CN110358568A - A kind of method and its catalyst of biomass preparation bio oil - Google Patents

A kind of method and its catalyst of biomass preparation bio oil Download PDF

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Publication number
CN110358568A
CN110358568A CN201910807167.1A CN201910807167A CN110358568A CN 110358568 A CN110358568 A CN 110358568A CN 201910807167 A CN201910807167 A CN 201910807167A CN 110358568 A CN110358568 A CN 110358568A
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China
Prior art keywords
bio oil
biomass
catalyst
pickling
zsm
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CN201910807167.1A
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Inventor
李攀
蒋璐瑶
方书起
常春
白净
陈俊英
韩秀丽
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Zhengzhou University
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Zhengzhou University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Abstract

The invention belongs to Biomass Energy Utilization technical fields, more particularly to the method and its catalyst of a kind of biomass preparation bio oil, the following steps are included: (1) pickling-baking pretreatment: by biomass pickling processes, after washing, filtering, drying, 20-30min is baked at inert atmosphere, 200-300 DEG C；(2) be pyrolyzed: in 450-600 DEG C, ZSM-5 molecular sieve catalyst is pyrolyzed 20-30min, obtains bio oil, bio oil rate of oxygen of the present invention is low, quality is high.

Description

A kind of method and its catalyst of biomass preparation bio oil
Technical field
The invention belongs to Biomass Energy Utilization technical fields, and in particular to a kind of method of biomass preparation bio oil and Its catalyst.
Background technique
With scientific and technological progress and economic development, demand of the people to the energy increasingly increases, the use pair of traditional fossil energy Environment causes negative effect, while large-scale exploitation is so that fossil energy is increasingly depleted, to renewable money in world wide The demand in source is continuously increased.Biomass has very big prospect as a kind of resourceful and reproducible cleaning resource.
Biomass pyrolytic is a kind of effective ways of biomass recycling use, can get three kinds of shapes of solid, liquid, gas after pyrolysis The product of state, wherein the yield of product liquid can be improved in fast pyrogenation.Bio oil is the product liquid after biomass fast pyrogenation, The complex mixture that it is made of a variety of oxygenatedchemicals, but complicated component, high oxygen content, acidity height, stability difference etc. lack Point limits it and is widely applied.The shortcomings that bio oil and Biomass Characteristics have inseparable relationship, and biomass itself first contains There are a large amount of alkali and alkaline earth metal ions, these substances have larger impact to bio oil.Alkali and alkaline earth metal ions in biomass There is catalytic action to pyrolytic reaction, can promote the second pyrolysis of bio oil that biological oil yield is caused to reduce and generate acid, aldehyde, ketone etc. Small-molecule substance；And alkali and alkaline earth metal ions condense into big solid under high temperature action, so that containing glue in bio oil The problems such as charcoal particle causes its poor quality, and big solid also will cause equipment slagging, abrasion.Its secondary substance is mainly by fiber Element, hemicellulose and three big groups of lignin are grouped as, and the product after each component pyrolysis is different, wherein the thermal cracking of hemicellulose Large quantity of moisture and acid compounds can be generated, the generation of unstable component will affect quality of bio-oil.
A kind of method of existing biomass production bio oil, as " high level based on comprehensive pyrolysis is raw for Chinese invention patent Object oil preparation method ", Publication No. CN103265968A, the preparation method carry out particulate biomass to bake pre- place first Reason, is crushed and is sieved to biomass after baking, bio oil moisture content, oxygen content and the acidity drop obtained after fast pyrogenation Low, calorific value and energy density improve, but baking processing can not eliminate the alkali and alkaline earth metal ions in biomass, therefore, single Preprocess method possibly can not comprehensively improve the characteristic of biomass material.For another Chinese invention patent: " catalytic pyrolysis purification The method of bio oil " Publication No. CN1432626A, this method are to be catalyzed by adding catalyst HZSM-5 to bio oil Cracking, so that bio oil oxygen content is reduced to promote quality, but catalysis upgrading process needs to condense the certain temperature of bio oil heating Degree is refined again, and process is complicated and increases cost；And the easy coking deactivation of catalyst, reduce its catalytic efficiency.Therefore, existing There is technology to need further improve.
Summary of the invention
The purpose of the present invention is to provide the methods and its catalyst of a kind of biomass preparation bio oil, utilize party's legal system Standby bio oil rate of oxygen is low, quality is high.
Based on above-mentioned purpose, the present invention is adopted the following technical scheme that:
A kind of method of biomass preparation bio oil, comprising the following steps:
(1) pickling-baking pretreatment: by biomass pickling processes, after washing, filtering, drying, in inert atmosphere, 200-300 DEG C Lower baking 20-30min；
(2) be pyrolyzed: in 450-600 DEG C, ZSM-5 molecular sieve catalyst is pyrolyzed 20-30min, obtains bio oil.
Further, pickling solution used in pickling processes is acetic acid aqueous solution, acetic acid aqueous solution in the step (1) Mass concentration be 2%-5%.
Further, the mass volume ratio of biomass and pickling solution is 0.5-2g in pickling processes in the step (1): 15-25ml。
Further, the inert atmosphere is N2。
Further, the mass ratio of biomass and catalyst is 0.5-2g: 0.5-1.5g in the step (1).
The method of biomass preparation bio oil, catalyst is ZSM-5 Type Zeolites in the step (2) Agent, method of modifying are as follows: by Fe (NO3)3· 9H2O is dissolved in water, adds ZSM-5 molecular sieve catalyst, stirs evenly, then It is dried into powder at 100-110 DEG C, calcines to obtain Fe through 600-700 DEG C3+Mass content is the modified ZSM-5 catalyst of 2%-6%.
It this invention takes pickling and bakes two kinds of pretreatment modes and uses modified molecular sieve catalyst, overcome life The low disadvantage of raw material of substance energy density reduces its influence to quality of bio-oil, promotes calorific value and stability of bio oil etc. Quality.Low using bio oil oxygen content prepared by the present invention compared with being directly pyrolyzed obtained bio oil, stability is high.
Specific embodiment
Embodiment 1:
A kind of method of biomass preparation bio oil, comprising the following steps:
(1) pickling-baking pretreatment: by biomass pickling processes, after washing, filtering, drying, in inert atmosphere N2, at 200 DEG C Bake 20min；Pickling solution used in pickling processes is acetic acid aqueous solution, and the mass concentration of acetic acid aqueous solution is 2%, biology The mass volume ratio of matter and pickling solution is 0.5g: 15ml；The mass ratio of biomass and catalyst is 0.5g: 0.5g；
(2) be pyrolyzed: in 450 DEG C, ZSM-5 molecular sieve catalyst is pyrolyzed 20min, obtains bio oil；The catalyst is to be modified ZSM-5 molecular sieve catalyst, method of modifying are as follows: by Fe (NO3)3· 9H2O is dissolved in water, adds ZSM-5 molecular sieve catalysis Agent stirs evenly, and is then dried into powder at 100 DEG C, calcines to obtain Fe through 600 DEG C3+The modified ZSM-5 that mass content is 2% is urged Agent.
Embodiment 2:
A kind of method of biomass preparation bio oil, comprising the following steps:
(1) pickling-baking pretreatment: by biomass pickling processes, after washing, filtering, drying, in inert atmosphere N2, at 250 DEG C Bake 25min；Pickling solution used in pickling processes is acetic acid aqueous solution, and the mass concentration of acetic acid aqueous solution is 3%, biology The mass volume ratio of matter and pickling solution is 1g: 20ml；The mass ratio of biomass and catalyst is 1g: 1g；
(2) be pyrolyzed: in 500 DEG C, ZSM-5 molecular sieve catalyst is pyrolyzed 25min, obtains bio oil；The catalyst is to be modified ZSM-5 molecular sieve catalyst, method of modifying are as follows: by Fe (NO3)3· 9H2O is dissolved in water, adds ZSM-5 molecular sieve catalysis Agent stirs evenly, and is then dried into powder at 105 DEG C, calcines to obtain Fe through 650 DEG C3+The modified ZSM-5 that mass content is 4% is urged Agent.
Embodiment 3:
A kind of method of biomass preparation bio oil, comprising the following steps:
(1) pickling-baking pretreatment: by biomass pickling processes, after washing, filtering, drying, in inert atmosphere N2, at 300 DEG C Bake 30min；Pickling solution used in pickling processes is acetic acid aqueous solution, and the mass concentration of acetic acid aqueous solution is 5%, biology The mass volume ratio of matter and pickling solution is 2g: 25ml；The mass ratio of biomass and catalyst is 2g: 1.5g；
(2) be pyrolyzed: in 600 DEG C, ZSM-5 molecular sieve catalyst is pyrolyzed 30min, obtains bio oil；The catalyst is to be modified ZSM-5 molecular sieve catalyst, method of modifying are as follows: by Fe (NO3)3· 9H2O is dissolved in water, adds ZSM-5 molecular sieve catalysis Agent stirs evenly, and is then dried into powder at 110 DEG C, calcines to obtain Fe through 700 DEG C3+The modified ZSM-5 that mass content is 6% is urged Agent.
Test example 1:
Take three groups of equivalent weights for the biomass of 6g, first group: being made using the method in embodiment 3, and without using catalyst Bio oil, second group: bio oil, third is made using the method in embodiment 3 and using traditional ZSM-5 molecular sieve catalyst Bio oil is made using the method in embodiment 3 and using modified ZSM-5 molecular sieve catalyst in group, by above three groups of bio oils Following characteristic is detected using PH meter, elemental analyser, gas chromatography-mass spectrometry detector is respectively adopted, testing result is such as Under:
Table 1:
By upper table 1 it is found that bio oil is made relative to ZSM-5 molecular sieve after non-property using modified ZSM-5 molecular sieve catalyst Bio oil is made in catalyst, and rate of oxygen is low, stay in grade, obtained bio oil its rate of oxygen height when not using catalyst, Quality is unstable.

Claims (6)

1. a kind of method of biomass preparation bio oil, which comprises the following steps:
(1) pickling-baking pretreatment: by biomass pickling processes, after washing, filtering, drying, in inert atmosphere, 200-300 DEG C Lower baking 20-30min；
(2) be pyrolyzed: in 450-600 DEG C, ZSM-5 molecular sieve catalyst is pyrolyzed 20-30min, obtains bio oil.
2. the method for biomass preparation bio oil according to claim 1, which is characterized in that in the step (1) at pickling Pickling solution used in reason is acetic acid aqueous solution, and the mass concentration of acetic acid aqueous solution is 2%-5%.
3. the method for biomass preparation bio oil according to claim 1, which is characterized in that in the step (1) at pickling The mass volume ratio of biomass and pickling solution is 0.5-2g: 15-25ml in reason.
4. the method for biomass preparation bio oil according to claim 1, which is characterized in that the inert atmosphere is N2。
5. the method for biomass preparation bio oil according to claim 1, which is characterized in that biomass in the step (1) Mass ratio with catalyst is 0.5-2g: 0.5-1.5g.
6. the method for any biomass preparation bio oil of claim 1-5, which is characterized in that catalysis in the step (2) Agent is ZSM-5 Type Zeolites agent, method of modifying are as follows: by Fe (NO3)3· 9H2O is dissolved in water, adds ZSM-5 molecule Sieve catalyst stirs evenly, and is then dried into powder at 100-110 DEG C, calcines to obtain Fe through 600-700 DEG C3+Mass content is The modified ZSM-5 catalyst of 2%-6%.
CN201910807167.1A 2019-08-29 2019-08-29 A kind of method and its catalyst of biomass preparation bio oil Pending CN110358568A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111073671A (en) * 2019-12-24 2020-04-28 山东理工大学 Green and cyclic comprehensive utilization method of red mud and lignin waste
CN112899067A (en) * 2021-01-14 2021-06-04 湖南大学 Method for increasing sugar content in biological oil
CN116328849A (en) * 2023-05-12 2023-06-27 郑州大学 Biochar-based MOFs catalyst and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104941695A (en) * 2015-06-08 2015-09-30 清华大学 Nano ZSM-5 molecular sieve based catalyst and preparation and use methods
CN104962309A (en) * 2008-03-04 2015-10-07 马萨诸塞大学 Catalytic pyrolysis of solid biomass and related biofuels and aromatics

Patent Citations (2)

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CN104962309A (en) * 2008-03-04 2015-10-07 马萨诸塞大学 Catalytic pyrolysis of solid biomass and related biofuels and aromatics
CN104941695A (en) * 2015-06-08 2015-09-30 清华大学 Nano ZSM-5 molecular sieve based catalyst and preparation and use methods

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HUIYAN ZHANG等: "Catalytic Pyrolysis of Willow Wood with Me/ZSM-5 (Me = Mg, K, Fe, Ga, Ni) to Produce Aromatics and Olefins", 《BIORESOURCES》 *
陈涛等: "酸洗-烘焙预处理对生物质热解产物的影响", 《化工进展》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111073671A (en) * 2019-12-24 2020-04-28 山东理工大学 Green and cyclic comprehensive utilization method of red mud and lignin waste
CN112899067A (en) * 2021-01-14 2021-06-04 湖南大学 Method for increasing sugar content in biological oil
CN116328849A (en) * 2023-05-12 2023-06-27 郑州大学 Biochar-based MOFs catalyst and preparation method and application thereof
CN116328849B (en) * 2023-05-12 2024-05-28 郑州大学 Biochar-based MOFs catalyst and preparation method and application thereof

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