CN112048327A - Method for preparing low-carbon olefin by using biomass as raw material - Google Patents

Method for preparing low-carbon olefin by using biomass as raw material Download PDF

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CN112048327A
CN112048327A CN202010799302.5A CN202010799302A CN112048327A CN 112048327 A CN112048327 A CN 112048327A CN 202010799302 A CN202010799302 A CN 202010799302A CN 112048327 A CN112048327 A CN 112048327A
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biomass
pyrolysis
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carbon olefin
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CN112048327B (en
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肖睿
胡昌淞
刘超
张会岩
吴石亮
雷鸣
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Southeast University
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    • 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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/334—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing molecular sieve catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/02—Dust removal
    • 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
    • C10G2300/1088—Olefins
    • C10G2300/1092—C2-C4 olefins
    • 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
    • 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
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a method for preparing low-carbon olefin by using biomass as a raw material, which belongs to the field of biomass resource conversion and utilization and comprises the following steps: continuously adding a biomass raw material into a pyrolysis reactor which is kept at a pyrolysis temperature and is continuously filled with carrier gas containing a certain amount of water vapor, and enabling the biomass to generate a fast pyrolysis reaction to generate gaseous pyrolysis vapor; step two, keeping mixed steam consisting of pyrolysis steam and carrier gas at the pyrolysis temperature for a period of time, and performing high-temperature dust removal; and step three, introducing the mixed vapor after dust removal into a catalytic reactor kept at the catalytic temperature, carrying out catalytic reaction under the action of a ZSM-5 catalyst, and condensing the product to obtain a gaseous product rich in low-carbon olefin. By adopting the technical scheme provided by the invention, the problem of low yield of low-carbon olefin in the existing biomass catalytic pyrolysis technology is solved, the low-carbon olefin is prepared by high-selectivity conversion of biomass, and a new way is provided for high-value utilization of biomass resources.

Description

Method for preparing low-carbon olefin by using biomass as raw material
Technical Field
The invention belongs to the field of biomass resource conversion and utilization, and particularly relates to a method for preparing low-carbon olefin by using biomass as a raw material.
Background
The low-carbon olefin refers to olefin with 2 to 4 carbon atoms, such as ethylene, propylene, butylene and the like, is widely used for producing plastics, fibers and the like, and is the most basic raw material for petrochemical production. At present, the preparation of low-carbon olefins highly depends on fossil energy such as petroleum and natural gas, the non-renewable property of the fossil energy and the problem of greenhouse gas emission caused by the consumption of the fossil energy bring great challenges to the sustainable development of the low-carbon olefins industry, and the development of clean and sustainable low-carbon olefins preparation methods becomes a necessary trend.
Biomass refers to various organisms formed through photosynthesis, and typical biomass resources mainly include agricultural and forestry wastes, including straws, rice hulls, wood chips and the like. The biomass is the only renewable organic carbon source in the nature, and the growth of the biomass comes from the absorption of carbon dioxide in the air by photosynthesis, so that the near zero emission of the carbon dioxide can be realized in the whole life cycle. The method for preparing the low-carbon olefin by using the biomass as the raw material can effectively get rid of the influence of the fossil energy shortage and the greenhouse gas emission problem on the low-carbon olefin industry, has important significance on the sustainable development of the low-carbon olefin industry, and can realize the high-value utilization of agricultural and forestry wastes.
Biomass can be converted into aromatic hydrocarbon and low-carbon olefin by a biomass catalytic pyrolysis technology, a catalyst is generally arranged in a pyrolysis reactor in the conventional catalytic pyrolysis technology and is mostly used as a bed material of a fluidized bed pyrolysis reactor, and on the other hand, carrier gas generally adopts inert gas which is mainly one or more of carbon monoxide, carbon dioxide, hydrogen, nitrogen, helium and argon, and water vapor is not additionally introduced. The products of the existing biomass catalytic pyrolysis process mainly comprise aromatic hydrocarbons, and the yield of low-carbon olefin products is low and is usually used as a byproduct for preparing the aromatic hydrocarbons. Therefore, the existing biomass catalytic pyrolysis process is improved, the yield of the low-carbon olefin is greatly improved, and the problem that the high-efficiency preparation of the low-carbon olefin by biomass catalytic pyrolysis needs to be solved urgently is solved.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects in the prior art, the invention provides a method for preparing low-carbon olefin by using biomass as a raw material based on a catalytic pyrolysis process, which effectively improves the yield of the low-carbon olefin in the biomass catalytic pyrolysis process.
The technical scheme is as follows: the invention relates to a method for preparing low-carbon olefin by using biomass as a raw material, which comprises the following steps:
continuously adding a biomass raw material into a pyrolysis reactor which is kept at a pyrolysis temperature and is continuously filled with carrier gas containing a certain amount of water vapor, and enabling the biomass to generate a fast pyrolysis reaction to generate gaseous pyrolysis vapor;
step two, keeping mixed steam consisting of pyrolysis steam and carrier gas at the pyrolysis temperature for a period of time, and performing high-temperature dust removal;
and step three, introducing the mixed vapor after dust removal into a catalytic reactor kept at the catalytic temperature, carrying out catalytic reaction under the action of a ZSM-5 catalyst, and condensing the product to obtain a gaseous product rich in low-carbon olefin.
Further, the particle size of the biomass raw material in the first step is not more than 5.0 mm.
Further, the mass space velocity of the biomass raw material relative to the catalyst in the first step is in the range of 1-2h-1。
Further, the carrier gas in the first step is a mixture of water vapor and an inert gas, the inert gas is one or more of carbon monoxide, carbon dioxide, hydrogen, nitrogen, helium and argon, and the volume content of the water vapor in the carrier gas is not less than 20 vol%.
Further, the pyrolysis temperature range in the first step is 500-.
Further, the retention time of the mixed steam at the pyrolysis temperature in the second step is 1-5 s.
Further, the temperature of the catalytic reaction in the third step is 500-.
Further, the ZSM-5 catalyst in the third step is a hydrogen type ZSM-5 zeolite molecular sieve.
Further, the condensation temperature of the catalytic reaction product in the third step is in the range of 0-40 ℃.
Effective gain: the pyrolysis reaction and the catalytic reaction are respectively arranged in two different stages of reactors, and sufficient retention time is provided for steam products generated by the biomass pyrolysis reaction at the pyrolysis temperature before the catalytic reaction. In addition, the operation parameters of the two-stage reactor can be respectively adjusted and controlled, the two-stage reactor is beneficial to independent optimization of two-stage reaction, the catalyst is arranged in the catalytic reactor in a fixed bed mode, the problems of abrasion and pulverization caused by the fact that the catalyst is used as fluidized bed materials in the traditional catalytic pyrolysis process can be effectively avoided, meanwhile, the mixing of biomass pyrolytic carbon products and the catalyst is avoided, and the step of separating the pyrolytic carbon from the catalyst is omitted. On the other hand, the addition of the water vapor in the carrier gas can effectively promote the thermal cracking degree of the biomass raw material in the pyrolysis reaction, reduce the generation of pyrolytic carbon and generate more pyrolytic vapor which can be used for catalytic reaction, and meanwhile, the water vapor and the pyrolytic vapor have competitive adsorption on the active sites of the catalyst in the catalytic reaction, so that the aromatization capacity of the catalyst can be effectively inhibited, and the generation of low-carbon olefin products is facilitated. By adopting the technical scheme provided by the invention, the problem of low yield of low-carbon olefin in the existing biomass catalytic pyrolysis technology is solved, the low-carbon olefin is prepared by high-selectivity conversion of biomass, and a new way is provided for high-value utilization of biomass resources.
Detailed Description
The invention provides a method for preparing low-carbon olefin by using biomass as a raw material, and in order to make the purpose, technical scheme and effect of the invention more clear, the scheme is further explained by the following examples. The specific examples described herein are intended to be illustrative only and are not intended to be limiting.
Example 1:
step one, continuously adding pine wood chip raw material with the particle range of 0.4-1.4mm into a fluidized bed pyrolysis reactor maintained at the pyrolysis temperature of 550 ℃, and maintaining the mass space velocity of the biomass raw material relative to the catalyst at 1.33h-1The carrier gas in the pyrolysis reactor consists of 60vol% of water vapor and 40vol% of nitrogen, and the biomass is subjected to a fast pyrolysis reaction in the pyrolysis reactor to generate gaseous pyrolysis vapor;
step two, keeping mixed steam consisting of pyrolysis steam and carrier gas for 5s at the pyrolysis temperature, and performing high-temperature dust removal;
and step three, introducing the mixed steam after dust removal into a fixed bed catalytic reactor kept at the catalytic temperature of 550 ℃, performing catalytic reaction under the action of a hydrogen type ZSM-5 catalyst activated by water vapor, and condensing the product at 0 ℃ to obtain a gaseous product rich in low-carbon olefin.
After the reaction is finished, the gas product is quantitatively analyzed by a gas chromatographic analyzer, and the result shows that the carbon yield of the low-carbon olefin product relative to the biomass raw material is 16.8%. Wherein, the carbon selectivity of ethylene, propylene and butylene is respectively 40.7 percent, 53.5 percent and 5.8 percent.
Example 2:
step one, continuously adding pine wood chip raw material with the particle range of 0.4-1.4mm into a fluidized bed pyrolysis reactor maintained at the pyrolysis temperature of 550 ℃, and maintaining the mass space velocity of the biomass raw material relative to the catalyst at 1.33h-1The carrier gas in the pyrolysis reactor consists of 60vol% of water vapor and 40vol% of nitrogen, and the biomass is subjected to a fast pyrolysis reaction in the pyrolysis reactor to generate gaseous pyrolysis vapor;
step two, keeping mixed steam consisting of pyrolysis steam and carrier gas for 5s at the pyrolysis temperature, and performing high-temperature dust removal;
and step three, introducing the mixed steam after dust removal into a fixed bed catalytic reactor kept at the catalytic temperature of 550 ℃, carrying out catalytic reaction under the action of a hydrogen type ZSM-5 catalyst, and condensing the product at the temperature of 0 ℃ to obtain a gaseous product rich in low-carbon olefin.
After the reaction is finished, the gas product is quantitatively analyzed by a gas chromatographic analyzer, and the result shows that the carbon yield of the low-carbon olefin product relative to the biomass raw material is 14.8%. Wherein, the carbon selectivity of ethylene, propylene and butylene is 59.9 percent, 36.7 percent and 3.4 percent respectively.
Example 3:
step one, continuously adding pine wood chip raw material with the particle range of 0.4-1.4mm into a fluidized bed pyrolysis reactor maintained at the pyrolysis temperature of 550 ℃, and maintaining the mass space velocity of the biomass raw material relative to the catalyst at 1.33h-1The carrier gas in the pyrolysis reactor consists of 40vol% of water vapor and 60vol% of nitrogen, and the biomass is subjected to a fast pyrolysis reaction in the pyrolysis reactor to generate gaseous pyrolysis vapor;
step two, keeping mixed steam consisting of pyrolysis steam and carrier gas for 5s at the pyrolysis temperature, and performing high-temperature dust removal;
and step three, introducing the mixed steam after dust removal into a fixed bed catalytic reactor kept at the catalytic temperature of 550 ℃, carrying out catalytic reaction under the action of a hydrogen type ZSM-5 catalyst, and condensing the product at the temperature of 0 ℃ to obtain a gaseous product rich in low-carbon olefin.
After the reaction is finished, the gas product is quantitatively analyzed by a gas chromatographic analyzer, and the result shows that the carbon yield of the low-carbon olefin product relative to the biomass raw material is 12.8%. Wherein, the carbon selectivity of ethylene, propylene and butylene is 69.2 percent, 28.0 percent and 2.8 percent respectively.
Example 4:
step one, continuously adding pine wood chip raw material with the particle range of 0.4-1.4mm into a fluidized bed pyrolysis reactor maintained at the pyrolysis temperature of 550 ℃, and maintaining the mass space velocity of the biomass raw material relative to the catalyst at 1.33h-1The carrier gas in the pyrolysis reactor consists of 20vol% of water vapor and 80vol% of nitrogen, and the biomass is subjected to a fast pyrolysis reaction in the pyrolysis reactor to generate gaseous pyrolysis vapor;
step two, keeping mixed steam consisting of pyrolysis steam and carrier gas for 5s at the pyrolysis temperature, and performing high-temperature dust removal;
and step three, introducing the mixed steam after dust removal into a fixed bed catalytic reactor kept at the catalytic temperature of 550 ℃, carrying out catalytic reaction under the action of a hydrogen type ZSM-5 catalyst, and condensing the product at the temperature of 0 ℃ to obtain a gaseous product rich in low-carbon olefin.
After the reaction is finished, the gas product is quantitatively analyzed by a gas chromatographic analyzer, and the result shows that the carbon yield of the low-carbon olefin product relative to the biomass raw material is 11.9%. Wherein, the carbon selectivity of ethylene, propylene and butylene is 71.5 percent, 25.9 percent and 2.6 percent respectively.
Example 5:
step one, continuously adding straw raw materials with the particle range of 1.0-5.0mm into a fluidized bed pyrolysis reactor kept at the pyrolysis temperature of 500 ℃, and keeping the mass space velocity of the biomass raw materials relative to a catalyst at 2h-1The gas-carrying component in the pyrolysis reactor is 80vol% of water vapor and 20vol% of argon, and the biomass is subjected to a fast pyrolysis reaction in the pyrolysis reactor to generate gaseous pyrolysis vapor;
step two, keeping the mixed steam composed of pyrolysis steam and carrier gas for 1s at the pyrolysis temperature, and performing high-temperature dust removal;
and step three, introducing the mixed steam after dust removal into a fixed bed catalytic reactor kept at the catalytic temperature of 700 ℃, carrying out catalytic reaction under the action of a hydrogen type ZSM-5 catalyst, and condensing the product at 40 ℃ to obtain a gaseous product rich in low-carbon olefin.
After the reaction is finished, the gas product is quantitatively analyzed by a gas chromatography analyzer, and the result shows that the carbon yield of the low-carbon olefin product relative to the biomass raw material is 13.9%.
Example 6:
step one, continuously adding straw raw materials with the particle range of 1.0-5.0mm into a fluidized bed pyrolysis reactor kept at the pyrolysis temperature of 500 ℃, and keeping the mass space velocity of the biomass raw materials relative to a catalyst at 2h-1The gas-carrying component in the pyrolysis reactor is 80vol% of water vapor and 20vol% of argon, and the biomass is subjected to a fast pyrolysis reaction in the pyrolysis reactor to generate gaseous pyrolysis vapor;
step two, keeping the mixed steam composed of pyrolysis steam and carrier gas for 1s at the pyrolysis temperature, and performing high-temperature dust removal;
and step three, introducing the mixed steam after dust removal into a fixed bed catalytic reactor kept at the catalytic temperature of 500 ℃, carrying out catalytic reaction under the action of a hydrogen type ZSM-5 catalyst, and condensing the product at 40 ℃ to obtain a gaseous product rich in low-carbon olefin.
After the reaction is finished, the gas product is quantitatively analyzed by a gas chromatographic analyzer, and the result shows that the carbon yield of the low-carbon olefin product relative to the biomass raw material is 12.4%.
Example 7:
step one, continuously adding straw raw materials with the particle range of 1.0-5.0mm into a fluidized bed pyrolysis reactor kept at the pyrolysis temperature of 500 ℃, and keeping the mass space velocity of the biomass raw materials relative to a catalyst at 1h-1The gas-carrying component in the pyrolysis reactor is 80vol% of water vapor and 20vol% of argon, and the biomass is subjected to a fast pyrolysis reaction in the pyrolysis reactor to generate gaseous pyrolysis vapor;
step two, keeping the mixed steam composed of pyrolysis steam and carrier gas for 1s at the pyrolysis temperature, and performing high-temperature dust removal;
and step three, introducing the mixed steam after dust removal into a fixed bed catalytic reactor kept at the catalytic temperature of 500 ℃, carrying out catalytic reaction under the action of a hydrogen type ZSM-5 catalyst, and condensing the product at 40 ℃ to obtain a gaseous product rich in low-carbon olefin.
After the reaction is finished, the gas product is quantitatively analyzed by a gas chromatographic analyzer, and the result shows that the carbon yield of the low-carbon olefin product relative to the biomass raw material is 11.2%.
Example 8:
step one, continuously adding straw raw materials with the particle range of 1.0-5.0mm into a fluidized bed pyrolysis reactor kept at the pyrolysis temperature of 700 ℃, and keeping the mass airspeed of the biomass raw materials relative to a catalyst at 2h-1The gas-carrying component in the pyrolysis reactor is 80vol% of water vapor and 20vol% of argon, and the biomass is subjected to a fast pyrolysis reaction in the pyrolysis reactor to generate gaseous pyrolysis vapor;
step two, keeping the mixed steam composed of pyrolysis steam and carrier gas for 1s at the pyrolysis temperature, and performing high-temperature dust removal;
and step three, introducing the mixed steam after dust removal into a fixed bed catalytic reactor kept at the catalytic temperature of 500 ℃, carrying out catalytic reaction under the action of a hydrogen type ZSM-5 catalyst, and condensing the product at 40 ℃ to obtain a gaseous product rich in low-carbon olefin.
After the reaction is finished, the gas product is quantitatively analyzed by a gas chromatographic analyzer, and the result shows that the carbon yield of the low-carbon olefin product relative to the biomass raw material is 12.8%.
Comparative example 1:
continuously adding pine wood chip raw material with particle range of 0.4-1.4mm into a fluidized bed pyrolysis reactor maintained at a pyrolysis temperature of 550 ℃, wherein a hydrogen type ZSM-5 catalyst is adopted as a bed material in the reactor, and the mass space velocity of the biomass raw material relative to the catalyst is maintained at 1h-1The carrier gas in the pyrolysis reactor consists of 100vol% nitrogen. The biomass is subjected to fast pyrolysis reaction in the pyrolysis reactor to generate gaseous pyrolysis steam, and the pyrolysis steam escaping from the biomass raw material particles is rapidly contacted with the catalyst to perform catalytic reaction. And (3) performing high-temperature dust removal and condensation at 0 ℃ on the product to obtain a gaseous product containing the low-carbon olefin.
After the reaction is finished, the gas product is quantitatively analyzed by a gas chromatographic analyzer, and the result shows that the carbon yield of the low-carbon olefin product relative to the biomass raw material is 4.6%. Wherein, the carbon selectivity of ethylene, propylene and butylene is 73.3 percent, 24.2 percent and 2.5 percent respectively.
Comparative example 2:
continuously adding straw raw materials with the particle range of 1.0-5.0mm into a fluidized bed pyrolysis reactor kept at the pyrolysis temperature of 500 ℃, wherein a hydrogen type ZSM-5 catalyst is adopted as a bed material in the reactor, and the mass airspeed of the biomass raw materials relative to the catalyst is kept at 1h-1The carrier gas in the pyrolysis reactor consists of 100vol% argon. The biomass is subjected to fast pyrolysis reaction in the pyrolysis reactor to generate gaseous pyrolysis steam, and the pyrolysis steam escaping from the biomass raw material particles is rapidly contacted with the catalyst to perform catalytic reaction. And dedusting the product at high temperature and condensing the product at 40 ℃ to obtain a gaseous product containing the low-carbon olefin.
After the reaction is finished, the gas product is quantitatively analyzed by a gas chromatographic analyzer, and the result shows that the carbon yield of the low-carbon olefin product relative to the biomass raw material is 3.9%.
It should be noted that the above embodiments are only preferred embodiments of the present invention, and not intended to limit the technical scope of the present invention, so that any minor modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention are within the technical scope of the present invention.

Claims (9)

1. A method for preparing low-carbon olefin by using biomass as a raw material is characterized by comprising the following steps:
continuously adding a biomass raw material into a pyrolysis reactor which is kept at a pyrolysis temperature and is continuously filled with carrier gas containing water vapor, and enabling the biomass to generate a fast pyrolysis reaction to generate gaseous pyrolysis vapor;
step two, keeping the mixed steam composed of pyrolysis steam and carrier gas for 1-5s at the pyrolysis temperature, and removing dust;
and step three, introducing the mixed vapor after dust removal into a catalytic reactor kept at the catalytic temperature, carrying out catalytic reaction under the action of a ZSM-5 catalyst, and condensing the product to obtain a gaseous product rich in low-carbon olefin.
2. The method for preparing the low-carbon olefin by using the biomass as the raw material according to claim 1, wherein the method comprises the following steps: in the first step, the particle size of the biomass raw material is not more than 5.0 mm.
3. The method for preparing the low-carbon olefin by using the biomass as the raw material according to claim 1, wherein the method comprises the following steps: in the first step, the carrier gas is a mixture of water vapor and inert gas, the inert gas is one or more of carbon dioxide, nitrogen, helium and argon, and the volume content of the water vapor in the carrier gas is not less than 20 vol%.
4. The method for preparing the low-carbon olefin by using the biomass as the raw material according to claim 1, wherein the method comprises the following steps: in the first step, the pyrolysis temperature range is 500-.
5. The method for preparing the low-carbon olefin by using the biomass as the raw material according to claim 1, wherein the method comprises the following steps: in the second step, the temperature of the dust removing equipment is kept consistent with the pyrolysis temperature.
6. The method for preparing the low-carbon olefin by using the biomass as the raw material according to claim 1, wherein the method comprises the following steps: in the third step, the catalytic reaction temperature is 500-700 ℃, and the type of the catalytic reactor is a fixed bed.
7. The method for preparing the low-carbon olefin by using the biomass as the raw material according to claim 1, wherein the method comprises the following steps: in the third step, the ZSM-5 catalyst is a hydrogen type ZSM-5 zeolite molecular sieve.
8. The method for preparing the low-carbon olefin by using the biomass as the raw material according to claim 1, wherein the method comprises the following steps: in the third step, the dosage of the catalyst is required to ensure that the mass airspeed range of the biomass raw material relative to the catalyst is 1-2h-1。
9. The method for preparing the low-carbon olefin by using the biomass as the raw material according to claim 1, wherein the method comprises the following steps: in the third step, the condensation temperature range of the catalytic reaction product is 0-40 ℃.
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CN110002934A (en) * 2019-04-15 2019-07-12 广西大学 A method of low-carbon alkene is prepared by oleic acid

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