，所述第二次注入的高压高温氢气的温度为360～510℃；
    当所述反应为二级反应，所述流动介质为水时，在向所述生物质煤浆料中第一次注入高压中温氢气后，并将所述生物质煤浆料换热升温至200～350℃，而后再向所述生物质煤浆料中第二次注入高压高温氢气；
    其中，所述高压中温氢气的温度为180～350℃，所述第二次注入的高压高温氢气的温度为360～510℃。
  24. 根据权利要求22或23所述的生物质的水解加氢工艺，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％。
  25. 根据权利要求14-24任一项所述的生物质的水解加氢工艺，其特征在于，当所述反应为一级反应，所述流动介质为油品时，所述反应的时间为30～90min，所述流动介质为水时，所述反应的时间为30～60min；
    当所述反应为二级反应，所述流动介质为油品时，所述一级加氢反应的时间为30～60min，所述二级加氢反应的时间为30～90min；所述流动介质为水时，所述一级加氢反应的时间为30～60min，所述二级加氢反应的时间为30～60min。
  26. 根据权利要求24-25任一项所述的生物质的水解加氢工艺，其特征在于，当所述反应为二级反应时，还包括在压力为7～23MPa、温度为250～460℃的条件下对所述二级加氢产物进行加氢重整的步骤。
  27. 根据权利要求24-26任一项所述的生物质的水解加氢工艺，其特征在于，当所述反应为一级反应时，所述催化剂为经硫化处理的负载有活性组分的生物质炭，所述活性组分为氧化铁、羟基氧化铁或氢氧化铁中的一种或多种；
    或所述催化剂为经硫化处理的无定型羟基氧化铁；
    当所述反应为二级反应时，所述第一催化剂为经硫化处理的负载有第一活性组分的 生物质炭，所述第一活性组分为氧化铁、羟基氧化铁或氢氧化铁中的一种或多种；所述第二催化剂为经硫化处理的负载有第二活性组分的生物质炭，所述第二活性组分为Mo、W、Fe、Co、Ni或Pd的氧化物中的一种或多种；
    或第一催化剂为经硫化处理的无定型羟基氧化铁，所述第二催化剂为经硫化处理的负载有第三活性组分的无定型氧化铝，所述第三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。
PCT/CN2018/122667 2017-12-25 2018-12-21 一种生物质的水解加氢工艺 Ceased WO2019128867A1 (zh)

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