WO2019019539A1 - 利用生物油催化加氢耦合催化裂化制备芳香烃和烯烃的方法及装置 - Google Patents

利用生物油催化加氢耦合催化裂化制备芳香烃和烯烃的方法及装置 Download PDF

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WO2019019539A1
WO2019019539A1 PCT/CN2017/117053 CN2017117053W WO2019019539A1 WO 2019019539 A1 WO2019019539 A1 WO 2019019539A1 CN 2017117053 W CN2017117053 W CN 2017117053W WO 2019019539 A1 WO2019019539 A1 WO 2019019539A1
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oil
cracking
bio
catalytic
unit
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French (fr)
Inventor
陈冠益
张瑞雪
马文超
刘彬
杜桂月
颜蓓蓓
程占军
钟磊
李湘萍
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Tianjin University
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Tianjin University
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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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/22—Higher olefins
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics
    • 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
    • Y02P30/40—Ethylene production

Definitions

  • the invention relates to the field of biomass resource utilization and low-temperature low-pressure catalytic hydrogenation, in particular to a method and a device for preparing aromatic hydrocarbons and olefins by catalytic hydrogenation coupled catalytic cracking of bio-oil.
  • Fossil energy (such as oil, coal, natural gas, etc.) is the main source of energy in today's society. With the development of industrialization, the world's demand for energy has increased with time. In the 21st century, in the face of the shortage of fossil fuel energy and non-renewable problems and the environmental pollution and greenhouse effect caused by the use of fossil fuels, the development of renewable new energy and environmentally friendly energy has shown its necessity and urgent Sex. Compared with other renewable energy sources (such as wind, solar, tidal and hydropower), biomass energy is the only renewable energy source that can be directly converted into liquid fuel, which has attracted much attention.
  • renewable energy sources such as wind, solar, tidal and hydropower
  • Pyrolysis technology is a thermochemical method with the following characteristics: reducing secondary pollution, generating storable energy, and harmful elements such as heavy metals are fixed in carbon black to recover heavy metals.
  • the energy density of bio-oil prepared by pyrolysis technology is greatly improved, and the obtained bio-oil has the characteristics of high viscosity, strong acidity, high oxygen content, high water content, low ash content and low calorific value.
  • Bio-oil has the potential to replace fossil fuel oil.
  • bio-oil has a high water content (15% to 30%), high oxygen content (including furans, phenols, aldehydes, ketones, etc.), high viscosity, and low calorific value (engine fuel is generally 42MJ/ Kg, while the crude bio-oil heat value is generally 20MJ/kg), and the acidity is strong (pH is about 2.5).
  • engine fuel is generally 42MJ/ Kg, while the crude bio-oil heat value is generally 20MJ/kg
  • the acidity is strong (pH is about 2.5).
  • bio-oil purification methods include emulsification, catalytic hydrogenation, catalytic cracking, catalytic esterification, etc., but all have the disadvantage of being difficult to industrialize.
  • CN1916135A discloses a method for producing fuel oil from biological fats and oils: directly catalyzing cracking of a mixture of bio-fat or a mixture with catalytic cracking raw materials or catalytic gasoline under the catalysis of a solid acid catalyst to produce liquefied gas and gasoline , diesel mixture.
  • CN101720349A discloses a process for preparing a biogasoline component: (I) obtaining at least one bio-oil to liquefy the bio-oil component; (II) adding the liquid bio-oil together with at least one mineral oil to the fluidization a catalytic cracking unit; (III) splitting the group added to the fluid catalytic cracking unit to form at least a bioliquefied petroleum gas fraction and a bio-naphtha fraction; (IV) at least a portion of the alkane of the bioliquefied petroleum gas fraction Base or catalytic polymerization; (V) combining at least a portion of the product of step (IV) with at least a portion of the bio-naphtha fraction to form a biogasoline component.
  • CN101463272A discloses a method for producing diesel oil by bio-oil hydrotreating: contacting a feedstock oil containing bio-oil with a catalyst under the condition of hydrogen presence and hydrotreating reaction, wherein the catalyst contains an effective amount of cracking active component An effective amount of a hydrogenation active metal component and a matrix.
  • the above process has the problem that the catalyst is easily coked and loses catalytic activity, resulting in problems of poor process stability and continuity.
  • CN103102907A discloses a two-stage hydrogenation method for producing low aromatic hydrocarbon solvent oil from bio-oil and fat: using bio-oil as raw material oil, under the hydrogenation condition, the feedstock oil and hydrogen are mixed through the first-stage hydrogenation reaction zone, and hydrogenation is generated.
  • the hydrogen-rich gas obtained by the separation of the stream is recycled in the first stage, and the separated liquid enters the second stage hydrocracking reaction zone, and the second hydrogen gas obtained by the second stage hydrogenation oil separation is recycled in the second stage, and is separated.
  • the liquid product is fractionated to obtain various low aromatic hydrocarbon solvent oils.
  • the hydrogenation active components of the hydrogenation catalyst used in the first stage are all one or more of the reduced states of W, Mo, Ni and Co.
  • the hydrogenation active component of the hydrogenation catalyst used in the second stage is one or more of the sulfided states of W, Mo, Ni and Co.
  • the method can partially ensure the activity stability of the catalyst, but there is a problem that the energy consumption of the hydrogenation operation is high.
  • CN101885986A discloses a method for refining bio-oil: (1) catalytically hydrogenating crude bio-oil at 140 ° C to 300 ° C for 10 minutes to 120 minutes to obtain a mixture, separating the resulting mixture to obtain an oil phase product; (2) by step (1) The obtained oil phase product is mixed with paraffin oil, and is subjected to catalytic cracking at 200 ° C to 550 ° C to obtain a refined bio-oil; wherein: the catalyst Pd/ ⁇ -Al 2 O 3 or Pd/C used in catalytic hydrogenation.
  • This method can partially solve the coking problem of the catalytic cracking catalyst, but requires the addition of paraffin oil, thereby increasing the manufacturing cost.
  • the invention aims to solve the problems in the process of upgrading the bio-oil quality by the thermochemical catalytic method for the whole component of the bio-oil, the catalyst is easy to coke and lose the catalytic performance, and the stability and continuity of the process are reduced.
  • the present invention is also directed to solving the thermochemical catalytic conversion upgrade for the heavy oil phase and the light oil phase component in the bio-oil, without realizing the full-component utilization of the bio-oil.
  • the inventors of the present application conducted intensive studies.
  • the invention finds that the aromatic hydrocarbon component and the olefin component can be prepared by catalytic cracking of the heavy oil component bio-oil and the hydrogenated and upgraded light oil component bio-oil, thereby avoiding catalyst coking and causing degradation of catalytic performance. , thereby improving the stability and continuity of the process.
  • the present invention can achieve full component utilization of bio-oil.
  • the invention provides a method for the preparation of aromatic hydrocarbons and olefins by biohydrogen catalytic hydrogenation coupled catalytic cracking, comprising the steps of:
  • the temperature of the thermal cracking reaction is 500 to 600 ° C, and the biomass raw material is heated to a temperature of 105 to 600 ° C at a heating rate of 105 to 500 ° C / s.
  • the condensation rate of the condenser is 40 to 70 ° C / s.
  • the hydrogenation reaction process conditions are: using a carbon-supported ruthenium-based catalyst or an activated carbon-supported ruthenium-based catalyst, the reaction temperature is 80 to 125 ° C, and the reaction pressure is 2 ⁇ 3MPa.
  • the process strip of the cracking reaction The working temperature of the catalytic cracking reactor is 400-700 ° C; the cracking catalyst is MCM-41/ZSM-5 composite micro-molecular molecular sieve or SBA-15/ZSM-5 composite micro-molecular molecular sieve as carrier and metal Pt or Al is used as the active metal.
  • an apparatus for producing aromatic hydrocarbons and olefins by catalytic hydrogenation-catalyzed catalytic cracking of bio-oil comprising:
  • a biomass pyrolysis oil production unit for thermally cracking a biomass feedstock to form a thermal cracking product; it is also used to separate the thermal cracking product into solid particles and oil and gas After the heat exchange, quenching is performed to obtain bio-oil;
  • a catalytic hydrogenation unit (300), which is used for mixing the light oil with mixed hydrogen, and performing catalytic hydrogenation reaction after heat exchange to obtain a hydrogenation reaction product, and the hydrogenation reaction product is subjected to gas-liquid separation. Thereby forming a gaseous product and a liquid product; it is also used to treat the gaseous product to obtain recycled hydrogen, and the recycled hydrogen is compressed and mixed with fresh hydrogen to form the mixed hydrogen;
  • a bio-oil catalytic cracking unit (400) for mixing the liquid product from the catalytic hydrogenation unit (300) with the heavy oil from a bio-oil standing stratification unit (200) to obtain a mixture, And heating the mixture, and then cracking reaction to obtain a cracking reaction product; it is also used for regenerating the catalyst to be formed formed after the reaction to obtain a regenerated catalyst, and re-involving the regenerated catalyst in the cracking reaction;
  • a purification unit (500) is used for separating and purifying the cracking reaction product to obtain an aromatic hydrocarbon and an olefin.
  • the biomass pyrolysis oil-making unit (100) comprises a thermal cracking device (1) and a cyclone separator (2) a heat exchanger (3) and a condenser (4); wherein an inlet of the thermal cracking device (1) is used to introduce a biomass feedstock, an outlet of the thermal cracking device (1) and the spin An inlet of the air separator (2) is connected; an outlet of the cyclone (2) is connected to an inlet of the condenser (4) through the heat exchanger (3); an outlet of the condenser (4) It is connected to the bio-oil standing layer unit (200).
  • the bio-oil standing stratification unit (200) comprises a static separator (5); wherein the static An inlet of the separator (5) is connected to an outlet of the condenser (4); an outlet of the upper end of the stationary separator (5) passes through the heat exchanger in the biomass pyrolysis oil production unit (100) (3) connected to the catalytic hydrogenation unit (300); the lower end outlet of the stationary separator (5) is connected to the bio-oil catalytic cracking unit (400).
  • the catalytic hydrogenation unit (300) comprises a fixed-bed catalytic hydrogenation reactor (6), a gas-liquid separator ( 7) a recycle gas treatment device (8) and a recycle hydrogen compressor (9); wherein the inlet of the fixed bed catalytic hydrogenation reactor (6) passes through the biomass pyrolysis oil production unit (100)
  • the heat exchanger (3) is connected to an upper end outlet of the stationary separator (5), and an outlet of the fixed bed catalytic hydrogenation reactor (6) is connected to an inlet of the gas-liquid separator (7) a gas product outlet of the gas-liquid separator (7) is connected to an inlet of the recycle gas treatment unit (8), a liquid product outlet of the gas-liquid separator (7) and the bio-oil catalytic cracking unit ( 400) connected;
  • the hydrogen outlet of the circulating gas treatment device (8) is connected to the inlet of the circulating
  • the bio-oil catalytic cracking unit (400) comprises a heating furnace (10), a catalytic cracking reactor (11) and a catalyst a regenerator (12);
  • the separation and purification unit (500) comprises a rectification column (13);
  • reaction raw material inlet of the catalytic cracking reactor (11) is passed through a heating furnace (10) a liquid product outlet of the gas-liquid separator (7) of the catalytic hydrogenation unit (300) and a lower end of the stationary separator (5) of the bio-oil standing layer unit (200), respectively
  • An outlet of the catalytic cracking reactor (11) is connected to an outlet of the catalyst regenerator (12); an outlet of the catalytic cracking reactor (11) and a chamber of the separation and purification unit (500)
  • the inlet of the rectification column (13) is connected; the catalyst outlet of the catalytic cracking reactor (11) is connected to the inlet of the catalyst regenerator (12);
  • the outlet of the rectification column (13) is used for discharging aromatic hydrocarbons and olefins.
  • the invention starts from the physical and chemical properties of different components of the bio-oil (heavy oil and light oil), and the liquid product obtained by low-temperature low-pressure catalytic hydrogenation of the light oil is mixed with the heavy oil, and then subjected to catalytic cracking, thereby realizing the bio-oil. "Coupling conversion" of full-component catalytic hydrogenation and catalytic cracking upgrade.
  • the invention processes the bio-oil step by step, and adopts different processing operations on the components of different physical and chemical properties, thereby avoiding catalyst coking and losing catalytic performance, thereby improving process stability and continuity.
  • the light oil catalytic hydrogenation of the present invention adopts low temperature and low pressure conditions, and adopts an activated carbon-supported ruthenium-based catalyst or an activated carbon-supported ruthenium-based catalyst, and thus the reaction conditions are milder than the conventional catalytic hydrogenation conditions. This saves hydrogen consumption and reduces costs.
  • the thermal cracking device of the present invention adopts a down-circulating fluidized bed rapid thermal cracking technology due to a pyrolysis process.
  • the catalyst regenerator of the present invention can improve the utilization rate of the catalyst, and can further solve the problem that the catalyst is easy to coke and lose the catalytic performance, thereby further solving the stability and continuity of the process. The problem of reduced sex.
  • Figure 1 is a schematic view of a bio-oil catalytic hydrogenation coupled catalytic cracking process for the preparation of aromatic hydrocarbons and olefins.
  • 100-biomass pyrolysis oil production unit 200-bio-oil static layering unit, 300-catalytic hydrogenation unit, 400-bio-oil catalytic cracking unit, 500-separation purification unit;
  • 1-Thermal cracking unit 2-cyclone separator, 3-heat exchanger, 4-condenser, 5-static separator, 6-fixed bed catalytic hydrogenation reactor, 7-gas liquid separator, 8-cycle Gas treatment unit, 9-cycle hydrogen compressor, 10-heat furnace, 11-catalyst cracking reactor, 12-catalyst regenerator, 13-rectification column.
  • bio-oil is obtained using biomass raw materials.
  • the biomass material of the present invention includes bio-fat or bio-waste, and the like.
  • the bio-fat is selected from the group consisting of vegetable oils and/or animal fats and oils, and may also be selected from vegetable oils and/or animal fats and oils.
  • the vegetable oil is selected from one or more of a herbal oil and a woody vegetable oil.
  • the herbal oil is selected from one or more of soybean oil, peanut oil, rapeseed oil, sunflower oil, and cottonseed oil.
  • the woody vegetable oil is selected from one or more of olive oil, palm tung oil, coconut oil, walnut oil, and camellia seed oil.
  • the animal oil is selected from one or more of lard, butter, sheep oil, chicken oil, duck oil, whale oil, and deep sea fish oil.
  • the above biomass feedstock is subjected to thermal cracking to obtain a bio-oil.
  • the bio-oil is liquid at room temperature.
  • the biological waste is selected from straw (eg, corn stalks, cotton stalks), wood chips, chaff, rice husks, forest waste, and the like.
  • the biomass material of the present invention is preferably straw.
  • coupling means that there is a close fit and interaction between the input and output of two or more operating processes or operating units.
  • the catalytic hydrogenation operation is closely coordinated with the catalytic cracking operation.
  • the aromatic hydrocarbon means a hydrocarbon having an aromatic ring (e.g., benzene ring) structure in the molecule.
  • the aromatic ring has a conjugated planar ring system, and the bonds between the atoms are not discontinuous single-double bonds, but are covered by the delocalized ⁇ electron cloud.
  • An olefin means a hydrocarbon containing a carbon-carbon double bond.
  • the heavy oil has the same meaning as the heavy oil phase
  • the light oil has the same meaning as the light oil phase and can be used interchangeably.
  • Mixed hydrogen has the same meaning as mixed hydrogen.
  • Circulating hydrogen has the same meaning as circulating hydrogen.
  • Fresh hydrogen and new hydrogen have the same meaning and can be used interchangeably.
  • the apparatus for preparing aromatic hydrocarbons and olefins is an aggregate of a plurality of apparatuses and/or units. Units have the same meaning as systems and can be used interchangeably.
  • the heavy oil phase of the bio-oil is separated from the light oil phase according to the properties of the bio-oil, and then the light oil phase is catalytically hydrogenated at a low temperature and a low pressure, and the aldehydes in the light oil phase are Ketones, acids and the like are converted into stable alcohols and saturated furan compounds, and the liquid products are mixed with heavy oils for hydrocracking and separation and purification to obtain aromatic hydrocarbon components and olefin components. . Due to the selection of low temperature and low pressure catalytic hydrogenation light bio-oil and catalytic hydrogenation coupled catalytic cracking technology, this is of great significance for energy saving and emission reduction.
  • the preparation process of the invention comprises the steps of: 1) a thermal cracking step; 2) a static separation step; 3) a catalytic hydrogenation step; 4) a hydrogenation step; 5) a catalytic cracking step: 6)
  • the separation and purification steps are carried out.
  • the thermal cracking step of the present invention involves the thermal cracking reaction of the biomass feedstock into a thermal cracking unit to form a thermal cracking product, which is separated into solid particles and oil and gas by a cyclone separator.
  • the thermal cracking device and the cyclone separator are not particularly limited, and those known in the art can be employed. Any separation device capable of separating the pyrolysis product into solid particles and oil and gas can be used. Separation devices similar or equivalent to cyclones are within the scope of the invention.
  • the temperature of the thermal cracking reaction is from 500 to 600 ° C, preferably from 530 to 580 ° C.
  • the biomass raw material is heated to a heating rate of 105 to 500 ° C / s, preferably 150 to 300 ° C / s, to 500 to 600 ° C, preferably 530 to 580 ° C.
  • the biomass raw material is added from the top of the thermal cracking device, and in the downward process of the biomass raw material, the heating is carried out at a heating rate of 105 to 500 ° C / s to 500 to 600 ° C, and the biomass raw material is generated. Rapid thermal cracking reaction to form a thermal cracking product.
  • the biomass raw material may be straw particles having a particle diameter of less than 2 mm
  • the oxygen carrier may be an iron-based oxygen carrier Fe 2 O 3 /Al 2 O 3 (with Al 2 O 3 as a carrier).
  • Fe 2 O 3 is the active ingredient
  • the catalyst may be a nickel-based molecular sieve catalyst Ni/HZSM-5.
  • the outlet of the thermal cracker is connected to a cyclone, and the pyrolysis product separates the solid particles from the oil and gas via a cyclone.
  • the static separation step of the present invention is to exchange the oil and gas through the heat exchanger and then enter the condenser to be quenched to obtain the bio-oil, and the bio-oil is divided into the heavy oil and the light oil in the static separator.
  • the pure oil and gas passes through the heat exchanger and then enters the condenser to be quenched to obtain liquid fuel bio-oil.
  • the condenser has a condensation rate of 40 to 70 ° C / s, preferably 50 to 60 ° C / s.
  • the standing separator the heavy components in the bio-oil sink and the light components rise, thereby achieving stratification, and then separating the two into heavy oil and light oil.
  • the catalytic hydrogenation step of the present invention is to mix the light oil with mixed hydrogen, heat exchange with a heat exchanger, and then pass through a fixed bed catalytic hydrogenation reactor for catalytic hydrogenation reaction to obtain a hydrogenation reaction product, which will
  • the hydrogenation reaction product is passed to a gas-liquid separator for gas-liquid separation to form a gaseous product and a liquid product.
  • the mixed hydrogen of the present invention is as follows.
  • the light oil is mixed with mixed hydrogen to form a mixture, and the mixture is heated and exchanged with the heat exchanger to save energy.
  • the catalytic hydrogenation reaction of the present invention is carried out in a fixed bed catalytic hydrogenation reactor. Due to the catalytic hydrogenation using light oil, the problem of catalyst coking is not easy to occur.
  • the light oil reacts with the mixed hydrogen under the action of a hydrogenation catalyst to convert unsaturated components (such as aldehydes, ketones, acids, etc.) in the light oil into hydrogenation.
  • unsaturated components such as aldehydes, ketones, acids, etc.
  • Saturated components in the reaction product for example, alcohols and saturated furan compounds, etc.
  • examples of the hydrogenation catalyst include, but are not limited to, an activated carbon-supported rhodium-based catalyst or an activated carbon-supported rhodium-based catalyst.
  • the reaction temperature for catalytic hydrogenation is 80 to 125 ° C, preferably 90 to 120 ° C; and the reaction pressure is 2 to 3 MPa, preferably 2 to 2.3 MPa.
  • the hydrogenation reaction process conditions are: using a carbon-supported rhodium-based catalyst or an activated carbon-supported rhodium-based catalyst as a hydrogenation catalyst, the reaction temperature is 80 to 125 ° C, and the reaction pressure is 2 to 3 MPa. Hydrogenation at low temperature and low pressure can significantly reduce energy consumption and cost.
  • the hydrogenation reaction product is passed to a gas-liquid separator for gas-liquid separation to form a gaseous product and a liquid product.
  • Gas-liquid separators known in the art may be employed, and are not described herein.
  • the mixed hydrogen step of the present invention is to pass the gaseous product into a circulating gas treatment device for treatment to obtain circulating hydrogen, and the remaining gas in the circulating gas treatment device is directly discharged; after the circulating hydrogen is compressed by the circulating hydrogen compressor It is mixed with fresh hydrogen to form the mixed hydrogen.
  • the recycle gas treatment device the recycle hydrogen compressor may employ those known in the art.
  • the gas product is separated into circulating hydrogen and the remaining gas (exhaust gas) in the circulating gas treatment device, thereby realizing the recycling of the hydrogen, thereby achieving the purpose of reducing the cost.
  • the circulating hydrogen is mixed with fresh hydrogen to form a mixed hydrogen.
  • the catalytic cracking step of the present invention comprises mixing the liquid product from the gas-liquid separator with heavy oil from the stationary separator to obtain a mixture; heating the mixture through a heating furnace and then entering a catalytic cracking reaction
  • the mixture undergoes a cracking reaction under the action of a cracking catalyst to obtain a cracking reaction product; the catalyst to be produced formed after the reaction enters the catalyst regenerator to be regenerated to obtain a regenerated catalyst, and the flue gas formed by the catalyst regenerator is directly discharged; the regenerated catalyst Re-entering the catalytic cracking reactor participates in the cracking reaction.
  • the mixing ratio of the liquid product to the heavy oil is not particularly limited. In liquid products The amount of unsaturated components is small, which prevents coking of the catalyst.
  • the catalytic cracking reactor has an operating temperature of from 400 to 700 ° C, for example from 500 to 600 ° C.
  • the cracking reaction can be carried out at 400 to 700 ° C, for example, 500 to 600 ° C.
  • the carrier of the cracking catalyst may be a MCM-41/ZSM-5 composite micro-molecular sieve or a SBA-15/ZSM-5 composite micro-molecular sieve as a carrier, and the active metal may be Pt or Al.
  • the catalyst is a Pt-loaded MCM-41/ZSM-5 composite micro-molecular molecular sieve. Under the above conditions, the catalyst is less prone to coking.
  • the catalyst to be formed formed after the reaction enters the catalyst regenerator for regeneration to obtain a regenerated catalyst, and the regenerated catalyst re-enters the catalytic cracking reactor to participate in the cracking reaction. This saves the amount of catalyst and allows the catalytic cracking reaction to continue.
  • the flue gas formed by the catalyst regenerator is directly discharged or recycled.
  • the separation and purification step of the present invention comprises separating and purifying the cracked reaction product through a rectification column to obtain an aromatic hydrocarbon and an olefin.
  • Any apparatus that can achieve the purpose of separation and purification can be used in the present invention, such as a rectification column. Separation equipment similar or equivalent to the rectification column is within the scope of the invention. Separation and purification process parameters known in the art can be employed and will not be described again here.
  • the method of the present invention for producing aromatic hydrocarbons and olefins using bio-oil catalytic hydro-coupled catalytic cracking comprises the steps of:
  • the biomass raw material is added to the thermal cracking device to undergo thermal cracking reaction;
  • the thermal cracking product is separated into solid particles and oil and gas through a cyclone;
  • the bed catalytic hydrogenation reactor carries out a hydrogenation upgrading reaction, and the reaction product enters a gas-liquid separator for gas-liquid separation;
  • the obtained circulating hydrogen gas is compressed into a circulating hydrogen compressor and mixed with new hydrogen to form a mixed hydrogen, and the remaining gas in the circulating gas treatment device is directly discharged;
  • the liquid product separated by the separator is mixed with the heavy oil from the stationary separator, heated by the heating furnace and then introduced into the catalytic cracking reactor;
  • the generated catalyst is introduced into the catalyst regenerator for regeneration, and the regenerated catalyst regenerated by the catalyst regenerator is reintroduced into the catalytic cracking reactor reaction, and the catalyst is regenerated.
  • the flue gas is discharged, and the reaction product of the catalytic cracking reactor enters the rectification column for separation and purification, and the rectification column product is an aromatic hydrocarbon and an olefin component.
  • the thermal cracking reaction temperature of step 1) is from 500 to 600 ° C and the cracking process is heated to the thermal cracking reaction temperature using a ramp rate of from 105 to 500 ° C/s.
  • the condenser of step 2) has a condensation rate of from 40 to 70 ° C/s.
  • the catalytic hydrogenation reactor process of step 3) is carried out using a carbon-supported rhodium-based catalyst and a rhodium-based catalyst at a reaction temperature of 80 to 125 ° C and a reaction pressure of 2 to 3 MPa. Hydrogenation and upgrading reaction.
  • the catalytic cracking reactor process of step 5) is: the catalytic cracking reactor is operated at a temperature of 400 to 700 ° C, using MCM-41/ZSM-5 or SBA-15/ZSM-5 micro mesopores.
  • the molecular sieve is used as a carrier, and the metal Pt or Al is used as a catalyst for the active metal.
  • the catalyst to be produced enters the catalyst regenerator for regeneration.
  • the apparatus for producing aromatic hydrocarbons and olefins by bio-oil catalytic hydro-coupled catalytic cracking comprises biomass pyrolysis oil-making unit, bio-oil static stratification unit, catalytic hydrogenation unit, biological An oil catalytic cracking unit and a separation and purification unit.
  • the liquid product of the catalytic hydrogenation unit is output to the bio-oil catalytic cracking unit, and is catalytically cracked together with the heavy oil from the bio-oil standing stratification unit, and the cracking reaction product enters the separation and purification unit.
  • the method of operation of the apparatus of the present invention is as described above and will not be described herein.
  • the biomass pyrolysis oil producing unit of the present invention is used for thermally cracking a biomass raw material to form a thermal cracking product; and is also used for separating the thermal cracking product into solid particles and oil and gas, and after the heat exchange of the oil and gas Quenching to obtain bio-oil.
  • the biomass pyrolysis oil production unit may include a thermal cracking unit, a cyclone separator, a heat exchanger, and a condenser. These devices can employ those known in the art. Examples of condensers include, but are not limited to, a rapid condenser.
  • the inlet of the thermal cracker is used to introduce biomass feedstock, and the outlet of the thermal cracker is connected to the inlet of the cyclone.
  • the biomass feedstock undergoes a thermal cracking reaction to form a thermal cracking product.
  • the operating temperature of the thermal cracking unit may be from 500 to 600 ° C, preferably from 530 to 580 ° C.
  • the thermal cracking unit has a heating rate of 105 to 500 ° C / s, preferably 150 to 300 ° C / s.
  • the thermal cracking unit is provided with a catalyst, preferably a catalyst and an oxygen carrier. The specific materials are as described above and will not be described herein.
  • the outlet of the cyclone is connected to the inlet of the condenser via a heat exchanger.
  • the outlet of the condenser is connected to the bio-oil standing layer unit.
  • the condenser has a condensation rate of 40 to 70 ° C / s, preferably 50 to 60 ° C / s.
  • the bio-oil standing layering unit of the present invention is used to divide the bio-oil into heavy oil and light oil.
  • the bio-oil standing layering unit includes a stationary separator having an inlet, an upper outlet, and a lower outlet.
  • the inlet of the stationary separator is connected to the outlet of the condenser; the outlet of the upper end of the stationary separator is connected to the catalytic hydrogenation unit through a heat exchanger in the biomass pyrolysis oil production unit; the lower end outlet of the static separator is separated from the bio-oil
  • the catalytic cracking unit is connected.
  • the heavy components in the bio-oil sink and the light components rise, thereby achieving stratification, and then separating the two into heavy oil and light oil.
  • the catalytic hydrogenation unit of the invention is used for mixing the light oil with mixed hydrogen, and performing catalytic hydrogenation reaction after heat exchange to obtain a hydrogenation reaction product, and the hydrogenation reaction is produced.
  • the gas and liquid separation is carried out to form a gaseous product and a liquid product; it is also used to treat the gaseous product to obtain recycled hydrogen, and the recycled hydrogen is compressed and mixed with fresh hydrogen to form the mixed hydrogen.
  • the catalytic hydrogenation unit comprises a fixed bed catalytic hydrogenation reactor, a gas-liquid separator, a recycle gas treatment device and a circulating hydrogen compressor.
  • the inlet of the fixed bed catalytic hydrogenation reactor is connected to the upper end outlet of the stationary separator through a heat exchanger in the biomass pyrolysis oil producing unit, and the outlet of the fixed bed catalytic hydrogenation reactor is connected to the inlet of the gas-liquid separator.
  • a hydrogenation catalyst is present in the fixed bed catalytic hydrogenation reactor.
  • the catalyst includes, but is not limited to, a ruthenium based catalyst supported on activated carbon or a ruthenium based catalyst supported on activated carbon.
  • the working temperature of the fixed bed catalytic hydrogenation reactor may be from 80 to 125 ° C, preferably from 90 to 120 ° C; and the working pressure is from 2 to 3 MPa, preferably from 2 to 2.3 MPa. Hydrogenation at low temperature and low pressure can significantly reduce energy consumption and cost.
  • the gas-liquid separator has a gas product outlet and a liquid product outlet.
  • the gas product outlet is connected to the inlet of the recycle gas treatment unit; the liquid product outlet is connected to the bio-oil catalytic cracking unit.
  • the hydrogen outlet of the recycle gas treatment unit is connected to the inlet of the recycle hydrogen compressor; the outlet of the recycle hydrogen compressor is catalyzed by a heat exchanger and a fixed bed of the biomass pyrolysis oil production unit.
  • the inlets of the hydrogenation reactor are connected.
  • the recycle gas treatment unit, the recycle hydrogen compressor compression may employ those known in the art.
  • the gas product is separated into circulating hydrogen and the remaining gas (exhaust gas) in the circulating gas treatment device, thereby realizing the recycling of the hydrogen, thereby achieving the purpose of reducing the cost.
  • the circulating hydrogen is mixed with fresh hydrogen to form a mixed hydrogen.
  • the bio-oil catalytic cracking unit of the present invention is for mixing a liquid product from a catalytic hydrogenation unit with a heavy oil from a bio-oil standing stratification unit to obtain a mixture, and heating the mixture, and then undergoing a cracking reaction to obtain a cracking reaction product; It is also used to regenerate the catalyst to be formed formed after the reaction to obtain a regenerated catalyst, and to re-engage the regenerated catalyst in the cracking reaction.
  • Bio-oil catalytic cracking unit includes heating furnace, catalytic cracking reactor and reminder Reagent regenerator.
  • the reaction raw material inlet of the catalytic cracking reactor is connected to the liquid product outlet of the gas-liquid separator of the catalytic hydrogenation unit through a heating furnace, and the reaction raw material inlet of the catalytic cracking reactor is separated from the static separation unit of the bio-oil by the heating furnace.
  • the lower end outlets of the unit are connected. This mixes the liquid product with the heavy oil and introduces it into the catalytic cracking reactor.
  • the catalyst inlet of the catalytic cracking reactor is connected to the outlet of the catalyst regenerator; the catalyst outlet of the catalytic cracking reactor is connected to the inlet of the catalyst regenerator. This facilitates regeneration and injection of the catalyst to ensure continuous catalytic cracking.
  • the separation and purification unit of the present invention is used for separating and purifying a cracking reaction product to obtain an aromatic hydrocarbon and an olefin.
  • the separation and purification unit comprises a rectification column.
  • the outlet of the catalytic cracking reactor is connected to the inlet of the rectification column.
  • the outlet of the rectification column is used to discharge aromatic hydrocarbons and olefins. Rectification processes known in the art can be used and will not be described again here.
  • the apparatus for the production of aromatic hydrocarbons and olefins using bio-oil catalytic hydro-coupled catalytic cracking of the present invention includes biomass pyrolysis oil production systems, bio-oil static stratification systems, catalytic hydrogenation systems, bio-oils Catalytic cracking system and separation and purification system.
  • the liquid product of the catalytic hydrogenation system is output to the catalytic cracking system for catalytic cracking together with the heavy oil, and the catalytically cracked product enters the separation and purification system.
  • the biomass pyrolysis oil production system includes a thermal cracking unit, a cyclone separator, a heat exchanger, and a rapid condenser; wherein the inlet end of the thermal cracking unit is a biomass feedstock, and the outlet of the thermal cracking unit is The inlet of the cyclone separator is connected, the pyrolysis residue at the outlet of the cyclone separator is discharged, and the pyrolysis gas at the outlet of the cyclone separator is connected to the inlet of the rapid condenser after passing through the heat exchanger, and the outlet of the rapid condenser is separated from the bio-oil.
  • the inlets of the stationary separators in the layer system are connected.
  • the bio-oil static stratification system comprises a stationary separator; wherein the inlet of the stationary separator is connected to the outlet of the rapid condenser, and the outlet of the upper end of the stationary separator is subjected to biomass pyrolysis to produce oil
  • the heat exchanger in the system is connected to the inlet of the fixed bed catalytic hydrogenation reactor in the catalytic hydrogenation system, and the lower end outlet of the stationary separator is biocatalyzed by catalytic cracking.
  • the furnace in the system is then connected to the reactant inlet end of the catalytic cracking reactor in the bio-oil catalytic cracking system.
  • the catalytic hydrogenation system comprises a fixed bed catalytic hydrogenation reactor, a gas liquid separator, a recycle gas treatment unit, and a recycle hydrogen compressor; wherein the inlet and the stationary separation of the fixed bed catalytic hydrogenation reactor
  • the upper end outlet of the unit is connected to the heat exchanger in the biomass pyrolysis oil production system, and the outlet of the fixed bed catalytic hydrogenation reactor is connected to the inlet of the gas-liquid separator, and the circulating gas outlet end of the gas-liquid separator and the circulating gas
  • the inlet of the treatment device is connected, and the liquid outlet end of the gas-liquid separator is connected to the inlet end of the reactant of the catalytic cracking reactor in the bio-oil catalytic cracking system through the heating furnace in the bio-oil catalytic cracking unit, and is processed by the circulating gas treatment device.
  • the hydrogen outlet end is connected to the inlet of the circulating hydrogen compressor, and the gaseous exhaust gas treated by the circulating gas treatment device is directly discharged, and the outlet end of the circulating hydrogen compressor is passed through the heat exchanger in the biomass pyrolysis oil production system and the fixed bed.
  • the raw material inlet ends of the catalytic hydrogenation reactor are connected.
  • the bio-oil catalytic cracking system comprises a heating furnace, a catalytic cracking reactor, and a catalyst regenerator; wherein the reaction feed inlet of the catalytic cracking reactor and the liquid product outlet of the gas-liquid separator in the catalytic hydrogenation system It is connected to the lower end outlet of the stationary separator in the bio-oil static stratification system, and the other inlet is connected to the regenerative catalyst outlet end from the catalyst regenerator, the product outlet of the catalytic cracking reactor and the rectification column of the separation and purification system.
  • the inlet is connected, the outlet end of the catalytic cracking reactor is connected to the inlet of the catalyst regenerator, and the flue gas of the catalyst regenerator is directly discharged;
  • the separation and purification system includes a rectification column; the inlet of the rectification column and the bio-oil catalytic cracking system
  • the product of the catalytic cracking reactor is connected at the outlet end, and the outlet of the distillation column is an aromatic hydrocarbon, an olefin and other chemical components.
  • Biomass raw material straw granules with a particle size of less than 2 mm.
  • the oxygen carrier iron-based oxygen carrier Fe 2 O 3 /Al 2 O 3 , with Al 2 O 3 as a carrier and Fe 2 O 3 as an active component.
  • Thermal cracking catalyst nickel-based molecular sieve catalyst 10 wt% Ni / HZSM-5, HZSM-5 silica-alumina ratio of 50.
  • Hydrogenation catalyst activated carbon supported ruthenium based catalyst. 1 wt% Rh/C, prepared by an equal volume impregnation method.
  • Cracking catalyst 2wt% Pt MCM-41/ZSM-5 composite micro-molecular molecular sieve.
  • Example 1 Apparatus for preparing aromatic hydrocarbons and olefins
  • FIG. 1 is a schematic view of a bio-oil catalytic hydrogenation coupled catalytic cracking process for the preparation of aromatic hydrocarbons and olefins.
  • the apparatus includes a biomass pyrolysis oil production unit 100, a bio-oil static stratification unit 200, a catalytic hydrogenation unit 300, a bio-oil catalytic cracking unit 400, and a separation and purification unit 500.
  • the biomass pyrolysis oil production unit 100 includes a thermal cracking unit 1, a cyclone separator 2, a heat exchanger 3, and a condenser 4, such as a rapid condenser.
  • the inlet of the thermal cracker 1 is for introducing biomass feedstock, the outlet of the thermal cracker 1 is connected to the inlet of the cyclone 2; the outlet of the cyclone 2 is connected to the inlet of the condenser 4 via a heat exchanger 3.
  • the bio-oil standing layering unit 200 includes a stationary separator 5.
  • the inlet of the stationary separator 5 is connected to the outlet of the condenser 4.
  • the upper end outlet of the stationary separator 5 is connected to the catalytic hydrogenation unit 300 through the heat exchanger 3.
  • the lower end outlet of the stationary separator 5 is connected to the bio-oil catalytic cracking unit 400.
  • the catalytic hydrogenation unit 300 includes a fixed bed catalytic hydrogenation reactor 6, a gas-liquid separator 7, a recycle gas treatment unit 8, and a recycle hydrogen compressor 9.
  • the inlet of the fixed bed catalytic hydrogenation reactor 6 is connected to the upper end outlet of the stationary separator 5 with a heat exchanger 3 interposed therebetween.
  • the outlet of the fixed bed catalytic hydrogenation reactor 6 is connected to the inlet of the gas-liquid separator 7.
  • the gas-liquid separator 7 has a gas product outlet and a liquid product outlet.
  • the gaseous product outlet is connected to the inlet of the recycle gas treatment unit 8, the liquid product outlet being associated with the bio-oil catalytic cracking unit 400 even.
  • the hydrogen outlet of the recycle gas treatment unit 8 is connected to the inlet of the recycle hydrogen compressor 9.
  • the outlet of the recycle hydrogen compressor 9 is connected to the inlet of the fixed bed catalytic hydrogenation reactor 6, with a heat exchanger 3 disposed therebetween.
  • the bio-oil catalytic cracking unit 400 includes a heating furnace 10, a catalytic cracking reactor 11, and a catalyst regenerator 12.
  • the separation and purification unit 500 includes a rectification column 13.
  • the liquid product outlet of the gas-liquid separator 7 is connected to the reaction raw material inlet of the catalytic cracking reactor 11, and a heating furnace 10 is disposed therebetween.
  • the lower end outlet of the stationary separator 5 is connected to the reaction raw material inlet of the catalytic cracking reactor 11; a heating furnace 10 is disposed therebetween.
  • the catalyst inlet of the catalytic cracking reactor 11 is connected to the outlet of the catalyst regenerator 12, and the catalyst outlet of the catalytic cracking reactor 11 is connected to the inlet of the catalyst regenerator 12.
  • the outlet of the catalytic cracking reactor 11 is connected to the inlet of the rectification column 13.
  • the outlet of the rectification column 13 is for discharging aromatic hydrocarbons and olefins.
  • the thermal cracking reaction of the biomass cracking unit 1 into the thermal cracking unit 100 of the biomass pyrolysis oil producing unit 100 generates a thermal cracking product, which is separated into solid particles and oil and gas by the cyclone separator 2.
  • the biomass feedstock is fed from the top of the thermal cracking unit 1, and in the downward process, the biomass feedstock is heated to a temperature of 200 ° C to 600 ° C at a heating rate of 200 ° C / s, for example, 550 ° C, and the temperature of the thermal cracking reaction is 500 to 600 ° C. For example, 550 ° C.
  • the thermal cracking reaction is carried out in the presence of an oxygen carrier and a thermal cracking catalyst.
  • the oil and gas are exchanged by the heat exchanger 3 and then cooled into the condenser 4 to obtain bio-oil.
  • the condenser 4 has a condensation rate of 40 to 70 ° C / s, for example, 50 ° C / s.
  • the bio-oil is layered in a stationary separator 5 and separated into a heavy oil and a light oil.
  • the activated carbon-supported rhodium-based catalyst had a reaction temperature of 120 ° C and a reaction pressure of 2 MPa.
  • the hydrogenation reaction product is passed to a gas-liquid separator 7 for gas-liquid separation to form a gas product and a liquid product.
  • the gaseous product is passed to a circulating gas treatment unit 8 for treatment to obtain circulating hydrogen and tail gas.
  • the exhaust gas is directly discharged.
  • the circulating hydrogen is compressed by the circulating hydrogen compressor 9 and mixed with fresh hydrogen to form the mixed hydrogen.
  • bio-oil standing layer unit 200 and the catalytic hydrogenation unit 300 are omitted, and the bio-oil is directly introduced into the bio-oil catalytic cracking unit 400 and the separation and purification unit 500.
  • Other units and operating conditions were the same as in Examples 1 and 2.
  • Example 2 Cracking catalyst is not coked Cracking catalyst a small amount of coking Comparative example 1 Pyrolysis catalyst partially coking Cracking catalyst is severely coked

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Abstract

一种利用生物油催化加氢耦合催化裂化制备芳香烃和烯烃的方法及装置，该装置包括生物质热裂解制油单元（100）、生物油静置分层单元（200）、催化加氢单元（300）、生物油催化裂化单元（400）和分离提纯单元（500）。生物油静置分层单元（200）形成轻质油和重质油；轻质油在催化加氢单元（300）进行加氢得到液体产物，并与生物油静置分层单元（200）的重质油混合，然后进行催化裂化，所得产物经分离提纯得到纯度较高的芳香烃和烯烃，可以实现生物油的全组分催化加氢与催化裂化，可以避免催化剂结焦而丧失催化性能。

Description

利用生物油催化加氢耦合催化裂化制备芳香烃和烯烃的方法及装置 技术领域
本发明涉及生物质资源利用和低温低压催化加氢的领域，具体涉及一种利用生物油催化加氢耦合催化裂化制备芳香烃和烯烃的方法及装置。
背景技术
化石能源(如石油、煤、天然气等)是当今社会主要的能源来源。随着工业化的发展，世界对能源的需求量与时俱增。在21世纪，面对化石燃料能源的短缺且不可再生问题和使用化石燃料过程中造成的环境污染和温室效应等严峻形势，开发可再生新能源以及环境友好型能源已经显示出其必要性和迫切性。与其他可再生能源(如风能、太阳能、潮汐能和水能等)相比，生物质能源是唯一一种可直接转化为液体燃料的可再生能源，因而备受关注。
热解技术是一种热化学方法，具有如下特点：减轻二次污染，生成可储存性能源，重金属等有害元素被固定在炭黑中，可以回收重金属。通过热解技术制备的生物油的能量密度得到大幅提升，所得生物油还具有高粘度、强酸性、高含氧量、含水分多、灰分低和热值低等特点。
生物油具有替代化石燃料油的潜质。然而，生物油的含水量高(15％～30％)、含氧量高(包含呋喃类、酚类、醛类、酮类等物质)、粘度高、热值低(发动机燃料一般为42MJ/kg，而粗生物油热值一般20MJ/kg)、酸性较强(pH为2.5左右)。这些因素导致生物油的化学稳定性差、燃烧值低、不互溶和具有腐蚀性。由此，生物油通常只能作为锅炉燃料，而不能作为车用燃料。由于生物油的高含氧量，当其 与空气接触时，很容易粘结变硬。因此，如果希望采用生物油替代化石燃料油，必须对生物油进行精制。
目前，生物油的精制方法包括乳化、催化加氢、催化裂化、催化酯化等，但均存在难以工业化的缺点。CN1916135A公开了一种由生物油脂生产燃料油的方法：在固体酸催化剂的催化作用下，直接将生物油脂、或与催化裂化原料的混合物、或与催化汽油的混合物，催化裂解生成液化气、汽油、柴油混合物。CN101720349A公开了一种制备生物汽油组分的方法：(I)获得至少一种生物油，将该生物油组分液化；(II)将液态的该生物油连同至少一种矿物油一起加入流化催化裂化装置；(III)将加入所述流化催化裂化装置的组分裂化，以至少形成生物液化石油气馏分和生物石脑油馏分；(IV)将该生物液化石油气馏分的至少一部分烷基化或者催化聚合；(V)将步骤(IV)的产物的至少一部分与所述生物石脑油馏分的至少一部分合并，以形成生物汽油组分。CN101463272A公开了一种生物油加氢处理生产柴油的方法：在氢气存在和加氢处理反应条件下，将含有生物油的原料油与催化剂接触，其中，所述催化剂含有效量的裂化活性组分、有效量的加氢活性金属组分和基质。上述工艺方法存在催化剂易结焦而丧失催化活性的问题，从而导致工艺稳定性和连续性差的问题。
CN103102907A公开了一种生物油脂生产低芳烃溶剂油的两段法加氢方法：以生物油脂为原料油，在加氢条件下，原料油与氢气混合通过第一段加氢反应区，加氢生成物流分离得到的富氢气体在第一段循环利用，分离得到的液体进入第二段加氢裂化反应区，第二段加氢生成油分离得到的副氢气体在第二段循环使用，分离得到的液体产品分馏得到各种低芳烃溶剂油，在反应状态下，第一段使用的加氢催化剂的加氢活性组分均为还原态的W、Mo、Ni和Co中一种或几种，第二段使用的加氢催化剂的加氢活性组分为硫化态的W、Mo、Ni和 Co中一种或几种。该方法可以部分保证催化剂的活性稳定性，但存在加氢操作能耗较高的问题。CN101885986A公开了一种生物油的精制方法：(1)将粗品生物油于140℃～300℃催化氢化10分钟至120分钟，得混合物，分离所得混合物得油相产物；(2)将由步骤(1)所得的油相产物与石蜡油混合，于200℃～550℃催化裂化后得精制生物油；其中：在催化氢化中所用催化剂Pd/γ-Al2O3或Pd/C。该方法可以部分解决催化裂解催化剂的结焦问题，但需要添加石蜡油，从而增加了制造成本。
发明内容
本发明旨在解决针对生物油全组分进行的热化学催化方法升级生物油品质过程中，催化剂易结焦而丧失催化性能，带来工艺的稳定性与连续性降低等问题。此外，本发明也旨在解决针对生物油中的重质油相和轻质油相组分单独进行热化学催化转化升级，没有实现生物油的全组分利用问题。为了解决这些问题，本申请的发明人进行了深入研究。
本发明的一个目的在于提供一种利用生物油催化加氢耦合催化裂化制备芳香烃和烯烃的方法。本发明的另一个目的在于提供一种利用生物油催化加氢耦合催化裂化制备芳香烃和烯烃的装置。本发明发现，将重质油组分生物油和经加氢提质后的轻质油组分生物油共同进行催化裂化可以制备芳香烃组分和烯烃组分，从而避免催化剂结焦导致催化性能降低，进而提高工艺的稳定性与连续性。本发明可以实现生物油的全组分利用。
根据本发明的一个方面，本发明提供一种利用生物油催化加氢耦合催化裂化制备芳香烃和烯烃的方法，包括如下步骤：
1)将生物质原料加入热裂解装置发生热裂解反应，从而形成热裂解产物，将该热裂解产物通过旋风分离器分离为固体颗粒和油气；
2)将所述油气通过换热器换热后进入冷凝器急冷，从而获得生物油，将该生物油在静置分离器分为重质油和轻质油；
3)将所述轻质油与混合氢气混合，再与换热器换热升温，然后通入固定床催化加氢反应器进行催化加氢反应得到加氢反应产物，将所述加氢反应产物通入气液分离器进行气液分离，从而形成气体产物和液体产物；
4)将所述气体产物通入循环气处理装置进行处理，得到循环氢气，该循环气处理装置内的其余气体则直接排放；将所述循环氢气经过循环氢气压缩机压缩后与新鲜氢气混合，从而形成所述混合氢气；
5)将所述液体产物与来自所述静置分离器的重质油混合得到混合物；将所述混合物经过加热炉加热，然后进入催化裂化反应器，所述混合物在裂解催化剂的作用下发生裂化反应得到裂化反应产物；反应后形成的待生催化剂进入催化剂再生器进行再生得到再生催化剂，催化剂再生器形成的烟气直接排放；所述再生催化剂重新进入所述催化裂化反应器参与裂化反应；
6)将所述裂化反应产物通过精馏塔进行分离提纯，得到芳香烃和烯烃。
根据本发明的方法，优选地，在步骤1)中，所述热裂解反应的温度为500～600℃，且将生物质原料以105～500℃/s的升温速率加热至500～600℃。
根据本发明的方法，优选地，在步骤2)中，所述冷凝器的冷凝速度为40～70℃/s。
根据本发明的方法，优选地，在步骤3)中，加氢反应的工艺条件为：采用活性炭负载的钌基催化剂或活性炭负载的铑基催化剂，反应温度为80～125℃，反应压力为2～3MPa。
根据本发明的方法，优选地，在步骤5)中，裂化反应的工艺条 件为：催化裂化反应器的工作温度为400～700℃；裂化催化剂以MCM-41/ZSM-5复合微介孔分子筛或SBA-15/ZSM-5复合微介孔分子筛作为载体、且以金属Pt或Al作活性金属。
根据本发明的另一个方面，本发明提供一种利用生物油催化加氢耦合催化裂化制备芳香烃和烯烃的装置，包括：
生物质热裂解制油单元(100)，其用于使生物质原料发生热裂解反应，从而形成热裂解产物；其还用于将所述热裂解产物分离为固体颗粒和油气，将所述油气换热后进行急冷，从而获得生物油；
生物油静置分层单元(200)，其用于将所述生物油分为重质油和轻质油；
催化加氢单元(300)，其用于将所述轻质油与混合氢气混合，经过换热升温后进行催化加氢反应得到加氢反应产物，将所述加氢反应产物进行气液分离，从而形成气体产物和液体产物；其还用于将所述气体产物进行处理得到循环氢气，并将所述循环氢气经过压缩后与新鲜氢气混合，从而形成所述混合氢气；
生物油催化裂化单元(400)，其用于将来自所述催化加氢单元(300)的所述液体产物与来自生物油静置分层单元(200)的所述重质油混合得到混合物，并将所述混合物加热，然后发生裂化反应得到裂化反应产物；其还用于将反应后形成的待生催化剂进行再生得到再生催化剂，并使所述再生催化剂重新参与裂化反应；
分离提纯单元(500)，其用于将所述裂化反应产物进行分离提纯，得到芳香烃和烯烃。
根据本发明的利用生物油催化加氢耦合催化裂化制备芳香烃和烯烃的装置，优选地，所述生物质热裂解制油单元(100)包括热裂解装置(1)、旋风分离器(2)、换热器(3)和冷凝器(4)；其中，所述热裂解装置(1)的入口用于引入生物质原料，所述热裂解装置(1)的出口与所述旋 风分离器(2)的入口相连；所述旋风分离器(2)的出口通过所述换热器(3)与所述冷凝器(4)的入口相连；所述冷凝器(4)的出口与所述生物油静置分层单元(200)相连。
根据本发明的利用生物油催化加氢耦合催化裂化制备芳香烃和烯烃的装置，优选地，所述生物油静置分层单元(200)包括静置分离器(5)；其中，所述静置分离器(5)的入口与所述冷凝器(4)的出口相连；所述静置分离器(5)的上端出口通过生物质热裂解制油单元(100)中的所述换热器(3)与所述催化加氢单元(300)相连；所述静置分离器(5)的下端出口与所述生物油催化裂化单元(400)相连。
根据本发明的利用生物油催化加氢耦合催化裂化制备芳香烃和烯烃的装置，优选地，所述催化加氢单元(300)包括固定床催化加氢反应器(6)、气液分离器(7)、循环气处理装置(8)和循环氢气压缩机(9)；其中，所述固定床催化加氢反应器(6)的入口通过所述生物质热裂解制油单元(100)中的所述换热器(3)与所述静置分离器(5)的上端出口相连，所述固定床催化加氢反应器(6)的出口与所述气液分离器(7)的入口相连；所述气液分离器(7)的气体产物出口与所述循环气处理装置(8)的入口相连，所述气液分离器(7)的液体产物出口与所述生物油催化裂化单元(400)相连；所述循环气处理装置(8)的氢气出口与所述循环氢气压缩机(9)的入口相连；所述循环氢气压缩机(9)的出口通过所述生物质热裂解制油单元(100)的所述换热器(3)与所述固定床催化加氢反应器(6)的入口相连。
根据本发明的利用生物油催化加氢耦合催化裂化制备芳香烃和烯烃的装置，优选地，所述生物油催化裂化单元(400)包括加热炉(10)、催化裂化反应器(11)和催化剂再生器(12)；所述分离提纯单元(500)包括精馏塔(13)；
其中，所述催化裂化反应器(11)的反应原料入口通过加热炉(10) 分别与所述催化加氢单元(300)的所述气液分离器(7)的液体产物出口和所述生物油静置分层单元(200)的所述静置分离器(5)的下端出口相连；所述催化裂化反应器(11)的催化剂入口与所述催化剂再生器(12)的出口相连；所述催化裂化反应器(11)的出口与所述分离提纯单元(500)的所述精馏塔(13)的入口相连；所述催化裂化反应器(11)的催化剂出口与所述催化剂再生器(12)的入口相连；
其中，精馏塔(13)的出口用于排放芳香烃和烯烃。
本发明从生物油不同组分(重质油和轻质油)的理化特性出发，轻质油低温低压催化加氢后所得液体产物与重质油混合，然后进行催化裂化，从而实现生物油的全组分催化加氢与催化裂化提质的“耦合转化”。本发明对生物油进行分步处理，并对不同理化特性的组分采取不同的处理操作，从而可以避免催化剂结焦而丧失催化性能，进而使得工艺稳定性与连续性得到提高。此外，本发明的轻质油催化加氢采取低温低压条件，并采用活性炭负载的钌基催化剂或活性炭负载的铑基催化剂，因而反应条件比传统催化加氢条件温和。这样可以节约氢耗能耗，进而降低成本。根据本发明优选的技术方案，与主流的生物质(循环)流化床快速热裂解制备生物油技术不同，本发明的热裂解装置采用下行式循环流化床快速热裂解技术，由于热解过程没有使用流化气，因而成本低，且热解气与半焦分离后易于冷凝，液体产率高。根据本发明进一步优选的技术方案，本发明设置催化剂再生器，可以提高催化剂的利用率，并且可以进一步解决催化剂易结焦而丧失催化性能的问题，进而进一步解决由此带来工艺的稳定性与连续性降低的问题。
附图说明
图1是本发明的一种生物油催化加氢耦合催化裂化制备芳香烃和烯烃的装置示意图。
附图标记说明如下：
100-生物质热裂解制油单元、200-生物油静置分层单元、300-催化加氢单元、400-生物油催化裂化单元、500-分离提纯单元；
1-热裂解装置、2-旋风分离器、3-换热器、4-冷凝器、5-静置分离器、6-固定床催化加氢反应器、7-气液分离器、8-循环气处理装置、9-循环氢气压缩机、10-加热炉、11-催化裂化反应器、12-催化剂再生器、13-精馏塔。
具体实施方式
下面对本发明进行更加详细的说明，但本发明并不限于此。
在本发明中，生物油采用生物质原料获得。本发明的生物质原料包括生物油脂或生物废料等。生物油脂选自植物油脂和/或动物油脂，也可以选自植物油脂和/或动物油脂精炼后的下脚料。植物油脂选自草本植物油和木本植物油中的一种或多种。草本植物油选自大豆油、花生油、油菜籽油、葵花籽油、棉籽油中的一种或多种。木本植物油选自橄榄油、棕桐油、椰子油、核桃油、油茶籽油中的一种或多种。动物油脂选自猪油、牛油、羊油、鸡油、鸭油、鲸油、深海鱼油中的一种或多种。上述生物质原料经过热裂解得到生物油。该生物油在常温下是液态的。生物废料选自秸杆(例如玉米秆、棉花秆)、木屑、谷壳、稻壳、森林废弃物等。本发明的生物质原料优选为秸秆。
在本发明中，耦合表示两个或两个以上的操作过程或操作单元的输入与输出之间存在紧密配合与相互影响。例如，催化加氢操作和催化裂化操作紧密配合。
在本发明中，芳香烃表示分子中含有芳香环(例如苯环)结构的碳氢化合物。芳香环拥有共轭的平面环体系，原子间成键并不是不连续的单双键交替，而是被离域π电子云覆盖。烯烃表示含有碳-碳双键的碳氢化合物。
在本发明中，重质油与重质油相具有相同的含义，轻质油与轻质油相具有相同的含义，可以相互替换使用。混合氢与混合氢气具有相同的含义，循环氢与循环氢气具有相同的含义，新鲜氢气和新氢具有相同含义，可以相互替换使用。
在本发明中，制备芳香烃和烯烃的装置是多个设备和/或单元的集合体。单元与系统具有相同的含义，可以替换使用。
<利用生物油催化加氢耦合催化裂化制备芳香烃和烯烃的方法>
在本发明中，根据生物油的性质将生物油的重质油相和轻质油相分开，然后将轻质油相在低温低压下进行催化加氢，将轻质油相中的醛类、酮类、酸类等转化为稳定的醇类和饱和呋喃类化合物等，其中的液体产物与重质油相混合在一起，进行加氢裂化和分离提纯，从而获得芳香烃组分和烯烃组分。由于选择低温低压催化加氢轻质生物油和催化加氢耦合催化裂化技术，这对于节能减排具有重要意义。
根据本发明的一个方面，本发明的制备方法包括如下步骤：1)热裂解步骤；2)静置分离步骤；3)催化加氢步骤；4)混合氢气步骤；5)催化裂化步骤：6)分离提纯步骤。
本发明的热裂解步骤为将生物质原料加入热裂解装置发生热裂解反应，从而形成热裂解产物，将该热裂解产物通过旋风分离器分离为固体颗粒和油气。热裂解装置、旋风分离器并没有特别限定，可以采用本领域已知的那些。只要能够将热裂解产物分离为固体颗粒和油气的分离设备均可使用。与旋风分离器类似或等同的分离设备均属于 本发明的保护范围。在热裂解步骤中，所述热裂解反应的温度为500～600℃，优选为530～580℃。将生物质原料以105～500℃/s、优选为150～300℃/s的升温速率加热至500～600℃，优选为530～580℃。根据本发明的一个实施方式，将生物质原料从热裂解装置的顶部加入，在生物质原料的下行过程中，以105～500℃/s的升温速率加热至500～600℃，生物质原料发生快速热裂解反应，从而形成热裂解产物。根据本发明的一个具体实施方式，生物质原料可以为粒径小于2mm的秸秆颗粒，载氧体可以采用铁基载氧体Fe2O3/Al2O3(以Al2O3为载体，Fe2O3为活性成分)，催化剂可以采用镍基分子筛催化剂Ni/HZSM-5。热裂解装置的出口与旋风分离器相连，热裂解产物经旋风分离器将固体颗粒和油气分离。
本发明的静置分离步骤为将所述油气通过换热器换热后进入冷凝器急冷，从而获得生物油，将该生物油在静置分离器分为重质油和轻质油。纯净的油气通过换热器换热后进入冷凝器急冷以获得液体燃料生物油。在本发明中，所述冷凝器的冷凝速度为40～70℃/s，优选为50～60℃/s。在静置分离器中，生物油中的重组分下沉、轻组分上升，从而实现分层，然后将二者分离为重质油和轻质油。
本发明的催化加氢步骤为将所述轻质油与混合氢气混合，再与换热器换热升温，然后通入固定床催化加氢反应器进行催化加氢反应得到加氢反应产物，将所述加氢反应产物通入气液分离器进行气液分离，从而形成气体产物和液体产物。本发明的混合氢气如下所述。将所述轻质油与混合氢气混合以形成混合物料，将该混合物料与换热器换热升温，从而节约能耗。本发明的催化加氢反应在固定床催化加氢反应器中进行。由于采用轻质油进行催化加氢，不容易产生催化剂结焦的问题。在加氢催化剂的作用下，所述轻质油与混合氢气反应，从而将轻质油中的不饱和组分(例如醛类、酮类、酸类等)转化为加氢 反应产物中的饱和组分(例如醇类和饱和呋喃类化合物等)。
在本发明的催化加氢步骤中，加氢催化剂的实例包括但不限于采用活性炭负载的钌基催化剂或活性炭负载的铑基催化剂。催化加氢的反应温度为80～125℃，优选为90～120℃；反应压力为2～3MPa，优选为2～2.3MPa。根据本发明的一个实施方式，加氢反应的工艺条件为：采用活性炭负载的钌基催化剂或活性炭负载的铑基催化剂为加氢催化剂，反应温度为80～125℃，反应压力为2～3MPa。在低温低压条件下进行加氢反应，可以显著降低能耗和成本。
在本发明的催化加氢步骤中，将所述加氢反应产物通入气液分离器进行气液分离，从而形成气体产物和液体产物。可以采用本领域已知的那些气液分离器，这里不再赘述。
本发明的混合氢气步骤为将所述气体产物通入循环气处理装置进行处理，得到循环氢气，该循环气处理装置内的其余气体则直接排放；将所述循环氢气经过循环氢气压缩机压缩后与新鲜氢气混合，从而形成所述混合氢气。循环气处理装置、循环氢气压缩机可以采用本领域已知的那些。将气体产物在循环气处理装置分离为循环氢气和其余气体(尾气)，从而实现氢气的循环使用，达到降低成本的目的。为了保证混合氢气中的氢气浓度，将循环氢气与新鲜氢气混合，从而形成混合氢气。
本发明的催化裂化步骤为将来自所述气液分离器的所述液体产物与来自所述静置分离器的重质油混合得到混合物；将所述混合物经过加热炉加热，然后进入催化裂化反应器，所述混合物在裂解催化剂的作用下发生裂化反应得到裂化反应产物；反应后形成的待生催化剂进入催化剂再生器进行再生得到再生催化剂，催化剂再生器形成的烟气直接排放；所述再生催化剂重新进入所述催化裂化反应器参与裂化反应。液体产物与重质油的混合比例并没有特别限制。液体产物中的 不饱和组分较少，这样可以防止催化剂的结焦现象。
在本发明的催化裂化步骤中，加热炉和催化裂化反应器可以使用本领域已知的那些。催化裂化反应器的工作温度为400～700℃，例如500～600℃。裂化反应可以在400～700℃，例如500～600℃下进行。裂化催化剂的载体可以为MCM-41/ZSM-5复合微介孔分子筛或SBA-15/ZSM-5复合微介孔分子筛作为载体，活性金属可以为Pt或Al。根据本发明的一个实施方式，该催化剂为负载Pt的MCM-41/ZSM-5复合微介孔分子筛。在上述条件下，催化剂更加不容易发生结焦现象。
在本发明的催化裂化步骤中，反应后形成的待生催化剂进入催化剂再生器进行再生得到再生催化剂，再生催化剂重新进入所述催化裂化反应器参与裂化反应。这样可以节约催化剂用量，并且可以使得催化裂化反应持续进行。催化剂再生器形成的烟气直接排放或者回收利用。
本发明的分离提纯步骤为将所述裂化反应产物通过精馏塔进行分离提纯，得到芳香烃和烯烃。只要能够实现分离提纯目的的任何设备均可以用于本发明，例如精馏塔。与精馏塔类似或等同的分离设备均属于本发明的保护范围。可以采用本领域已知的分离提纯工艺参数，这里不再赘述。
在某些实施方案中，本发明的利用生物油催化加氢耦合催化裂化制备芳香烃和烯烃的方法包括如下步骤：
1)将生物质原料加入热裂解装置发生热裂解反应；热裂解产物经旋风分离器分离为固体颗粒和油气；
2)油气通过换热器换热后进入冷凝器急冷获得生物油，然后通入静置分离器，待生物油分层，分为重质油和轻质油；
3)轻质油与混合氢气混合后与换热器换热升温，然后通入固定 床催化加氢反应器进行加氢提质反应，反应产物进入气液分离器进行气液分离；
4)气液分离器分离的气体产物通入循环气处理装置处理后，得到的循环氢气进入循环氢气压缩机压缩后与新氢混合形成混氢，循环气处理装置内其余气体直接排放；气液分离器分离的液体产物与来自静置分离器的重质油混合，经加热炉加热后进入催化裂化反应器；
5)液体产物与重质油形成的混合物在催化裂化反应器反应后，产生的待生催化剂进入催化剂再生器进行再生，经催化剂再生器再生后的再生催化剂重新进入催化裂化反应器反应，催化剂再生器的烟气排放，催化裂化反应器的反应产物进入精馏塔进行分离提纯，精馏塔产品即为芳香烃和烯烃组分。
在某些实施方案中，步骤1)的热裂解反应温度为500～600℃，裂解过程采用105～500℃/s的升温速率加热至所述热裂解反应温度。
在某些实施方案中，步骤2)的冷凝器的冷凝速度为40～70℃/s。
在某些实施方案中，步骤3)的催化加氢反应器工艺为：使用活性炭负载的钌基催化剂和铑基催化剂，在反应温度为80～125℃和反应压力为2～3MPa的条件下进行加氢提质反应。
在某些实施方案中，步骤5)的催化裂化反应器工艺为：催化裂化反应器的工作温度为400～700℃，使用MCM-41/ZSM-5或SBA-15/ZSM-5微介孔分子筛作载体、金属Pt或Al作活性金属的催化剂，反应后待生催化剂进入催化剂再生器进行再生。
<利用生物油催化加氢耦合催化裂化制备芳香烃和烯烃的装置>
根据本发明的另一个方面，本发明的利用生物油催化加氢耦合催化裂化制备芳香烃和烯烃的装置包括生物质热裂解制油单元、生物油静置分层单元、催化加氢单元、生物油催化裂化单元和分离提纯单元。 催化加氢单元的液体产物输出至生物油催化裂化单元，并与来自生物油静置分层单元的重质油一同进行催化裂化，裂化反应产物进入分离提纯单元。本发明的装置的操作方法如前所述，这里不再赘述。
本发明的生物质热裂解制油单元用于使生物质原料发生热裂解反应，从而形成热裂解产物；还用于将所述热裂解产物分离为固体颗粒和油气，将所述油气换热后进行急冷，从而获得生物油。生物质热裂解制油单元可以包括热裂解装置、旋风分离器、换热器和冷凝器。这些设备可以采用本领域已知的那些。冷凝器的实例包括但不限于急速冷凝器。热裂解装置的入口用于引入生物质原料，热裂解装置的出口与旋风分离器的入口相连。在热裂解装置中，生物质原料发生热裂解反应，从而形成热裂解产物。热裂解装置的工作温度可以为500～600℃，优选为530～580℃。热裂解装置具有105～500℃/s、优选为150～300℃/s的升温速率。热裂解装置存在催化剂，优选地催化剂和载氧体，具体物质如前所述，这里不再赘述。旋风分离器的出口通过换热器与冷凝器的入口相连。冷凝器的出口与生物油静置分层单元相连。在本发明中，所述冷凝器具有40～70℃/s，优选为50～60℃/s的冷凝速度。
本发明的生物油静置分层单元用于将所述生物油分为重质油和轻质油。生物油静置分层单元包括静置分离器，其具有入口、上端出口和下端出口。静置分离器的入口与冷凝器的出口相连；静置分离器的上端出口通过生物质热裂解制油单元中的换热器与催化加氢单元相连；静置分离器的下端出口与生物油催化裂化单元相连。在静置分离器中，生物油中的重组分下沉、轻组分上升，从而实现分层，然后将二者分离为重质油和轻质油。
本发明的催化加氢单元用于将所述轻质油与混合氢气混合，经过换热升温后进行催化加氢反应得到加氢反应产物，将所述加氢反应产 物进行气液分离，从而形成气体产物和液体产物；其还用于将所述气体产物进行处理得到循环氢气，并将所述循环氢气经过压缩后与新鲜氢气混合，从而形成所述混合氢气。催化加氢单元包括固定床催化加氢反应器、气液分离器、循环气处理装置和循环氢气压缩机。固定床催化加氢反应器的入口通过生物质热裂解制油单元中的换热器与静置分离器的上端出口相连，固定床催化加氢反应器的出口与气液分离器的入口相连。固定床催化加氢反应器存在加氢催化剂。该催化剂包括但不限于采用活性炭负载的钌基催化剂或活性炭负载的铑基催化剂。固定床催化加氢反应器的工作温度可以为80～125℃，优选为90～120℃；工作压力为2～3MPa，优选为2～2.3MPa。在低温低压条件下进行加氢反应，可以显著降低能耗和成本。
在本发明的催化加氢单元中，气液分离器具有气体产物出口和液体产物出口。气体产物出口与循环气处理装置的入口相连；液体产物出口与生物油催化裂化单元相连。
在本发明的催化加氢单元中，循环气处理装置的氢气出口与循环氢气压缩机的入口相连；所述循环氢气压缩机的出口通过生物质热裂解制油单元的换热器与固定床催化加氢反应器的入口相连。循环气处理装置、循环氢气压缩机压缩可以采用本领域已知的那些。将气体产物在循环气处理装置分离为循环氢气和其余气体(尾气)，从而实现氢气的循环使用，达到降低成本的目的。为了保证混合氢气中的氢气浓度，将循环氢气与新鲜氢气混合，从而形成混合氢气。
本发明的生物油催化裂化单元用于将来自催化加氢单元的液体产物与来自生物油静置分层单元的重质油混合得到混合物，并将混合物加热，然后发生裂化反应得到裂化反应产物；还用于将反应后形成的待生催化剂进行再生得到再生催化剂，并使所述再生催化剂重新参与裂化反应。生物油催化裂化单元包括加热炉、催化裂化反应器和催 化剂再生器。催化裂化反应器的反应原料入口通过加热炉与催化加氢单元的气液分离器的液体产物出口相连，催化裂化反应器的反应原料入口通过加热炉与生物油静置分层单元的静置分离器的下端出口相连。这样将液体产物和重质油混合，并引入催化裂化反应器。催化裂化反应器的催化剂入口与催化剂再生器的出口相连；催化裂化反应器的催化剂出口与催化剂再生器的入口相连。这样便于催化剂的再生和注入，从而保证催化裂化连续进行。
本发明的分离提纯单元用于将裂化反应产物进行分离提纯，得到芳香烃和烯烃。分离提纯单元包括精馏塔。催化裂化反应器的出口与精馏塔的入口相连。精馏塔的出口用于排放芳香烃和烯烃。可以使用本领域已知的那些精馏工艺，这里不再赘述。
在某些实施方案中，本发明的利用生物油催化加氢耦合催化裂化制备芳香烃和烯烃的装置包括生物质热裂解制油系统、生物油静置分层系统、催化加氢系统、生物油催化裂化系统和分离提纯系统。催化加氢系统的液体产物输出至催化裂化系统与重质油一同进行催化裂化，催化裂化后的产品进入分离提纯系统。
在某些实施方案中，生物质热裂解制油系统包括热裂解装置、旋风分离器、换热器和急速冷凝器；其中，热裂解装置的入口端为生物质原料，热裂解装置的出口与旋风分离器的入口相连，旋风分离器出口的热解残渣被排放，旋风分离器出口的热解气经过换热器后与急速冷凝器的入口相连，急速冷凝器的出口与生物油静置分层系统中的静置分离器的入口相连。
在某些实施方案中，生物油静置分层系统包括静置分离器；其中，静置分离器的入口与急速冷凝器的出口相连，静置分离器的上端出口经生物质热裂解制油系统中的换热器后与催化加氢系统中的固定床催化加氢反应器的入口相连，静置分离器的下端出口经生物油催化裂 化系统中的加热炉后与生物油催化裂化系统内的催化裂化反应器的反应物入口端相连。
在某些实施方案中，催化加氢系统包括固定床催化加氢反应器、气液分离器、循环气处理装置和循环氢压缩机；其中，固定床催化加氢反应器的入口与静置分离器的上端出口经生物质热裂解制油系统中的换热器后相连，固定床催化加氢反应器的出口与气液分离器的入口相连，气液分离器的循环气体出口端与循环气处理装置的入口相连，气液分离器的液体出口端经生物油催化裂化单内的加热炉后与生物油催化裂化系统内的催化裂化反应器的反应物入口端相连，经循环气处理装置处理后的氢气出口端与循环氢压缩机的入口相连，循环气处理装置处理后的气体尾气直接排放，循环氢压缩机的出口端经生物质热裂解制油系统中的换热器后与固定床催化加氢反应器的原料入口端相连。
在某些实施方案中，生物油催化裂化系统包括加热炉、催化裂化反应器和催化剂再生器；其中，催化裂化反应器的反应原料入口与催化加氢系统中的气液分离器的液体产物出口和生物油静置分层系统中的静置分离器下端出口相连，另外一个入口是与来自催化剂再生器的再生催化剂出口端相连，催化裂化反应器的产品出口与分离提纯系统的精馏塔的入口相连，催化裂化反应器的待生催化剂出口端与催化剂再生器的入口相连，催化剂再生器的烟气直接排放；分离提纯系统包括精馏塔；精馏塔的入口与生物油催化裂化系统中的催化裂化反应器的产品出口端相连，精馏塔出口即为芳烃、烯烃和其他化学品组分。
下面对实施例和对比例中使用的原料进行说明：
生物质原料：粒径小于2mm的秸秆颗粒。
载氧体：铁基载氧体Fe2O3/Al2O3，以Al2O3为载体，Fe2O3为活 性成分。
热裂解催化剂：镍基分子筛催化剂10wt％Ni/HZSM-5，HZSM-5硅铝比为50。
加氢催化剂：活性炭负载的铑基催化剂。1wt％Rh/C，采用等体积浸渍法制备。
裂化催化剂：2wt％Pt MCM-41/ZSM-5复合微介孔分子筛。
实施例1-制备芳香烃和烯烃的装置
图1是本发明的一种生物油催化加氢耦合催化裂化制备芳香烃和烯烃的装置示意图。该装置包括生物质热裂解制油单元100、生物油静置分层单元200、催化加氢单元300、生物油催化裂化单元400和分离提纯单元500。
生物质热裂解制油单元100包括热裂解装置1、旋风分离器2、换热器3和冷凝器4，例如急速冷凝器。热裂解装置1的入口用于引入生物质原料，热裂解装置1的出口与旋风分离器2的入口相连；旋风分离器2的出口通过换热器3与冷凝器4的入口相连。
生物油静置分层单元200包括静置分离器5。静置分离器5的入口与冷凝器4的出口相连。静置分离器5的上端出口通过换热器3与催化加氢单元300相连。静置分离器5的下端出口与生物油催化裂化单元400相连。
催化加氢单元300包括固定床催化加氢反应器6、气液分离器7、循环气处理装置8和循环氢气压缩机9。固定床催化加氢反应器6的入口与静置分离器5的上端出口相连，二者之间设置有换热器3。固定床催化加氢反应器6的出口与气液分离器7的入口相连。气液分离器7具有气体产物出口和液体产物出口。该气体产物出口与循环气处理装置8的入口相连，该液体产物出口与生物油催化裂化单元400相 连。循环气处理装置8的氢气出口与循环氢气压缩机9的入口相连。循环氢气压缩机9的出口与固定床催化加氢反应器6的入口相连，二者之间设置有换热器3。
生物油催化裂化单元400包括加热炉10、催化裂化反应器11和催化剂再生器12。分离提纯单元500包括精馏塔13。气液分离器7的液体产物出口与催化裂化反应器11的反应原料入口相连，二者之间设置有加热炉10。静置分离器5的下端出口与催化裂化反应器11的反应原料入口相连；二者之间设置有加热炉10。催化裂化反应器11的催化剂入口与催化剂再生器12的出口相连，催化裂化反应器11的催化剂出口与催化剂再生器12的入口相连。催化裂化反应器11的出口与精馏塔13的入口相连。精馏塔13的出口用于排放芳香烃和烯烃。
实施例2-制备芳香烃和烯烃的方法
下面介绍采用实施例1的装置制备芳香烃和烯烃的过程。
1)将生物质原料加入生物质热裂解制油单元100的热裂解装置1发生热裂解反应，从而形成热裂解产物，将该热裂解产物通过旋风分离器2分离为固体颗粒和油气。生物质原料从热裂解装置1的顶部加入，在下行过程中，将生物质原料以200℃/s的升温速率加热至500～600℃，例如550℃，热裂解反应的温度为500～600℃，例如550℃。热裂解反应在载氧体和热裂解催化剂的存在下进行。
2)将油气通过换热器3换热后进入冷凝器4急冷，从而获得生物油。冷凝器4的冷凝速度为40～70℃/s，例如50℃/s。该生物油在静置分离器5进行分层，并分离为重质油和轻质油。
3)将轻质油与混合氢气混合，再与换热器3换热升温，然后通入固定床催化加氢反应器6进行催化加氢反应得到加氢反应产物。采 用活性炭负载的铑基催化剂，反应温度为120℃，反应压力为2MPa。将加氢反应产物通入气液分离器7进行气液分离，从而形成气体产物和液体产物。
4)将气体产物通入循环气处理装置8进行处理，得到循环氢气和尾气。尾气直接排放。将循环氢气经过循环氢气压缩机9压缩后与新鲜氢气混合，从而形成所述混合氢气。
5)将液体产物与重质油混合得到混合物。将该混合物经过加热炉10加热，然后进入催化裂化反应器11。该混合物在裂解催化剂的作用下发生裂化反应得到裂化反应产物。裂化反应的温度为600℃。反应后形成的待生催化剂进入催化剂再生器12进行再生得到再生催化剂，催化剂再生器12形成的烟气直接排放；再生催化剂重新进入催化裂化反应器11参与裂化反应。
6)将裂化反应产物通过精馏塔13进行分离提纯，得到芳香烃和烯烃。
对比例1-制备芳香烃和烯烃的装置和方法
省略生物油静置分层单元200和催化加氢单元300，将生物油直接进入生物油催化裂化单元400和分离提纯单元500。其他单元和操作条件与实施例1和2相同。
表1
编号 运行8小时 运行50小时
实施例2 裂解催化剂未结焦 裂解催化剂少量结焦
对比例1 裂解催化剂部分结焦 裂解催化剂结焦严重
本发明并不限于上述实施方式，在不背离本发明的实质内容的情 况下，本领域技术人员可以想到的任何变形、改进、替换均落入本发明的范围。

Claims (10)

  1. 一种利用生物油催化加氢耦合催化裂化制备芳香烃和烯烃的方法，其特征在于，包括如下步骤：
    1)将生物质原料加入热裂解装置发生热裂解反应，从而形成热裂解产物，将该热裂解产物通过旋风分离器分离为固体颗粒和油气；
    2)将所述油气通过换热器换热后进入冷凝器急冷，从而获得生物油，该生物油在静置分离器分为重质油和轻质油；
    3)将所述轻质油与混合氢气混合，再与换热器换热升温，然后通入固定床催化加氢反应器进行催化加氢反应得到加氢反应产物，将所述加氢反应产物通入气液分离器进行气液分离，从而形成气体产物和液体产物；
    4)将所述气体产物通入循环气处理装置进行处理，得到循环氢气，该循环气处理装置内的其余气体则直接排放；将所述循环氢气经过循环氢气压缩机压缩后与新鲜氢气混合，从而形成所述混合氢气；
    5)将所述液体产物与来自所述静置分离器的重质油混合得到混合物；将所述混合物经过加热炉加热，然后进入催化裂化反应器，所述混合物在裂解催化剂的作用下发生裂化反应得到裂化反应产物；反应后形成的待生催化剂进入催化剂再生器进行再生得到再生催化剂，催化剂再生器形成的烟气直接排放；所述再生催化剂重新进入所述催化裂化反应器参与裂化反应；
    6)将所述裂化反应产物通过精馏塔进行分离提纯，得到芳香烃和烯烃。
  2. 根据权利要求1所述的方法，其特征在于，在步骤1)中，所述热裂解反应的温度为500～600℃，且将生物质原料以105～500℃/s的升温速率加热至所述热裂解反应的温度。
  3. 根据权利要求1所述的方法，其特征在于，在步骤2)中，所 述冷凝器的冷凝速度为40～70℃/s。
  4. 根据权利要求1所述的方法，其特征在于，在步骤3)中，加氢反应的工艺条件为：采用活性炭负载的钌基催化剂或活性炭负载的铑基催化剂，反应温度为80～125℃，且反应压力为2～3MPa。
  5. 根据权利要求1～4任一项所述的方法，其特征在于，在步骤5)中，裂化反应的工艺条件为：催化裂化反应器的工作温度为400～700℃；裂化催化剂以MCM-41/ZSM-5复合微介孔分子筛或SBA-15/ZSM-5复合微介孔分子筛作为载体、且以金属Pt或Al作活性金属。
  6. 一种利用生物油催化加氢耦合催化裂化制备芳香烃和烯烃的装置，其特征在于，包括：
    生物质热裂解制油单元(100)，其用于使生物质原料发生热裂解反应，从而形成热裂解产物；其还用于将所述热裂解产物分离为固体颗粒和油气，将所述油气换热后进行急冷，从而获得生物油；
    生物油静置分层单元(200)，其用于将所述生物油分为重质油和轻质油；
    催化加氢单元(300)，其用于将所述轻质油与混合氢气混合，经过换热升温后进行催化加氢反应得到加氢反应产物，将所述加氢反应产物进行气液分离，从而形成气体产物和液体产物；其还用于将所述气体产物进行处理得到循环氢气，并将所述循环氢气经过压缩后与新鲜氢气混合，从而形成所述混合氢气；
    生物油催化裂化单元(400)，其用于将来自所述催化加氢单元(300)的所述液体产物与来自生物油静置分层单元(200)的所述重质油混合得到混合物，并将所述混合物加热，然后发生裂化反应得到裂化反应产物；其还用于将反应后形成的待生催化剂进行再生得到再生催化剂，并使所述再生催化剂重新参与裂化反应；
    分离提纯单元(500)，其用于将所述裂化反应产物进行分离提纯，得到芳香烃和烯烃。
  7. 根据权利要求6所述的利用生物油催化加氢耦合催化裂化制备芳香烃和烯烃的装置，其特征在于，所述生物质热裂解制油单元(100)包括热裂解装置(1)、旋风分离器(2)、换热器(3)和冷凝器(4)；其中，所述热裂解装置(1)的入口用于引入生物质原料，所述热裂解装置(1)的出口与所述旋风分离器(2)的入口相连；所述旋风分离器(2)的出口通过所述换热器(3)与所述冷凝器(4)的入口相连；所述冷凝器(4)的出口与所述生物油静置分层单元(200)相连。
  8. 根据权利要求7所述的装置，其特征在于，所述生物油静置分层单元(200)包括静置分离器(5)；其中，所述静置分离器(5)的入口与所述冷凝器(4)的出口相连；所述静置分离器(5)的上端出口通过生物质热裂解制油单元(100)中的所述换热器(3)与所述催化加氢单元(300)相连；所述静置分离器(5)的下端出口与所述生物油催化裂化单元(400)相连。
  9. 根据权利要求8所述的利用生物油催化加氢耦合催化裂化制备芳香烃和烯烃的装置，其特征在于，所述催化加氢单元(300)包括固定床催化加氢反应器(6)、气液分离器(7)、循环气处理装置(8)和循环氢气压缩机(9)；其中，所述固定床催化加氢反应器(6)的入口通过所述生物质热裂解制油单元(100)中的所述换热器(3)与所述静置分离器(5)的上端出口相连，所述固定床催化加氢反应器(6)的出口与所述气液分离器(7)的入口相连；所述气液分离器(7)的气体产物出口与所述循环气处理装置(8)的入口相连，所述气液分离器(7)的液体产物出口与所述生物油催化裂化单元(400)相连；所述循环气处理装置(8)的氢气出口与所述循环氢气压缩机(9)的入口相连；所述循环氢气压缩机(9)的出口通过所述生物质热裂解制油单元(100)的所述换热器(3)与所述固定床催化 加氢反应器(6)的入口相连。
  10. 根据权利要求9所述的利用生物油催化加氢耦合催化裂化制备芳香烃和烯烃的装置，其特征在于，所述生物油催化裂化单元(400)包括加热炉(10)、催化裂化反应器(11)和催化剂再生器(12)；所述分离提纯单元(500)包括精馏塔(13)；
    其中，所述催化裂化反应器(11)的反应原料入口通过加热炉(10)分别与所述催化加氢单元(300)的所述气液分离器(7)的液体产物出口和所述生物油静置分层单元(200)的所述静置分离器(5)的下端出口相连；所述催化裂化反应器(11)的催化剂入口与所述催化剂再生器(12)的出口相连；所述催化裂化反应器(11)的出口与所述分离提纯单元(500)的所述精馏塔(13)的入口相连；所述催化裂化反应器(11)的催化剂出口与所述催化剂再生器(12)的入口相连；
    其中，精馏塔(13)的出口用于排放芳香烃和烯烃。
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