CN105498741B - Nano-composite catalyst of cracking lignin and preparation method thereof - Google Patents

Nano-composite catalyst of cracking lignin and preparation method thereof Download PDF

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Publication number
CN105498741B
CN105498741B CN201510681381.9A CN201510681381A CN105498741B CN 105498741 B CN105498741 B CN 105498741B CN 201510681381 A CN201510681381 A CN 201510681381A CN 105498741 B CN105498741 B CN 105498741B
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solution
crystallizing kettle
stirred
catalyst
zirconium
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CN105498741A (en
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殷辉
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Beijing Hesheng Xinyuan Technology Co. Ltd.
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Beijing Hesheng Xinyuan Technology Co Ltd
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel

Abstract

The invention discloses a kind of nano-composite catalyst of cracking lignin and its method for preparing the catalyst, the nano-composite catalyst of the cracking lignin prepared by this method can reduce the growing amount of charcoal and tar of the biomass in thermal cracking processes, improve the yield of bio oil active principle;Improve the processing route of bio oil simultaneously, reduce bio oil difficulty of processing, it is only necessary to which high-quality biological oil product is directly obtained by single step reaction.After the completion of catalyst preparation, catalysis Pyrolysis Experiment is carried out to the catalyst in fluid bed, and contrasted with the pure Pyrolysis Experiment without catalyst.As a result show, the biological oily yield obtained by catalytic lignin thermal cracking is up to 67.3wt%, and pyrolysis carbon left is down to 11.2%, and biological flue gas amount is 21.5%;And the biological oily yield only 31.7% obtained by the pure pyrolysis without catalyst, pyrolysis carbon left are up to 54.6%, biological flue gas amount is 13.7%.

Description

Nano-composite catalyst of cracking lignin and preparation method thereof
Technical field
The present invention relates to a kind of catalyst, more particularly to a kind of nano-composite catalyst of cracking lignin and its preparation side Method.
Background technology
In the prior art, in view of the increasingly depleted of fossil energy, and pollution problem caused by fossil energy burning, Regenerative resource energy-consuming ratio shared in the rear fossil epoch is increasingly heavier.Biomass is rear fossil epoch " organic carbon " Exclusive source, be a kind of unique regenerative resource that can be changed into liquid fuel by effective transform mode, and China Crude oil largely relies on import, thus greatly develop biomass prepare liquid fuel technology have highly important scientific meaning and Strategic importance.
Biomass through pyrolysis is the technology that current maximally effective biomass prepares liquid fuel (bio oil), but biomass Also there are some problems urgently to be resolved hurrily in thermal cracking liquefaction process, one side biomass through pyrolysis process can produce a large amount of Jiao at present Charcoal, this can reduce biological oily yield;A large amount of high oxygen containing tar components in the bio oil that another aspect thermal cracking is produced be present, So that bio oil is difficult to directly apply.Main cause caused by both inferior positions needs to analyze from the composition of biomass, Biomass is typically by three kinds of cellulose (41wt%), hemicellulose (28wt%) and lignin (27wt%) high molecular polymer groups Into these three high polymers occupy the 96% of biomass gross mass.In above-mentioned biomass pyrolysis process caused by two kinds it is unfavorable As a result just because of caused by lignin pyrolysis behavior, and cellulose and hemicellulose only produce on a small quantity in thermal cracking processes Tar and coke, it is therefore desirable to by a kind of effective manner come avoid lignin during biomass through pyrolysis caused by Influence, so as to eliminate caused two kinds of unfavorable conditions in thermal cracking processes.
On how to reduce tar content in biomass pyrolysis oil, increase the utilizability of bio oil, existing researcher From different technology paths, the quality of biomass pyrolysis oil is effectively increased.KIOR house journals of U.S. CN Mentioned in 104602813 and UOP (UOP) patent CN 103502395 and two are carried out to bio oil with catalyst Secondary processing, wherein, KIOR uses the biomass thermal catalytic converting catalyst based on ZSM-5, can effectively reduce in process of production Oxygen content and coke yield in bio oil;And the deoxidation work that use " two-step method " carries out bio oil is then mentioned in UOP patent Make, the first step first carries out the preliminary deoxidation of bio oil using catalyst for cracking, and second step enters traveling one using deep hydrogenation technology Walk deoxidation.Although KIOR and UOP patent can partly solve two big drawbacks during biomass through pyrolysis, both Method does not solve the above problems from source, is all that secondary operation is carried out to bio oil caused by biomass through pyrolysis, and And UOP deoxidation decoking process can also consume a large amount of hydrogen, considerably increase the production cost of bio oil.Not yet retrieve at present Have any patent can be solved effectively from source biomass through pyrolysis processing caused by two it is big the drawbacks of, it is therefore desirable to take one A little means change the hot tearing solution path of lignin, and then solve above-mentioned two from source from the pyrolysis behavior of lignin Big drawback, maximize bio oil production capacity.
The content of the invention
For above-mentioned shortcoming and defect of the prior art, it is an object of the invention to provide a kind of energy catalytic pyrolysis wood Nano-composite catalyst of quality and preparation method thereof, to reduce the generation of charcoal and tar of the biomass in thermal cracking processes Amount, improve the yield of bio oil active principle;Improve the processing route of bio oil simultaneously, reduce bio oil difficulty of processing, only need High-quality biological oil product is directly obtained by single step reaction.
The purpose of the present invention is achieved through the following technical solutions:
A kind of nano-composite catalyst of cracking lignin, using carclazyte as carrier, there is titanium dioxide in carclazyte supported on carriers Silicon-magnesia cocrystallization thing, is loaded with zirconium dioxide, the silica-zirconia on silica-magnesia cocrystallization thing Magnesium cocrystallization thing accounts for the 10-15% of carrier quality, and zirconium dioxide accounts for the 0.5-1% of carrier quality.
Preferably, the specific surface area of the carclazyte carrier is 200-400m2/ g, particle diameter are 95-200 mesh, and moisture is less than 12%.
Preferably, the particle diameter of the carclazyte carrier is 100-140 mesh.
A kind of preparation method of the nano-composite catalyst of cracking lignin, in turn includes the following steps:
S1, load weighted waterglass is diluted with deionized water, prepares silicic acid gel solution;
S2, magnesium sulfate solution is added in silicic acid gel solution, stirred on stirred tank, stirred to magnesium sulfate molecule Untill the surface for being attracted to silicic acid gel core, both mixed solutions are obtained;
S3, ammoniacal liquor is added in the mixed solution obtained in S2, magnesium sulfate is precipitated in the form of magnesium hydroxide, generation Magnesium hydroxide can be attached to porous silica surface, form emulsion;
S4, the emulsion obtained in S3 is stirred into 16-24h, is put into crystallizing kettle, crystallizing kettle is placed in baking oven, and solution exists Crystallization 12-16h in crystallizing kettle, silica-magnesia cocrystallization thing precursor liquid can be formed;
S5, zirconium oxide is dissolved in hydrofluoric acid, obtains saturation fluorination zirconium solution, the fluorination zirconium solution configured is added to In the precursor liquid obtained in S4,16-24h is stirred, obtains new mixed solution;
S6, ammoniacal liquor is added in the mixed solution obtained into S5, zirconium fluoride will be precipitated in the form of zirconium hydroxide, to this Mixed liquor is stirred 6-8h, and the mixed liquor is put into crystallizing kettle after having stirred, then crystallizing kettle is placed in baking oven in 180 24-48h is continuously bakeed at a temperature of DEG C;
S7, mixed liquor in crystallizing kettle in S6 is taken out, advance load weighted carclazyte carrier is put into mixed liquor, stirred Mixed liquor is subjected to supersonic oscillations 12h again after 6h, then the mixed liquor after vibration is put into crystallizing kettle, and is carried to crystallizing kettle Preceding addition ammoniacal liquor, last crystallizing kettle continuous crystallization 24h at 200 DEG C, obtains loaded catalyst emulsion;
S8, the emulsion obtained in crystallizing kettle in S7 is filtered, cleaned repeatedly with deionized water, until solution Aobvious neutrality, solution is then pumped into spray dryer by feed shaping is dried, obtain silica-magnesia-two The spheric granules of the cocrystallization thing of zirconium oxide.
Compared with prior art, the embodiment of the present invention at least has advantages below:
The nano-composite catalyst of cracking lignin of the present invention can reduce charcoal and Jiao of the biomass in thermal cracking processes The growing amount of oil, improve the yield of bio oil active principle;Improve the processing route of bio oil simultaneously, reduce bio oil difficult processing Degree, it is only necessary to which high-quality biological oil product is directly obtained by single step reaction.
After the completion of catalyst preparation, carry out catalysis Pyrolysis Experiment to the catalyst in fluid bed, and with without catalyst Pure Pyrolysis Experiment contrasted.As a result showing, the biological oily yield obtained by catalytic lignin thermal cracking is up to 67.3wt%, Pyrolysis carbon left is down to 11.2%, and biological flue gas amount is 21.5%;And the bio oil production obtained by the pure pyrolysis without catalyst Rate only 31.7%, pyrolysis carbon left are up to 54.6%, and biological flue gas amount is 13.7%
Embodiment
With reference to embodiment, the invention will be further described, and following examples are descriptive, is not limited , it is impossible to protection scope of the present invention is limited with this.
A kind of nano-composite catalyst of cracking lignin, using carclazyte as carrier, there is titanium dioxide in carclazyte supported on carriers Silicon-magnesia cocrystallization thing, is loaded with zirconium dioxide, the silica-zirconia on silica-magnesia cocrystallization thing Magnesium cocrystallization thing accounts for the 10-15% of carrier quality, and zirconium dioxide accounts for the 0.5-1% of carrier quality.
The specific surface area of the carclazyte carrier is 200-400m2/ g, particle diameter are 100-140 mesh, and moisture is less than 12%.
A kind of preparation method of the nano-composite catalyst of cracking lignin, in turn includes the following steps:
S1, load weighted waterglass is diluted with deionized water, prepares silicic acid gel solution;
S2, magnesium sulfate solution is added in silicic acid gel solution, stirred on stirred tank, stirred to magnesium sulfate molecule Untill the surface for being attracted to silicic acid gel core, both mixed solutions are obtained;
S3, ammoniacal liquor is added in the mixed solution obtained in S2, magnesium sulfate is precipitated in the form of magnesium hydroxide, generation Magnesium hydroxide can be attached to porous silica surface, form emulsion;
S4, the emulsion obtained in S3 is stirred into 16-24h, is put into crystallizing kettle, crystallizing kettle is placed in baking oven, and solution exists Crystallization 12-16h in crystallizing kettle, silica-magnesia cocrystallization thing precursor liquid can be formed;
S5, zirconium oxide is dissolved in hydrofluoric acid, obtains saturation fluorination zirconium solution, the fluorination zirconium solution configured is added to In the precursor liquid obtained in S4,16-24h is stirred, obtains new mixed solution;
S6, ammoniacal liquor is added in the mixed solution obtained into S5, zirconium fluoride will be precipitated in the form of zirconium hydroxide, to this Mixed liquor is stirred 6-8h, and the mixed liquor is put into crystallizing kettle after having stirred, then crystallizing kettle is placed in baking oven in 180 24-48h is continuously bakeed at a temperature of DEG C;
S7, mixed liquor in crystallizing kettle in S6 is taken out, advance load weighted carclazyte carrier is put into mixed liquor, stirred Mixed liquor is subjected to supersonic oscillations 12h again after 6h, then the mixed liquor after vibration is put into crystallizing kettle, and is carried to crystallizing kettle Preceding addition ammoniacal liquor, last crystallizing kettle continuous crystallization 24h at 200 DEG C, obtains loaded catalyst emulsion;
S8, the emulsion obtained in crystallizing kettle in S7 is filtered, cleaned repeatedly with deionized water, until solution Aobvious neutrality, solution is then pumped into spray dryer by feed shaping is dried, obtain silica-magnesia-two The spheric granules of the cocrystallization thing of zirconium oxide.
After the completion of catalyst preparation, carry out catalysis Pyrolysis Experiment to the catalyst in fluid bed, and with without catalyst Pure Pyrolysis Experiment contrasted.As a result showing, the biological oily yield obtained by catalytic lignin thermal cracking is up to 67.3wt%, Pyrolysis carbon left is down to 11.2%, and biological flue gas amount is 21.5%;And the bio oil production obtained by the pure pyrolysis without catalyst Rate only 31.7%, pyrolysis carbon left are up to 54.6%, and biological flue gas amount is 13.7%.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto, Any one skilled in the art the invention discloses technical scope in, the change or replacement that can readily occur in, It should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims Enclose and be defined.

Claims (1)

1. a kind of preparation method of the nano-composite catalyst of cracking lignin, it is characterised in that in turn include the following steps:
S1, load weighted waterglass is diluted with deionized water, prepares silicic acid gel solution;
S2, magnesium sulfate solution is added in silicic acid gel solution, stirred on stirred tank, stirred to magnesium sulfate molecule and inhaled Untill the surface for being attached to silicic acid gel core, both mixed solutions are obtained;
S3, ammoniacal liquor is added in the mixed solution obtained in S2, magnesium sulfate is precipitated in the form of magnesium hydroxide, the hydrogen-oxygen of generation Porous silica surface can be attached to by changing magnesium, form emulsion;
S4, the emulsion obtained in S3 is stirred into 16-24h, is put into crystallizing kettle, crystallizing kettle is placed in baking oven, and solution is in crystallization Crystallization 12-16h in kettle, silica-magnesia cocrystallization thing precursor liquid can be formed;
S5, zirconium oxide is dissolved in hydrofluoric acid, obtains saturation fluorination zirconium solution, the fluorination zirconium solution configured is added in S4 In obtained precursor liquid, 16-24h is stirred, obtains new mixed solution;
S6, ammoniacal liquor is added in the mixed solution obtained into S5, zirconium fluoride will be precipitated in the form of zirconium hydroxide, to the mixing Liquid is stirred 6-8h, and the mixed liquor is put into crystallizing kettle after having stirred, then crystallizing kettle is placed in baking oven in 180 DEG C of temperature The lower continuous baking 24-48h of degree;
S7, mixed liquor in crystallizing kettle in S6 is taken out, advance load weighted carclazyte carrier is put into mixed liquor, after stirring 6h Mixed liquor is subjected to supersonic oscillations 12h again, then the mixed liquor after vibration is put into crystallizing kettle, and adds in advance to crystallizing kettle Enter ammoniacal liquor, last crystallizing kettle continuous crystallization 24h at 200 DEG C, obtain loaded catalyst emulsion;
S8, the emulsion obtained in crystallizing kettle in S7 is filtered, cleaned repeatedly with deionized water, until during solution is aobvious Property, then solution is pumped into spray dryer by feed is dried shaping, obtains the silica-zirconia of carclazyte load The spheric granules of the cocrystallization thing of magnesium-zirconium dioxide.
CN201510681381.9A 2015-10-20 2015-10-20 Nano-composite catalyst of cracking lignin and preparation method thereof Expired - Fee Related CN105498741B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101768052A (en) * 2008-12-26 2010-07-07 中国科学院大连化学物理研究所 Method for preparing aromatic compound by catalytic hydrocracking of lignin
CN102335606A (en) * 2011-07-19 2012-02-01 华中师范大学 Biomass tar cracking catalyst
CN103055933A (en) * 2011-10-24 2013-04-24 中国石油化工股份有限公司 Hydrocracking catalyst as well as preparation method and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101824330B (en) * 2010-04-30 2012-12-26 中国科学技术大学 Catalytic thermal cracking method for lignin
WO2014070587A1 (en) * 2012-10-31 2014-05-08 Shell Oil Company Methods and systems for processing lignin during hydrothermal digestion of cellulosic biomass solids

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101768052A (en) * 2008-12-26 2010-07-07 中国科学院大连化学物理研究所 Method for preparing aromatic compound by catalytic hydrocracking of lignin
CN102335606A (en) * 2011-07-19 2012-02-01 华中师范大学 Biomass tar cracking catalyst
CN103055933A (en) * 2011-10-24 2013-04-24 中国石油化工股份有限公司 Hydrocracking catalyst as well as preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Catalytic Upgrading of Biomass Fast Pyrolysis Vapors Using Ordered Mesoporous ZrO2, TiO2 and SiO2";Qiang Lu et.al;《Energy Procedia》;20141231;第61卷;第1937-1941页 *

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Inventor after: Yin Hui

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