WO2014180212A1 - 一种生物质热解油的改性方法 - Google Patents

一种生物质热解油的改性方法 Download PDF

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WO2014180212A1
WO2014180212A1 PCT/CN2014/074975 CN2014074975W WO2014180212A1 WO 2014180212 A1 WO2014180212 A1 WO 2014180212A1 CN 2014074975 W CN2014074975 W CN 2014074975W WO 2014180212 A1 WO2014180212 A1 WO 2014180212A1
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pyrolysis oil
biomass pyrolysis
catalyst
biomass
oil
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French (fr)
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汪大闪
宋德臣
刘倩倩
郑申棵
詹晓东
金家琪
张岩丰
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Wuhan Kaidi Engineering Technology Research Institute Co Ltd
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Wuhan Kaidi Engineering Technology Research Institute Co Ltd
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Priority to EP14794452.4A priority Critical patent/EP2995672B1/en
Publication of WO2014180212A1 publication Critical patent/WO2014180212A1/zh
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Priority to US14/935,429 priority patent/US10005966B2/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/04—Breaking emulsions
    • B01D17/047—Breaking emulsions with separation aids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/088—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • 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
    • C10G33/00—Dewatering or demulsification of hydrocarbon oils
    • C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/36—Steaming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the invention provides a method for modifying biomass pyrolysis oil. Specifically, it is a technique for directly producing catalytic oil by desulfurization of biomass pyrolysis oil. Background technique
  • Biomass energy is the fourth largest energy source after petroleum, coal and natural gas. It has the advantages of wide-ranging, safe, renewable recycling and zero carbon dioxide emissions.
  • Biomass sources mainly include crops, trees, other plants and straws.
  • Biomass can produce different types of energy fuels through a series of conversion technologies. For example, biomass carbonization can produce high quality solid fuels, biomass gasification can produce gaseous fuels.
  • Biomass liquefaction can obtain liquid fuels and the like. Direct conversion of biomass to liquids
  • Fuel technology converts low-quality, low-calorie biomass into high-quality, high-calorie, liquid fuels that are easy to store and transport.
  • the biomass pyrolysis oil obtained by pyrolysis liquefaction of biomass can be directly used as a substitute for petrochemical fuel after being modified and refined.
  • Biomass pyrolysis technology is a process in which biomass is rapidly heated to a high temperature under anaerobic conditions, and thermal energy is used to cut the chemical bonds of biomass macromolecules into low molecular substances.
  • This technology has developed rapidly since the 1980s and has developed a variety of biomass pyrolysis technology processes.
  • biomass pyrolysis oil production rate is 60% (mass percentage). the above.
  • biomass pyrolysis oil has a water content of 30% ⁇ 40% (mass percentage), mainly derived from the moisture and heat in the raw materials.
  • biomass pyrolysis oil contains hundreds of organic compounds. Substances such as acids, alcohols, ethers, esters, aldehydes, ketones, phenols, etc., cause biomass pyrolysis oil to have high oxygen content, high acid value, high viscosity, low calorific value, and very unstable physicochemical properties.
  • the high oxygen content causes the biomass pyrolysis oil to increase in viscosity as the storage time becomes longer; the phenolic substances contained are easily oxidized with increasing temperature, causing the pyrolysis oil to harden and agglomerate; the biomass pyrolysis oil has a high acid value. Extremely corrosive equipment during storage and use. Therefore, biomass pyrolysis oil can not be widely used as a fuel, and needs to be modified and refined to improve the quality of biomass pyrolysis oil and meet the quality requirements of liquid fuel.
  • CN1376766 A method for directly hydrorefining and refining biomass pyrolysis oil is introduced.
  • the specific method is to directly hydrotreat biomass pyrolysis oil with CoMo hydrogenation catalyst at 350 ° C or higher and 10 MPa.
  • Oxygen a modified pyrolysis oil is obtained.
  • hydrogenation is the most effective method for deoxidation, the biomass pyrolysis oil contains more than 40% oxygen. It requires a large amount of hydrogen to be completely removed, and the hydrogenation conditions are harsh, the equipment process is complicated, and the cost is high. Not feasible.
  • CN101381611 A method for esterifying etherified modified biomass pyrolysis oil is introduced.
  • the specific method is to add a lower alcohol to a biomass pyrolysis oil without water removal, and the ester is at 90 ° C to 11 (TC conditions).
  • the reaction or etherification reaction is carried out for 5 to 8 hours, and then after 80 ° C to 13 (TC decompression and evaporation to remove water.
  • the biomass of the biomass pyrolysis oil described in this patent is 20% to 30%, and the presence of a large amount of water will undoubtedly increase.
  • the invention discloses a method for removing water from biomass pyrolysis oil and then performing esterification reaction to achieve the purpose of removing biomass and removing acid from biomass pyrolysis oil.
  • the specific method is to add isooctyl alcohol to the biomass pyrolysis oil to form an azeotrope with water, and distill off most of the water in a 0.02Mpa, 80°C water bath under reduced pressure, and then dehydrate the biomass pyrolysis oil.
  • acetyl chloride removing residual water by hydrolysis of acetyl chloride; the biomass pyrolysis oil after complete water removal is esterified with ethanol, and a small amount of water formed by the esterification reaction is removed by adding anhydrous magnesium sulfate, and finally reaches The effect of dehydration and acid removal of biomass pyrolysis oil.
  • the acetyl chloride reacts with the water in the biomass pyrolysis oil to achieve the purpose of removing water. The dehydration also consumes acetyl chloride, which undoubtedly greatly increases the cost.
  • anhydrous magnesium sulfate is added to continue dehydration, and the magnesium sulfate needs to be separated again. Increasing the process difficulty will inevitably increase the loss during the modification of biomass pyrolysis oil.
  • the method for modifying and refining the existing biomass pyrolysis oil is as follows: First, the water in the biomass pyrolysis oil is removed by fine boring, including decompression fine, reaction fine, and extracting fine; second, after dehydration The biomass pyrolysis oil undergoes catalytic esterification to reduce acidity and viscosity; and third, direct hydrogenation modification of biomass pyrolysis oil.
  • first, the water in the biomass pyrolysis oil is removed by fine boring, including decompression fine, reaction fine, and extracting fine; second, after dehydration
  • the biomass pyrolysis oil undergoes catalytic esterification to reduce acidity and viscosity; and third, direct hydrogenation modification of biomass pyrolysis oil.
  • When heating fine sputum it is easy to make the viscosity of biomass pyrolysis oil become larger or even agglomerate.
  • the biomass pyrolysis oil contains more low-boiling components, the fine process will cause the loss of these low-boiling components
  • the object of the present invention is to develop an efficient biomass pyrolysis oil modification method to improve the physical and chemical quality of the modified biomass pyrolysis oil to overcome the deficiencies of the prior art.
  • the method for modifying biomass pyrolysis oil of the present invention specifically comprises the following steps: First step of emulsification layering and water removal: adding inorganic salt ions and organic demulsifiers to the biomass pyrolysis oil, wherein The mass ratio of inorganic salt to biomass pyrolysis oil is 1: 2000 ⁇ 1: 800, the mass ratio of organic demulsifier to biomass pyrolysis oil is 1: 4000 ⁇ 1: 1000, after shaking or stirring, fully mixed and then static When the lower aqueous solution becomes clear and the oil-water interface is clear, the upper biomass pyrolysis oil and the lower aqueous solution are separated to obtain the upper biomass pyrolysis oil; the second step is to carry out catalytic cracking modification of the biomass pyrolysis oil: catalytic The cracking reaction adopts a conventional catalytic cracking reactor, and the modified catalyst for the catalytic cracking reaction adopts a modified catalyst prepared by loading zeolite with zeolite molecular sieve:
  • the modified catalyst prepared by using zeolite molecular sieve loaded clay comprises REY/white earth, REUS Y/white earth, high silicon REUS Y/white earth, LREHY/white earth, ZSM-5/white earth; After ion exchange of lmol/L NH 4 N0 3 solution, 150 ° C ⁇ 30 (TC roasting for 2 to 4 hours, to obtain a modified catalyst with strong deoxidation selectivity.
  • the inorganic salt used for the water-repellent layer separation is an inorganic salt containing ions Ca 2+ , Na+, K+, Al 3+ , Fe 2+ , ⁇ 4 +, Cl_, S0 4 2 _, N0 3 _.
  • the organic demulsifier used in the emulsion breaking layer water removal is one of polyoxypropylene ether, polyoxyethylene ether, propylene glycol, and n-propanol.
  • the inorganic salt used in the water-repellent layered dewatering is ion-containing Na+, NH 4 +, Cl_, S0 4 2 — Inorganic salt.
  • the mass ratio of the first step inorganic salt to the biomass pyrolysis oil is 1: 1500 ⁇ 1: 1000, and the mass ratio of the organic demulsifier to the biomass pyrolysis oil is 1: 2000 ⁇ 1: 1300.
  • the catalyst is ion-exchanged with 1 mol/L of the NH 4 N0 3 solution, and then calcined at 150 ° C to 30 (TC for 2 to 4 hours, A modified catalyst having strong deoxidation selectivity is obtained.
  • the shaking or stirring time is 3 to 60 minutes, and the mixture is allowed to stand for 20 ⁇ 5 minutes after being fully mixed.
  • oil-water separation can be carried out at room temperature to achieve the effect of biomass pyrolysis oil removal.
  • Demulsifier can accelerate the separation of oil and water; inorganic salt destroys the electric double layer of emulsion, the rate of inward water precipitation increases, and the hydrophilic-lipophilic balance of emulsifier is changed, and the oil-water separation effect is increased; oil-water separation at normal temperature can avoid biomass Pyrolysis oil aging.
  • oil-water separation can remove most of the water in the original biomass pyrolysis oil, and obtain the upper biomass pyrolysis oil having a water content of not more than 8% (mass ratio).
  • the presence of a small amount of water reduces the viscosity of the pyrolysis oil, maintains good fluidity of the biomass pyrolysis oil, and facilitates the feed of the catalytic cracking reaction.
  • the catalytic cracking reaction time of the process of the invention is extremely short, and the biomass pyrolysis oil can be cracked to form stable short-chain hydrocarbons and cracked gas before aging.
  • Modification of the catalytic cracking catalyst increases the acidity of the catalyst, improves the deoxidation selectivity of the catalyst, and is more effective in deoxidizing the biomass pyrolysis oil.
  • the catalyst has high activity and high deoxidation selectivity, and the oxygen in the biomass pyrolysis oil can be removed in the form of H 2 O, CO or CO 2 without consuming a reducing gas.
  • the biomass pyrolysis oil is determined by GB11146 Karl Fischer moisture titration; the pyrolysis oil acidity is determined by the acid value of GB/T264-1991 petroleum product; the viscosity of the pyrolysis oil is measured by capillary kinematic viscosity meter
  • the low calorific value of pyrolysis oil is determined by the calorimetric method of GB/T18856 coal water slurry; the C, H and 0 in the pyrolysis oil are determined by elemental analyzer.
  • biomass pyrolysis oil 1000 g was placed in a 1500 ml three-necked flask, and 0.5 g of sodium chloride and 0.25 g of polyoxypropylene ether were slowly added during the stirring. Stirring was continued for 5 minutes. After the biomass pyrolysis oil was thoroughly mixed with the added demulsifier, the mixture was transferred to a separatory funnel and allowed to stand for 20 minutes. At this time, the lower aqueous solution becomes clear and the water-oil interface is clear, and the upper biomass pyrolysis oil I and the lower aqueous solution are separated.
  • the formed high-silicon REUSY/white earth catalyst was immersed in a 1 mol/L NH 4 N0 3 solution at 80 ° C for 6 hours, and the soaked catalyst was dried and calcined at 15 CTC for 3 hours. The calcined catalyst was further aged at 600 ° C, 100% steam for 3 hours. 200 g of this catalyst was weighed into a fixed fluidized bed, and a catalytic cracking reaction was carried out under the conditions of a mass space velocity of 6 ⁇ of oil to oil 8, a reaction temperature of 450 ° C, and a reaction pressure of 0.2 MPa. The results of analysis of cracked products are shown in Table 1.
  • biomass pyrolysis oil 1000 g was placed in a 1500 ml three-necked flask, and lg sodium sulfate and lg propanediol were slowly added during the stirring. Stirring was continued for 5 minutes. After the biomass pyrolysis oil was thoroughly mixed with the added demulsifier, the mixture was transferred to a separatory funnel and allowed to stand for 20 minutes. At this time, the lower aqueous solution became clear and the water-oil interface was clear, and the upper biomass pyrolysis oil II and the lower aqueous solution were separated.
  • the formed REY/white earth catalyst was immersed in a 100 ° C, lmol/L NH 4 N0 3 solution for 6 hours, dipping The bubbled catalyst was dried and baked at 30 CTC for 4 hours. The calcined catalyst was further aged by 80 CTC, 100% steam for 5 hours. 200 g of the catalyst was weighed into a fixed fluidized bed, and catalytic cracking reaction was carried out under the conditions of mass space velocity 101, ratio of solvent to oil 8, reaction temperature of 550 ° C, and reaction pressure of 0.3 MPa. The results of the product analysis are shown in Table 2.
  • biomass pyrolysis oil 1000 g was placed in a 1500 ml three-necked flask, and 0.6 g of sodium chloride and 0.3 g of polyoxypropylene ether were slowly added during the stirring. Stirring was continued for 5 minutes. After the biomass pyrolysis oil was thoroughly mixed with the added demulsifier, the mixture was transferred to a separatory funnel and allowed to stand for 20 minutes. At this time, the lower aqueous solution became clear and the water-oil interface was clear, and the upper biomass pyrolysis oil III and the lower aqueous solution were separated.
  • the molded high silicon REUSY / clay catalyst were placed in 80 ° C, lmol / L of NH 4 N0 3 solution soak for 6 hours after the catalyst was soaked calcined at 15CTC dried for 3 hours.
  • the calcined catalyst was further aged at 600 ° C, 100% steam for 3 hours. 200 g of this catalyst was weighed into a fixed fluidized bed, and a catalytic cracking reaction was carried out under the conditions of a mass space velocity of 6 ⁇ of oil to oil 8, a reaction temperature of 450 ° C, and a reaction pressure of 0.2 MPa.
  • the results of analysis of cracked products are shown in Table 3.
  • a lOOOOg of biomass pyrolysis oil was placed in a 1500 ml three-necked flask, and 0.5 g of ammonium sulfate and 0.5 g of polyoxyethylene ether were slowly added during the shaking. Continue to shake for 8 minutes. After the biomass pyrolysis oil is thoroughly mixed with the added demulsifier, the mixture is transferred to a separatory funnel and allowed to stand for 20 minutes. At this time, the lower aqueous solution becomes clear and the water-oil interface is clear, and the upper biomass pyrolysis oil IV and the lower aqueous solution are separated.
  • the shaped REUSY/white earth catalyst was immersed in a 1 mol/L NH 4 N0 3 solution at 80 ° C for 6 hours, and the soaked catalyst was dried and then calcined at 20 CTC for 2 hours.
  • the calcined catalyst was further aged by 70 CTC 100% steam for 6 hours.
  • 200 g of the catalyst was weighed into a riser reactor, and a catalytic cracking reaction was carried out under the conditions of a mass space velocity of 15 h - a ratio of a solvent to oil of 3, a reaction temperature of 550 ° C, and a reaction pressure of 0.3 MPa.
  • the product analysis results are shown in Table 4.
  • the shaped REY/white earth catalyst was immersed in a 1 mol/L NH 4 N0 3 solution at 80 ° C for 6 hours, and the soaked catalyst was dried and baked at 30 CTC for 4 hours.
  • the calcined catalyst was further aged by 80 CTC, 100% steam for 5 hours.
  • 200 g of the catalyst was weighed into a fixed fluidized bed, and catalytic cracking reaction was carried out under the conditions of mass space velocity 101, ratio of solvent to oil 8, reaction temperature of 550 ° C, and reaction pressure of 0.3 MPa.
  • the product analysis results are shown in Table 5.
  • biomass pyrolysis oil 1000 g was placed in a 1500 ml three-necked flask, and 1.2 g of calcium chloride and 0.3 g of n-propanol were slowly added during the stirring. Stirring was continued for 5 minutes. After the biomass pyrolysis oil was thoroughly mixed with the added demulsifier, the mixture was transferred to a separatory funnel and allowed to stand for 20 minutes. At this time, the lower aqueous solution became clear and the water-oil interface was clear, and the upper biomass pyrolysis oil VI and the lower aqueous solution were separated.
  • the formed LREHY/white earth catalyst was immersed in a 1 mol/L NH 4 N0 3 solution at 80 ° C for 6 hours, and the immersed catalyst was dried and then calcined at 20 CTC for 2 hours.
  • the calcined catalyst was aged for an additional 8 hours via 50 CTC, 100% steam. 200 g of this catalyst was weighed into a fixed fluidized bed, and catalytic cracking reaction was carried out under the conditions of a mass space velocity of 151 °, a ratio of the agent to the oil of 12, a reaction temperature of 600 ° C, and a reaction pressure of 0.3 MPa.
  • the product analysis results are shown in Table 6.
  • biomass pyrolysis oil 1000 g was placed in a 1500 ml three-necked flask, and 0.8 g of sodium chloride and 0.4 g of polyoxyethylene ether were slowly added during the shaking. Continue to shake for 8 minutes. After the biomass pyrolysis oil is thoroughly mixed with the added demulsifier, the mixture is transferred to a separatory funnel and allowed to stand for 20 minutes. At this time, the lower aqueous solution becomes clear and the water-oil interface is clear, and the upper biomass pyrolysis oil W and the lower aqueous solution are separated.
  • the formed high-silicon REUSY/white earth catalyst was immersed in a solution of 1 mol/L NH 4 N0 3 at 80 ° C for 6 hours, and the immersed catalyst was dried and calcined at 15 CTC for 3 hours.
  • the calcined catalyst was further aged by 60 (TC 100% steam for 3 hours. 200 g of the catalyst was weighed into a riser reactor at a mass space velocity of 12 h. The ratio of the agent to the oil was 16, the reaction temperature was 650 ° C, and the reaction pressure was 0.5.
  • the catalytic cracking reaction was carried out under the conditions of Mpa. The analysis results of the product are shown in Table 7.
  • biomass pyrolysis oil 1000 g was placed in a 1500 ml three-necked flask, and 0.8 g of sodium chloride and 0.6 g of polyoxypropylene ether were slowly added during the shaking. Continue to shake for 8 minutes. After the biomass pyrolysis oil is thoroughly mixed with the added demulsifier, the mixture is transferred to a separatory funnel and allowed to stand for 20 minutes. At this time, the lower aqueous solution becomes clear and the water-oil interface is clear, and the upper biomass pyrolysis oil ring and the lower aqueous solution are separated.
  • the formed ZSM-5/white earth catalyst was immersed in a 1 mol/L NH 4 N0 3 solution at 80 ° C for 6 hours, and the immersed catalyst was dried and calcined at 15 CTC for 3 hours.
  • the calcined catalyst was further aged at 500 ° C, 100% steam for 2 hours. 200 g of this catalyst was weighed into a fixed fluidized bed, and catalytic cracking reaction was carried out under the conditions of a mass space velocity of 1211 oil ratio of 16, a reaction temperature of 650 ° C, and a reaction pressure of 0.5 MPa.
  • the product analysis results are shown in Table 8.
  • the formed catalyst has low deoxygenation selectivity and is easy to deactivate due to its small acid center and uneven distribution. After ion exchange of 1 mol/L NH 4 N0 3 solution, the acid center of the catalyst is obviously increased and uniformly distributed in the catalyst, so that the deoxidation selectivity of the catalyst can be improved.

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Abstract

本发明提供一种生物质热解油的改性方法，具体包括以下步骤：第一步破乳分层除水：向生物质热解油中加入无机盐离子和有机破乳剂，其中无机盐与生物质热解油的质量比为1:2000～1:800，有机破乳剂与生物质热解油的质量比为1:4000～1: 1000，充分混合后静置，取上层生物质热解油；第二步对生物质热解油进行催化裂化改性：采用改性催化剂：1）改性催化剂：在500℃～800℃条件下，100%水蒸汽对沸石分子筛负载白土催化剂老化处理2～8h；2）取老化后的催化剂装入反应器内，将生物质热解油注入到装有催化剂的反应器中，剂油比为1:3～16；在质量空速6～15h-1、反应温度380℃～700℃、反应压力0.1Mpa～0.8Mpa的条件下进行生物质热解油催化裂化改性。

Description

一种生物质热解油的改性方法
技术领域
本发明提供一种生物质热解油的改性方法。具体地讲是将生物质热解油经过脱水后 直接催化裂化生产燃料油的技术。 背景技术
以石油、 煤炭、 天然气为主的化石能源日益枯竭。 生物质能源是仅次于石油、 煤 炭、 天然气的第四大能源， 具有来源广泛、 安全、 可再生循环、 零二氧化碳排放的优 点。 生物质来源主要包括农作物、 树木、 其他植物及秸秆等， 生物质经过一系列的转 换技术可以生产出不同类型能源燃料， 如生物质碳化可以生产优质的固体燃料、 生物 质气化可以生产气体燃料、 生物质液化可以获得液体燃料等。 生物质直接转化为液体 燃料技术可将低品质、 低热值的生物质能转化为高品质、 高热值、 易于储存和运输的 液体燃料。 生物质经热解液化获得的生物质热解油经过改性精制后可直接作为石化燃 料的替代产品。
生物质热解技术是在无氧条件下将生物质快速加热至高温， 利用热能切断生物质 大分子的化学键使之转变为低分子物质的过程。该技术自上个世纪 80年代至今发展迅 速， 已经开发出多种生物质热解技术工艺。 如美国佐治亚理工学院的夹带流反应器 (entrained flow reactor)和太阳能研究所 (SERI)的漩涡反应器 (vortex reactor) 、 加拿大 DynaMotive Energy Systems的流化床反应器 (fluidized bed reactor)和 ENSYN的循环流 化床反应器 (upflow circulatingfluidized bed reactor)、 荷兰 Twente大学和 BTG的旋转锥 反应器 (rotating cone reactor)等。 其中荷兰 BTG禾口力口拿大 DynaMotive Energy Systems 已分别建成了日处理 30t棕榈壳和 100t木屑的热解液化工业示范装置， 生物质热解油 产油率均在 60 % (质量百分含量） 以上。 但是生物质的 3种主要组分纤维素、 半纤维 素和木质素， 在热裂解过程中受热裂解不完全同步， 热解过程也未达到热力学平衡， 产物组成非常复杂。 其中水是生物质热解油中含量最多的单种组分， 一般情况下生物 质热解油的含水量达 30%〜40% (质量百分含量）， 主要来源于原料中的水分和热裂解 过程生物质发生缩聚反应所生成的水分。 其次生物质热解油包含成百上千种有机化合 物， 如酸、 醇、 醚、 酯、 醛、 酮、 酚等， 导致生物质热解油含氧量高、 酸值高、 粘度 高、 热值低， 而且其物理化学性质非常不稳定。 含氧量高导致生物质热解油随着存储 时间变长粘度增加； 含有的酚类物质随温度升高容易氧化， 导致热解油结块硬化； 生 物质热解油的酸值高， 在存储和使用过程中极易腐蚀设备。 因此生物质热解油不能直 接作为燃料广泛使用， 需要经过改性精制， 提高生物质热解油品质， 满足液体燃料的 质量要求。
CN1376766 介绍了一种直接加氢改性精制生物质热解油的方法， 具体方法是在 350°C以上、 lOMPa的条件下用 CoMo加氢催化剂，直接加氢脱除生物质热解油中的氧， 得到改性热解油。 虽然加氢是脱氧最有效的方法， 但是生物质热解油中含氧量达 40% 以上， 完全脱除需消耗大量的氢气， 而且加氢条件苛刻， 设备工艺复杂， 成本昂贵， 工业生产中不具有可行性。
CN101381611 介绍了一种酯化醚化改性生物质热解油的方法， 具体方法是向未经 除水的生物质热解油中加入低碳醇，在 90°C〜11(TC条件下酯化或醚化反应 5〜8小时， 再经过 80°C〜13(TC减压蒸熘除去水分。 该专利描述的生物质热解油含水量 20%〜 30% , 大量水的存在无疑会加大酯化反应的难度； 酯化反应温度和蒸熘温度都高于 80°C， 而生物质热解油在高于 80°C时， 老化速度明显加快， 会析出大量固体颗粒， 稳 定性变差。
CN101899334A 介绍了一种对生物质热解油先除水， 再进行酯化反应， 达到生物 质热解油除水除酸改性的目的。 具体方法是向生物质热解油中加入异辛醇与水形成共 沸物， 在 0.02Mpa、 80°C水浴减压蒸熘分出大部分水分， 再向脱水后的生物质热解油中 加入乙酰氯， 通过乙酰氯的水解除去剩余水分； 完全除水后的生物质热解油与乙醇进 行酯化反应， 酯化反应生成的少量水经加入的无水硫酸镁脱除， 最终达到生物质热解 油的脱水除酸的效果。 乙酰氯和生物质热解油中的水发生反应达到除水目的， 脱水的 同时也消耗了乙酰氯， 无疑大大增加成本； 酯化反应后加入无水硫酸镁继续脱水， 需 要重新分离硫酸镁， 增加工艺难度同时必然增加了生物质热解油改性过程中的损耗。
现有生物质热解油改性精制的方法大致如下： 第一， 通过精熘， 包含减压精熘、 反应精熘、 萃取精熘除去生物质热解油中的水分； 第二， 脱水后的生物质热解油经过 催化酯化降低酸度和粘度； 第三， 对生物质热解油直接加氢改性。 在这些工艺过程中， 加热精熘时极易使生物质热解油粘度变大甚至结块变质。 同时由于生物质热解油含有 较多低沸点组分， 精熘过程将造成这些低沸点组分和一些有机共沸物的损耗。 而催化 加氢的设备一般较复杂， 成本高， 在生产过程中容易发生反应器堵塞和催化剂失活。 发明内容
本发明的目的在于开发一种高效的生物质热解油改性方法， 提高改性后生物质热 解油的物理化学品质， 以克服现有技术的不足。
本发明的技术方案： 本发明的生物质热解油的改性方法具体包括以下步骤： 第一步破乳分层除水： 向生物质热解油中加入无机盐离子和有机破乳剂， 其中无 机盐与生物质热解油的质量比为 1 : 2000〜1： 800， 有机破乳剂与生物质热解油的质量 比为 1 : 4000〜1： 1000, 经震荡或者搅拌， 充分混合后静置， 待下层水溶液变得澄清 且油水界面清晰时， 分出上层生物质热解油和下层水溶液， 取上层生物质热解油； 第二步对生物质热解油进行催化裂化改性： 催化裂化反应采用常规催化裂化反应 器， 催化裂化反应的改性催化剂采用沸石分子筛负载白土制备的改性催化剂：
1 ) 改性催化剂： 在 500°C〜80(TC条件下， 100%水蒸汽对沸石分子筛负载白土催 化剂老化处理 2〜8h;
2)取一定量老化后的催化剂装入反应器内， 用柱塞泵将生物质热解油注入到装有 催化剂的反应器中，剂油比为 1 : 3〜16；在质量空速 6〜151^、反应温度 380°C〜70(TC、 反应压力 0.1Mpa〜0.8Mpa的条件下进行生物质热解油催化裂化改性。
所述的第二步的步骤 1 ) 采用沸石分子筛负载白土制备的改性催化剂包含 REY/白 土、 REUS Y/白土、高硅 REUS Y/白土、 LREHY/白土、 ZSM-5/白土；成型催化剂经 lmol/L 的 NH4N03溶液离子交换后， 150°C〜30(TC焙烧 2〜4小时， 得到脱氧选择性强的改 性催化剂。
所述的破乳分层除水所用的无机盐为含有离子 Ca2+、 Na+、 K+、 Al3+、 Fe2+、 ΝΗ4+、 Cl_、 S04 2_、 N03_的无机盐。
所述的破乳分层除水所用的有机破乳剂为聚氧丙烯醚、 聚氧乙烯醚、 丙二醇、 正 丙醇中的一种。
优选地， 所述的破乳分层除水所用的无机盐为含有离子 Na+、 NH4+、 Cl_、 S04 2—的 无机盐。
优选地， 第一步无机盐与生物质热解油的质量比为 1 : 1500〜1： 1000, 有机破乳 剂与生物质热解油的质量比为 1 : 2000〜1： 1300。
优选地， 所述的第二步的步骤 1 ) 改性催化剂老化处理前， 催化剂经 lmol/L 的 NH4N03溶液离子交换后， 再在 150°C〜30(TC焙烧 2〜4小时， 得到脱氧选择性强的改 性催化剂。
优选地， 所述的第一步破乳分层除水时， 经震荡或者搅拌时间为 3〜60分钟， 充 分混合后静置 20±5分钟。
本发明的方法具有以下优点：
1.由于采用了破乳剂与无机盐进行破乳分层除水，可在常温下进行油水分离，达到 生物质热解油除水效果。 破乳剂可以加速油水分离； 无机盐破坏乳状液双电层， 内向 水析出速率加快， 同时改变了乳化剂的亲水亲油平衡， 增加油水分离效果； 在常温下 进行油水分离， 可以避免生物质热解油老化。
2.经本发明方法破乳除水， 油水分离可脱除原生物质热解油中大部分水，得含水量 不超过 8% (质量比） 的上层生物质热解油。 少量水的存在可以降低热解油的粘度， 保 持生物质热解油良好流动性， 使催化裂化反应进料容易。
3. 本发明方法催化裂化反应时间极短， 可在生物质热解油老化前对其进行裂化生 成稳定的短链烃类和裂化气。
4.对催化裂化催化剂进行改性， 特别是离子交换处理， 增加了催化剂酸性， 提高催 化剂脱氧选择性， 对生物质热解油脱氧更有效。
5.对催化裂化催化剂进行改性，催化剂具有高活性及高脱氧选择性，可以将生物质 热解油中的氧以 H20、 CO或 C02形式除去， 而不需要消耗还原性气体。
6.该工艺简单， 设备低廉， 成本低， 容易实现大规模工业化连续生产。 具体实施方式
下面以具体实施例来阐述本发明的技术方案：
实施例中， 生物质热解油水分采用 GB11146卡尔费休水分滴定法测定； 热解油酸 度采用 GB/T264-1991石油产品酸值测定法测定；热解油粘度采用毛细管运动粘度计测 定； 热解油低位热值采用 GB/T18856水煤浆发热量测定方法测定； 热解油中的 C、 H、 0采用元素分析仪测定。
实施例 1
取 1000g生物质热解油置于 1500ml的三口烧瓶中，在搅拌的过程中缓慢加入 0.5g 氯化钠和 0.25g聚氧丙烯醚。继续搅拌 5分钟， 生物质热解油与加入的破乳剂充分混合 后，将混合液转入分液漏斗中静置 20分钟。此时下层水溶液变的清澈且水油界面清晰， 分出上层生物质热解油 I和下层水溶液。
将成型的高硅 REUSY/白土催化剂放入 80°C、 lmol/L的 NH4N03溶液中浸泡 6小 时， 浸泡后的催化剂经干燥后在 15CTC的条件下焙烧 3 小时。 焙烧过的催化剂再经 600°C、 100%水蒸汽老化 3小时。 称取 200g该催化剂装入固定流化床内， 在质量空速 6Κ 剂油比为 8、 反应温度 450°C、 反应压力 0.2Mpa的条件下进行催化裂化反应。 对 裂化产物分析结果如表 1。
表 1生物质热解油 I催化裂化改性结果 （P=latm， T=28 °C ) 理化性质 元素分析（％) 收率
水含量 酸度 运动粘度 低位热值
wt% C H 0 wt% mgKOH/ 100ml 腿 2/s MJ/kg 热解原油 32. 3 6965 16. 5 12. 3 47. 03 6. 78 44. 92 脱水热解油 23. 4 6820 37. 7 13. 5 52. 67 5. 50 40. 11 改性后产物 75. 5 370 16. 9 20. 6 60. 65 6. 97 30. 75 实施例 2
取 1000g生物质热解油置于 1500ml的三口烧瓶中， 在搅拌的过程中缓慢加入 lg 硫酸钠和 lg丙二醇。 继续搅拌 5分钟， 生物质热解油与加入的破乳剂充分混合后， 将 混合液转入分液漏斗中静置 20分钟。 此时下层水溶液变的清澈且水油界面清晰， 分出 上层生物质热解油 II和下层水溶液。
将成型的 REY/白土催化剂放入 80°C、 lmol/L的 NH4N03溶液中浸泡 6小时， 浸 泡后的催化剂经干燥后在 30CTC的条件下焙烧 4小时。焙烧过的催化剂再经 80CTC、 100% 水蒸汽老化 5小时。称取 200g该催化剂装入固定流化床内， 以质量空速 101^、剂油比 为 8、 反应温度 550°C、 反应压力 0.3Mpa的条件下进行催化裂化反应。 对产物分析结 果如表 2。
表 2生物质热解油 II催化裂化改性结果 （P=latm， T=28 °C ) 理化性质 元素分析（％) 收率
水含量 酸度 运动粘度 低位热值
wt% C H 0 wt% mgKOH/ 100ml 腿 7s MJ/kg 热解原油 32. 3 6965 16. 5 12. 3 47. 03 6. 78 44. 92 脱水热解油 7. 5 6621 152. 8 21. 5 60. 59 5. 22 31. 59 改性后产物 90. 7 352 17. 4 30. 7 70. 82 8. 64 19. 89 实施例 3
取 1000g生物质热解油置于 1500ml的三口烧瓶中，在搅拌的过程中缓慢加入 0.6g 氯化钠和 0.3g聚氧丙烯醚。 继续搅拌 5分钟， 生物质热解油与加入的破乳剂充分混合 后，将混合液转入分液漏斗中静置 20分钟。此时下层水溶液变的清澈且水油界面清晰， 分出上层生物质热解油 III和下层水溶液。
将成型的高硅 REUSY/白土催化剂放入 80°C、 lmol/L的 NH4N03溶液中浸泡 6小 时， 浸泡后的催化剂经干燥后在 15CTC的条件下焙烧 3 小时。 焙烧过的催化剂再经 600°C、 100%水蒸汽老化 3小时。 称取 200g该催化剂装入固定流化床内， 在质量空速 6Κ 剂油比为 8、 反应温度 450°C、 反应压力 0.2Mpa的条件下进行催化裂化反应。 对 裂化产物分析结果如表 3。
表 3生物质热解油 III催化裂化改性结果 （P=latm， T=28 °C ) 收率 理化性质 元素分析（％) wt% 水含量 酸度 运动粘度 低位热值 C H 0 wt% mgKOH/ 100ml 7s MJ/kg 热解原油 32. 3 6965 16. 5 12. 3 47. 03 6. 78 44. 92 脱水热解油 18. 4 6753 107. 5 17. 6 59. 77 5. 66 33. 13 改性后产物 86. 5 374 15. 7 25. 3 65. 05 7. 97 23. 35 实施例 4
取 lOOOg生物质热解油置于 1500ml的三口烧瓶中，在震荡的过程中缓慢加入 0.5g 硫酸铵和 0.5g聚氧乙烯醚。 继续震荡 8分钟， 生物质热解油与加入的破乳剂充分混合 后，将混合液转入分液漏斗中静置 20分钟。此时下层水溶液变的清澈且水油界面清晰， 分出上层生物质热解油 IV和下层水溶液。
将成型的 REUSY/白土催化剂放入 80°C lmol/L的 NH4N03溶液中浸泡 6小时， 浸泡后的催化剂经干燥后在 20CTC的条件下焙烧 2小时。 焙烧过的催化剂再经 70CTC 100%水蒸汽老化 6小时。称取 200g该催化剂装入提升管反应器内， 以质量空速 15h— 剂油比为 3、 反应温度 550°C、 反应压力 0.3Mpa的条件下进行催化裂化反应。 对产物 分析结果如表 4
表 4生物质热解油 IV催化裂化改性结果 （P=latm T=28°C )
理化性质 元素分析（％) 收率
水含量 酸度 运动粘度 低位热值
wt% C H 0 wt% mgKOH/ 100ml 7s MJ/kg 热解原油 32. 3 6965 16. 5 12. 3 47. 03 6. 78 44. 92 脱水热解油 8. 3 6794 145. 5 19. 7 61. 78 5. 50 31. 56 改性后产物 80. 7 362 14. 6 28. 2 70. 73 7. 34 19. 63 实施例 5
取 1000g生物质热解油置于 1500ml的三口烧瓶中，在搅拌的过程中缓慢加入 0.5g 硫酸钠和 0.7g丙二醇。 继续搅拌 5分钟， 生物质热解油与加入的破乳剂充分混合后， 将混合液转入分液漏斗中静置 20分钟。 此时下层水溶液变的清澈且水油界面清晰， 分 出上层生物质热解油 V和下层水溶液。
将成型的 REY/白土催化剂放入 80°C、 lmol/L的 NH4N03溶液中浸泡 6小时， 浸 泡后的催化剂经干燥后在 30CTC的条件下焙烧 4小时。焙烧过的催化剂再经 80CTC、 100% 水蒸汽老化 5小时。称取 200g该催化剂装入固定流化床内， 以质量空速 101^、剂油比 为 8、 反应温度 550°C、 反应压力 0.3Mpa的条件下进行催化裂化反应。 对产物分析结 果如表 5。
表 5生物质热解油 V催化裂化改性结果 （P=latm， T=28°C )
理化性质 元素分析（％) 收率
水含量 酸度 运动粘度 低位热值
wt% C H 0 wt% mgKOH/ 100ml 腿 7s MJ/kg 热解原油 32. 3 6965 16. 5 12. 3 47. 03 6. 78 44. 92 脱水热解油 8. 7 6821 144. 7 19. 3 61. 25 5. 53 31. 86 改性后产物 82. 5 362 14. 4 28. 7 69. 73 8. 04 20. 91 实施例 6
取 1000g生物质热解油置于 1500ml的三口烧瓶中，在搅拌的过程中缓慢加入 1.2g 氯化钙和 0.3g正丙醇。 继续搅拌 5分钟， 生物质热解油与加入的破乳剂充分混合后， 将混合液转入分液漏斗中静置 20分钟。 此时下层水溶液变的清澈且水油界面清晰， 分 出上层生物质热解油 VI和下层水溶液。
将成型的 LREHY/白土催化剂放入 80°C、 lmol/L的 NH4N03溶液中浸泡 6小时， 浸泡后的催化剂经干燥后在 20CTC的条件下焙烧 2小时。 焙烧过的催化剂再经 50CTC、 100%水蒸汽老化 8小时。 称取 200g该催化剂装入固定流化床内， 以质量空速 151^、 剂油比为 12、 反应温度 600°C、 反应压力 0.3Mpa的条件下进行催化裂化反应。 对产物 分析结果如表 6。
表 6生物质热解油 VI催化裂化改性结果 （P=latm， T=28°C ) 理化性质 元素分析 (%) 收率
水含量 酸度 运动粘度 低位热值 wt% mgKOH/ 100ml 7s MJ/kg 热解原油 32. 3 6965 16. 5 12. 3 47. 03 6. 78 44. 92 脱水热解油 8. 1 7017 146. 4 20. 2 61. 57 5. 49 31. 41 改性后产物 78. 6 — 347 13. 3 29. 5 72. 27 7. 89 18. 49 实施例 7
取 1000g生物质热解油置于 1500ml的三口烧瓶中，在震荡的过程中缓慢加入 0.8g 氯化钠和 0.4g聚氧乙烯醚。 继续震荡 8分钟， 生物质热解油与加入的破乳剂充分混合 后，将混合液转入分液漏斗中静置 20分钟。此时下层水溶液变的清澈且水油界面清晰， 分出上层生物质热解油 W和下层水溶液。
将成型的高硅 REUSY/白土催化剂放入 80°C lmol/L的 NH4N03溶液中浸泡 6小 时， 浸泡后的催化剂经干燥后在 15CTC的条件下焙烧 3 小时。 焙烧过的催化剂再经 60(TC 100%水蒸汽老化 3小时。 称取 200g该催化剂装入提升管反应器内， 以质量空 速 12h_ 剂油比为 16、 反应温度 650°C、 反应压力 0.5Mpa的条件下进行催化裂化反 应。 对产物分析结果如表 7
表 7生物质热解油 W催化裂化改性结果 （P=latm T=28°C )
理化性质 元素分析（％) 收率
水含量 酸度 运动粘度 低位热值
wt% C H 0 wt% mgKOH/ 100ml 7s MJ/kg 热解原油 32. 3 6965 16. 5 12. 3 47. 03 6. 78 44. 92 脱水热解油 15. 7 6926 116. 4 18. 2 59. 89 5. 22 31. 61 改性后产物 74. 2 309 12. 4 32. 7 75. 55 7. 37 15. 72 实施例 8
取 1000g生物质热解油置于 1500ml的三口烧瓶中，在震荡的过程中缓慢加入 0.8g 氯化钠和 0.6g聚氧丙烯醚。 继续震荡 8分钟， 生物质热解油与加入的破乳剂充分混合 后，将混合液转入分液漏斗中静置 20分钟。此时下层水溶液变的清澈且水油界面清晰， 分出上层生物质热解油環和下层水溶液。
将成型的 ZSM-5/白土催化剂放入 80°C、 lmol/L的 NH4N03溶液中浸泡 6小时， 浸泡后的催化剂经干燥后在 15CTC的条件下焙烧 3小时。 焙烧过的催化剂再经 500°C、 100%水蒸汽老化 2小时。 称取 200g该催化剂装入固定流化床内， 以质量空速 1211 剂油比为 16、 反应温度 650°C、 反应压力 0.5Mpa的条件下进行催化裂化反应。 对产物 分析结果如表 8。
表 8生物质热解油環催化裂化改性结果 （P=latm， T=28°C ) 理化性质 元素分析（％) 收率
水含量 酸度 运动粘度 低位热值
wt% C H 0 wt% mgK0H/100ml 醒 7s MJ/kg 热解原油 32. 3 6965 16. 5 12. 3 47. 03 6. 78 44. 92 脱水热解油 14. 9 6875 126. 7 18. 6 60. 61 5. 28 31. 60 改性后产物 75. 3 286 10. 8 33. 9 81. 73 7. 41 8. 85
1、 从实施例中可以得出， 在本发明所给出的范围内， 随着无机盐、 有机破乳剂与 生物质热解油的质量比增大， 生物质热解油的脱水效果更明显。 这是因为无机盐质量 增加可以破坏油水双电层， 提高水相极性， 增加油水分离效果； 有机破乳剂质量增加 可以缩短油水分离时间。
2、 成型的催化剂由于其酸中心少， 分布不均匀导致其脱氧选择性低且容易失活。 经 lmol/L的 NH4N03溶液离子交换后， 明显增加了催化剂酸中心， 并且均匀分布于催 化剂， 因此可以提高催化剂脱氧选择性。

Claims

权利要求书
1.一种生物质热解油的改性方法，
第一步破乳分层除水： 向生物质热解油中加入无机盐离子和有机破乳剂， 其中无 机盐与生物质热解油的质量比为 1 : 2000〜1： 800， 有机破乳剂与生物质热解油的质量 比为 1 : 4000〜1： 1000, 经震荡或者搅拌， 充分混合后静置， 待下层水溶液变得澄清 且油水界面清晰时， 分出上层生物质热解油和下层水溶液， 取上层生物质热解油； 第二步对生物质热解油进行催化裂化改性： 催化裂化反应采用常规催化裂化反应 器， 催化裂化反应的改性催化剂采用沸石分子筛负载白土制备的改性催化剂：
1 ) 改性催化剂： 在 500°C〜80(TC条件下， 100%水蒸汽对沸石分子筛负载白土催 化剂老化处理 2〜8h;
2)取一定量老化后的催化剂装入反应器内， 用柱塞泵将生物质热解油注入到装有 催化剂的反应器中，剂油比为 1 : 3〜16；在质量空速 6〜151^、反应温度 380°C〜70(TC、 反应压力 0.1Mpa〜0.8Mpa的条件下进行生物质热解油催化裂化改性。
2.根据权利要求 1所述的生物质热解油的改性方法，其特征在于：第二步的步骤 1 ) 采用沸石分子筛负载白土制备的改性催化剂包含 REY/白土、 REUSY/白土、 高硅 REUSY/白土、 LREHY/白土、 ZSM-5/白土； 成型催化剂经 lmol/L的 NH4N03溶液离子 交换后， 150°C〜30(TC焙烧 2〜4小时， 得到脱氧选择性强的改性催化剂。
3.根据权利要求 1或 2所述的生物质热解油的改性方法， 其特征在于： 破乳分层除 水所用的无机盐为含有离子 Ca2+、 Na+、 K+、 Al3+、 Fe2+、 ΝΗ4 +、 Cl_、 S04 2、 N03-的无 机盐。
4.根据权利要求 1或 2所述的生物质热解油的改性方法， 其特征在于： 破乳分层除 水所用的有机破乳剂为聚氧丙烯醚、 聚氧乙烯醚、 丙二醇、 正丙醇中的一种。
5.根据权利要求 1或 2所述的生物质热解油的改性方法，其特征在于： 破乳分层除 水所用的无机盐为含有离子 Na+、 NH4 +、 Cl_、 S04 2_的无机盐。
6.根据权利要求 1或 2所述的生物质热解油的改性方法，其特征在于： 第一步无机 盐与生物质热解油的质量比为 1 : 1500〜1： 1000, 有机破乳剂与生物质热解油的质量 比为 1： 2000〜1： 1300。
7.根据权利要求 1或 2所述的生物质热解油的改性方法，其特征在于： 第二步的步 骤 1 ) 改性催化剂老化处理前， 催化剂经 lmol/L的 NH4N03溶液离子交换后， 再在 15(TC〜30(TC焙烧 2〜4小时， 得到脱氧选择性强的改性催化剂。
8.根据权利要求 3所述的生物质热解油的改性方法，其特征在于：第二步的步骤 1 ) 改性催化剂老化处理前， 催化剂经 lmol/L的 NH4N03溶液离子交换后， 再在 15CTC〜 30CTC焙烧 2〜4小时， 得到脱氧选择性强的改性催化剂。
9.根据权利要求 4所述的生物质热解油的改性方法，其特征在于：第二步的步骤 1 ) 改性催化剂老化处理前， 催化剂经 lmol/L的 NH4N03溶液离子交换后， 再在 15CTC〜 30CTC焙烧 2〜4小时， 得到脱氧选择性强的改性催化剂。
10.根据权利要求 1或 2所述的生物质热解油的改性方法， 其特征在于： 第一步破 乳分层除水时， 经震荡或者搅拌时间为 3〜60分钟， 充分混合后静置 20±5分钟。
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