CN102660312B - Method for preparing liquid fuel by performing catalytic pyrolysis on biomass by using magnetic zirconium-based catalyst - Google Patents

Method for preparing liquid fuel by performing catalytic pyrolysis on biomass by using magnetic zirconium-based catalyst Download PDF

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CN102660312B
CN102660312B CN201210144324.3A CN201210144324A CN102660312B CN 102660312 B CN102660312 B CN 102660312B CN 201210144324 A CN201210144324 A CN 201210144324A CN 102660312 B CN102660312 B CN 102660312B
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biomass
liquid fuel
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zirconium
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CN102660312A (en
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陆强
张智博
董长青
杨勇平
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North China Electric Power University
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    • 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
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    • 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

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Abstract

The invention belongs to the field of utilization of biomass energy and particularly relates to a method for preparing liquid fuel by performing catalytic pyrolysis on biomass by using a magnetic zirconium-based catalyst. Magnetic ZrO2-Fe3O4 or magnetic Pd-ZrO2-Fe3O4 which is used as a catalyst and biomass which is used as a raw material are subjected to mechanical mixing, the biomass is quickly pyrolyzed at the temperature of between 400 and 600 DEG C under an anaerobic condition, and pyrolysis gas is quickly cooled to room temperature so as to obtain the liquid fuel with high fuel quality. In the process of catalyzing the pyrolysis of the biomass by using the magnetic zirconium-based catalyst, the forming of acid and aldehydes products can be effectively inhibited, and hydrocarbon products can be promoted to be formed, so that the high-level liquid fuel can be obtained. Moreover, the catalyst can be separated and recovered from solid residues by directly using an external magnetic field.

Description

Utilize the method for magnetic Zirconium-base catalyst catalyse pyrolysis biomass prepare liquid fuel
Technical field
The invention belongs to the field that utilizes of biomass energy, be specifically related to a kind of method of utilizing magnetic Zirconium-base catalyst catalyse pyrolysis biomass prepare liquid fuel.
Background technology
Biomass fast pyrogenation is under oxygen free condition, to make the then process with acquisition liquid bio oil to the rapid condensation of pyrolysis product of the quick decomposes of biomass, is a new and effective biomass energy utilization technologies.Bio oil is expected, as a kind of novel liquid fuel substitute fossil fuels, to be applied to various heat power equipments.But the fuel grade of conventional elementary bio oil is poor, main manifestations is: moisture content is high, oxygen level is high, calorific value is low, have acidity and corrodibility, heat-resistant quality and chemical stability are poor, can not dissolve each other etc. with fossil fuel oil.Therefore, need to refine to improve its fuel grade to bio oil.Different researchers has proposed multiple physics and chemistry method bio oil has been refined, and wherein most methods are all after pyrolysis gas generates, the various physical or chemical treatments of carrying out before or after being condensed into bio oil, thereby the grade of raising bio oil.
In biomass fast pyrogenation process, directly introduce suitable catalyst, the effect by catalyzer changes the reaction path of biomass fast pyrogenation, can realize the directional thermal decomposition of biomass and directly obtains high-grade liquid fuel.But, this process for purification is not in widespread attention, major cause be when the biomass of mechanically mixing and catalyzer pyrolytic reaction complete after, catalyzer and coke produced mix, difficult separation and recycling, causes effectively recycle of catalyzer; In addition, in biomass fast pyrogenation process, can produce more easy carbon deposits, cause the very fast carbon distribution inactivation of catalyzer, thereby further limited being widely used of this process for purification.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of method of magnetic Zirconium-base catalyst catalyse pyrolysis biomass-making for higher-grade liquid fuel of utilizing is provided.
The method of magnetic Zirconium-base catalyst catalyse pyrolysis biomass-making for higher-grade liquid fuel of utilizing provided by the invention, with magnetic ZrO 2-Fe 3o 4or magnetic Pd-ZrO 2-Fe 3o 4for catalyzer, taking biomass as raw material, be (1:3) ~ (1:50) carry out mechanically mixing by catalyzer and biomass according to mass ratio, under oxygen free condition, under 400 ~ 600 ° of C, carry out fast pyrogenation, after gas solid separation, pyrolysis gas is carried out to condensation and obtain liquid fuel.
Described magnetic ZrO 2-Fe 3o 4adopt following step preparation:
(1) preparation of magnetic substrate:
Measure FeCl according to mass ratio (1:2.5)～(10:1) 24H 2o and FeCl 36H 2o, is mixed with mixing solutions and joins in there-necked flask, is positioned in the water bath with thermostatic control of 65 DEG C, slowly splashes into NaOH solution that concentration is 0.1mol/L until pH to 12 continues constant temperature and stirs and ageing certain hour in stirring; Then there-necked flask is shifted out to water bath with thermostatic control cool to room temperature, utilize magnetic field separation magnetic substrate and supernatant liquid, afterwards magnetic substrate is carried out to repetitive scrubbing to neutral, save backup with suspended state;
(2) magnetic ZrO 2-Fe 3o 4preparation:
Measure the magnetic substrate suspension of preparation in step (1) in three-necked bottle, under whipped state, be warming up to 65 DEG C, measure ZrOCl 28H 2the solution of the 0.5mol/L that O is mixed with, joins in above-mentioned suspension, by ammoniacal liquor regulator solution pH value to 13, utilize magnetic field separation to make it sedimentation, the supernatant liquor that inclines, is washed till without chlorion with deionized water, then gained material is carried out to suction filtration, dry, roasting, obtain magnetic ZrO 2-Fe 3o 4catalyzer, and make ZrO 2quality percentage composition be 50 ~ 90%.
Digestion time in described step (1) is 10～120min; Being dried as loft drier in step (2) is dry, and drying temperature is 60～120 DEG C, and be 2～24h time of drying; Maturing temperature is 350～600 DEG C, and temperature programming speed is 0.5～10 DEG C/min, and soaking time is 1～4h.
Described magnetic Pd-ZrO 2-Fe 3o 4preparation method as follows: measure a certain amount of Palladous nitrate and be dissolved in deionized water, by ZrO 2-Fe 3o 4powder adds in above-mentioned salts solution, slowly splashes into ammoniacal liquor under stirring state, until pH value reaches 9, continues to filter and be dried after 12 hours in stirring at room temperature, finally will be dried thing and reduce under hydrogen and nitrogen atmosphere, obtains Pd-ZrO 2-Fe 3o 4magnetic Zirconium-base catalyst, and to make the quality percentage composition of Pd be 0.1 ~ 3%.
Described being dried as loft drier is dried, drying temperature is 80～120 DEG C, be 2～12h time of drying; Reduction temperature is 260 ~ 300 DEG C, and temperature programming speed is 0.5～3 DEG C/min, and soaking time is 2～4h.
Described biomass are lignocellulose-like biomass.
Described oxygen free condition is to maintain reaction system under inertia anaerobic shielding gas environment.
The time of described pyrolytic reaction is no more than 20s.
Beneficial effect of the present invention is:
Catalyzer used in the present invention has magnetic, after catalyse pyrolysis reaction is complete, can directly utilizes external magnetic field by its Separation and Recovery from pyrolysis residue, thereby facilitate the recycle of catalyzer; Magnetic substrate Fe in this magnetic Zirconium-base catalyst 3o 4completely by ZrO 2(or Pd-ZrO 2) institute wrap up, therefore Fe 3o 4can not participate in any reaction, thereby can effectively prevent Fe 3o 4lose magnetism because being reduced or being oxidized; ZrO 2active ingredient itself has the effect of acid-alkali double-function catalyzing, and its surperficial catalytic active center can effectively affect the pyrolytic reaction approach of biomass, and suppressing aldehyde and acid etc. has the component of negative impact to the fuel performance of product liquid; When at ZrO 2after upper load P d, rely on the catalytic activity of Pd, can further promote the reactions such as decarbonylation, decarboxylation, hydrogenation, thereby obtain high-grade liquid fuel.
Embodiment
The invention provides a kind of magnetic Zirconium-base catalyst and catalyse pyrolysis biomass-making method for higher-grade liquid fuel of utilizing, below in conjunction with embodiment, the present invention will be further described.
Percentage composition in following embodiment is quality percentage composition if no special instructions.
Embodiment 1
ZrO 2-Fe 3o 4preparation:
(1) preparation of magnetic substrate: the FeCl that measures respectively 30g 24H 2the FeCl of O and 6g 36H 2o is mixed with the mixing solutions of 200mL and joins in there-necked flask, is positioned in the water bath with thermostatic control of 65 DEG C, slowly splashes into concentration and be the NaOH solution of 0.1mol/L until pH reaches 12 in stirring, and continues constant temperature and stirs and ageing 30min; Then there-necked flask is shifted out to water bath with thermostatic control cool to room temperature, utilize magnetic field separation magnetic substrate and supernatant liquid, afterwards magnetic substrate is carried out to repetitive scrubbing to neutral, save backup with suspended state.
(2) magnetic ZrO 2-Fe 3o 4preparation: the suspension in step (1) is all moved in three-necked bottle, under whipped state, is warming up to 65 DEG C, measure the ZrOCl of 100g 28H 2the solution of the 0.5mol/L that O is mixed with, joins in above-mentioned solution, by ammoniacal liquor regulator solution pH value to 13, utilizes magnetic field separation to make it sedimentation, and the supernatant liquor that inclines is washed till without chlorion (with the AgNO of 0.1 mol/L with deionized water 3solution inspection), then above-mentioned material is carried out to roasting (temperature programming speed is 3 DEG C/min, and soaking time is 3h) at 500 DEG C in dry 3h, retort furnace at 110 DEG C in suction filtration, common air dry oven, obtain the magnetic ZrO of 51.6g 2-Fe 3o 4catalyzer; Wherein ZrO 2quality percentage composition be 74.1%.
By above-mentioned magnetic ZrO 2-Fe 3o 4catalyzer is all ground to particle diameter and is about 0.5mm left and right, to be dried poplar as raw material (median size is as 2mm), both are carried out to mechanically mixing, the ratio of poplar and catalyzer is 15:1, then mixture is sent in a fluidized-bed fast pyrolysis reactor by feeding screw, fast pyrogenation 20s under 500 DEG C, nitrogen atmosphere, the productive rate that obtains product liquid is 53%.The product liquid of collecting is analyzed, and its moisture content is 13%, superior calorific value is that 24.4MJ/kg, pH value are that kinematic viscosity at 5.0,40 DEG C is 17cSt.
Embodiment 2
Adopt the 51.6g magnetic ZrO preparing in embodiment 1 2-Fe 3o 4catalyzer, it is all ground to particle diameter and is about 0.5mm left and right, taking the poplar of natural air drying, as raw material, (median size is as 2mm, moisture content is 8%), both are carried out to mechanically mixing, and the ratio of poplar and catalyzer is 10:1, then mixture is sent in a fluidized-bed fast pyrolysis reactor by feeding screw, fast pyrogenation 20s under 480 DEG C, nitrogen atmosphere, the productive rate that obtains product liquid is 57%.The product liquid of collecting is analyzed, and its moisture content is 26%, superior calorific value is that 20.8MJ/kg, pH value are that kinematic viscosity at 4.8,40 DEG C is 6cSt.
Embodiment 3
Pd-ZrO 2-Fe 3o 4preparation:
The Palladous nitrate dihydrate that measures 1.30g is dissolved in deionized water, by the 51.6g ZrO of preparation in embodiment 1 2-Fe 3o 4add in above-mentioned salts solution, under stirring state, slowly splash into ammoniacal liquor, until pH value reaches 9 left and right, 3h is filtered and under 100 ° of C, is dried in common air dry oven in continuation after 12 hours in stirring at room temperature, finally will be dried thing under hydrogen and nitrogen atmosphere 280 ° of C reduction (temperature programming speed is 1 DEG C/min, soaking time is 3h), obtain the mesoporous ZrO of the Pd load of 52.1g 2(Pd/ZrO 2), wherein the charge capacity of Pd is 1%.
By above-mentioned magnetic Pd-ZrO 2-Fe 3o 4catalyzer is all ground to particle diameter and is about 0.5mm left and right, to be dried poplar as raw material (median size is as 2mm), both are carried out to mechanically mixing, the ratio of poplar and catalyzer is 30:1, then mixture is sent in a fluidized-bed fast pyrolysis reactor by feeding screw, fast pyrogenation 20s under 500 DEG C, nitrogen atmosphere, the productive rate that obtains product liquid is 51%.The product liquid of collecting is analyzed, and its moisture content is 12%, superior calorific value is that 27.5MJ/kg, pH value are that kinematic viscosity at 5.0,40 DEG C is 19cSt.
Embodiment 4
Adopt the 52.1g magnetic Pd-ZrO preparing in embodiment 3 2-Fe 3o 4catalyzer, it is all ground to particle diameter and is about 0.5mm left and right, taking the poplar of natural air drying, as raw material, (median size is as 2mm, moisture content is 8%), both are carried out to mechanically mixing, and the ratio of poplar and catalyzer is 20:1, then mixture is sent in a fluidized-bed fast pyrolysis reactor by feeding screw, fast pyrogenation 20s under 480 DEG C, nitrogen atmosphere, the productive rate that obtains product liquid is 55%.The product liquid of collecting is analyzed, and its moisture content is 25%, superior calorific value is that 23.0MJ/kg, pH value are that kinematic viscosity at 4.8,40 DEG C is 7cSt.

Claims (8)

1. a method of utilizing magnetic Zirconium-base catalyst catalyse pyrolysis biomass prepare liquid fuel, is characterized in that: with magnetic ZrO 2-Fe 3o 4or magnetic Pd-ZrO 2-Fe 3o 4for catalyzer, taking biomass as raw material, be (1:3) ~ (1:50) carry out mechanically mixing by catalyzer and biomass according to mass ratio, under oxygen free condition, under 400 ~ 600 ° of C, carry out fast pyrogenation, after gas solid separation, pyrolysis gas is carried out to condensation and obtain liquid fuel.
2. the method for utilizing magnetic Zirconium-base catalyst catalyse pyrolysis biomass prepare liquid fuel according to claim 1, is characterized in that: described magnetic ZrO 2-Fe 3o 4adopt following step preparation:
(1) preparation of magnetic substrate:
Measure FeCl according to mass ratio (1:2.5)～(10:1) 24H 2o and FeCl 36H 2o, is mixed with mixing solutions and joins in there-necked flask, is positioned in the water bath with thermostatic control of 65 DEG C, slowly splashes into NaOH solution that concentration is 0.1mol/L until pH to 12 continues constant temperature and stirs and ageing certain hour in stirring; Then there-necked flask is shifted out to water bath with thermostatic control cool to room temperature, utilize magnetic field separation magnetic substrate and supernatant liquid, afterwards magnetic substrate is carried out to repetitive scrubbing to neutral, save backup with suspended state;
(2) magnetic ZrO 2-Fe 3o 4preparation:
Measure the magnetic substrate suspension of preparation in step (1) in three-necked bottle, under whipped state, be warming up to 65 DEG C, measure ZrOCl 28H 2the solution of the 0.5mol/L that O is mixed with, joins in above-mentioned suspension, by ammoniacal liquor regulator solution pH value to 13, utilize magnetic field separation to make it sedimentation, the supernatant liquor that inclines, is washed till without chlorion with deionized water, then gained material is carried out to suction filtration, dry, roasting, obtain magnetic ZrO 2-Fe 3o 4catalyzer, and make ZrO 2quality percentage composition be 50 ~ 90%.
3. the method for utilizing magnetic Zirconium-base catalyst catalyse pyrolysis biomass prepare liquid fuel according to claim 2, is characterized in that, the digestion time in described step (1) is 10～120min; Being dried as loft drier in step (2) is dry, and drying temperature is 60～120 DEG C, and be 2～24h time of drying; Maturing temperature is 350～600 DEG C, and temperature programming speed is 0.5～10 DEG C/min, and soaking time is 1～4h.
4. the method for utilizing magnetic Zirconium-base catalyst catalyse pyrolysis biomass prepare liquid fuel according to claim 1, is characterized in that: described magnetic Pd-ZrO 2-Fe 3o 4preparation method as follows: measure a certain amount of Palladous nitrate and be dissolved in deionized water, by ZrO 2-Fe 3o 4powder adds in above-mentioned salts solution, slowly splashes into ammoniacal liquor under stirring state, until pH value reaches 9, continues to filter and be dried after 12 hours in stirring at room temperature, finally will be dried thing and reduce under hydrogen and nitrogen atmosphere, obtains Pd-ZrO 2-Fe 3o 4magnetic Zirconium-base catalyst, and to make the quality percentage composition of Pd be 0.1 ~ 3%.
5. the method for utilizing magnetic Zirconium-base catalyst catalyse pyrolysis biomass prepare liquid fuel according to claim 4, is characterized in that: described being dried as loft drier is dried, and drying temperature is 80～120 DEG C, be 2～12h time of drying; Reduction temperature is 260 ~ 300 DEG C, and temperature programming speed is 0.5～3 DEG C/min, and soaking time is 2～4h.
6. the method for utilizing magnetic Zirconium-base catalyst catalyse pyrolysis biomass prepare liquid fuel according to claim 1, is characterized in that: described biomass are lignocellulose-like biomass.
7. the method for utilizing magnetic Zirconium-base catalyst catalyse pyrolysis biomass prepare liquid fuel according to claim 1, is characterized in that: it is characterized in that: described oxygen free condition is to maintain reaction system under inertia anaerobic shielding gas environment.
8. the method for utilizing magnetic Zirconium-base catalyst catalyse pyrolysis biomass prepare liquid fuel according to claim 1, is characterized in that: the time of described pyrolytic reaction is no more than 20s.
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CN102250158A (en) * 2011-05-23 2011-11-23 中国科学技术大学 Method for preparing levoglucosenone
CN102430414A (en) * 2011-08-25 2012-05-02 华北电力大学 Zirconium-based magnetic solid superacid catalyst, its preparation and method for preparing levoglucose ketone by catalytic pyrolysis of cellulose or biomass

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Publication number Priority date Publication date Assignee Title
CN102250158A (en) * 2011-05-23 2011-11-23 中国科学技术大学 Method for preparing levoglucosenone
CN102430414A (en) * 2011-08-25 2012-05-02 华北电力大学 Zirconium-based magnetic solid superacid catalyst, its preparation and method for preparing levoglucose ketone by catalytic pyrolysis of cellulose or biomass

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