CN105498741A - Nano composite catalyst for cracking lignin and preparation method thereof - Google Patents
Nano composite catalyst for cracking lignin and preparation method thereof Download PDFInfo
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- CN105498741A CN105498741A CN201510681381.9A CN201510681381A CN105498741A CN 105498741 A CN105498741 A CN 105498741A CN 201510681381 A CN201510681381 A CN 201510681381A CN 105498741 A CN105498741 A CN 105498741A
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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
- 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
Abstract
The present invention discloses a nano composite catalyst for cracking lignin and a preparation method thereof, the nano composite catalyst prepared by the method can reduce the production amount of tar and charcoal in the biomass thermal cracking process, and improve the yield of a bio-oil effective component, meanwhile improves the processing route of bio-oil, and reduces bio-oil processing difficulty, and a high-quality bio-oil product can be directly obtained by a one-step reaction. After the completion of the preparation of the catalyst, a catalytic thermal cracking test is performed on the catalyst in a fluidized bed, and is compared with a pure catalyst-free thermal cracking test, results show that the yield of the bio-oil obtained by the lignin catalytic thermal cracking can reach up to 67.3wt%, residual carbon amount after the thermal cracking is reduced 11.2%, the amount of biogas is 21.5%, the yield of the bio-oil obtained by the pure catalyst-free thermal cracking is only 31.7%, residual carbon amount after the pure catalyst-free thermal cracking is up to 54.6%, and the amount of the biogas is 13.7%.
Description
Technical field
The present invention relates to a kind of catalyst, particularly relate to nano-composite catalyst of a kind of cracking lignin and preparation method thereof.
Background technology
In the prior art, day by day exhausted in view of fossil energy, and fossil energy burn the pollution problem brought, the energy-consuming ratio of regenerative resource shared by the rear fossil epoch is more and more heavier.Living beings are exclusive source of rear fossil epoch " organic carbon ", it is unique a kind of regenerative resource that can be changed into liquid fuel by effective transform mode, and a large amount of dependence on import of crude oil in China, therefore greatly develop biomass-making, for liquid fuel technology, there is very important scientific meaning and strategic importance.
Biomass through pyrolysis is the technology of the most effective current biomass-making for liquid fuel (bio oil), but also there are some difficult problems urgently to be resolved hurrily at present in biomass through pyrolysis liquefaction process, biomass through pyrolysis process can produce a large amount of coke on the one hand, and this can reduce bio oil productive rate; There is a large amount of high oxygen containing tar component in the bio oil that thermal cracking is produced on the other hand, make bio oil be difficult to direct application.The main cause that these two kinds of inferior positions produce needs to analyze from the formation of living beings, living beings are generally made up of cellulose (41wt%), hemicellulose (28wt%) and lignin (27wt%) three kinds of high molecular polymers, and these three kinds of high polymers occupy 96% of living beings gross mass.The two kinds of unfavorable results produced in above-mentioned biomass pyrolysis process are brought just because of lignin pyrolysis behavior, and cellulose and hemicellulose only produce a small amount of tar and coke at thermal cracking processes, therefore need the impact avoiding lignin to bring in biomass through pyrolysis process by a kind of effective mode, thus eliminate the two kinds of unfavorable conditions produced in thermal cracking processes.
About how reducing tar content in biomass pyrolysis oil, increase the utilizability of bio oil, existing researcher, from different technology path, all effectively improves the quality of biomass pyrolysis oil.Mention in U.S. KIOR house journal CN104602813 and UOP (UOP) patent CN103502395, with catalyst, secondary operations is carried out to bio oil, wherein, KIOR adopts the biomass thermal catalytic converting catalyst based on ZSM-5, effectively can reduce the oxygen content in bio oil and coke yield in process of production; Then mention the deoxidation work that bio oil is carried out in employing " two-step method " in the patent of UOP, the first step first adopts catalyst for cracking to carry out the preliminary deoxidation of bio oil, and second step adopts deep hydrogenation technology to carry out further deoxidation.Although the patent of KIOR and UOP all partly can solve the large drawback of two in biomass through pyrolysis process, but these two kinds of methods all solve the problem less than from source, all that secondary operations is carried out to the bio oil that biomass through pyrolysis produces, and the deoxidation decoking process of UOP also can consume a large amount of hydrogen, considerably increases the production cost of bio oil.Not yet retrieve at present that any patent effectively can solve from source that biomass through pyrolysis machining brings two large drawbacks, therefore the pyrolysis behavior taking some means from lignin is needed, change the thermal cracking path of lignin, and then solve above-mentioned two large drawbacks from source, bio oil production capacity is maximized.
Summary of the invention
For above-mentioned shortcoming and defect of the prior art, the object of the present invention is to provide nano-composite catalyst of a kind of energy catalytic pyrolysis lignin and preparation method thereof, to reduce the charcoal of living beings in thermal cracking processes and the growing amount of tar, improve the yield of bio oil active principle; Improve the processing route of bio oil simultaneously, reduce bio oil difficulty of processing, only need directly to obtain high-quality biological oil product by single step reaction.
The object of the invention is to be achieved through the following technical solutions:
A kind of nano-composite catalyst of cracking lignin, take carclazyte as carrier, silica-magnesia cocrystallization thing is had at carclazyte supported on carriers, on silica-magnesia cocrystallization thing, load has zirconium dioxide, described silica-magnesia 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 area of described carclazyte carrier is 200-400m
2/ g, particle diameter is 95-200 order, and moisture is lower than 12%.
Preferably, the particle diameter of described carclazyte carrier is 100-140 order.
A preparation method for the nano-composite catalyst of cracking lignin, in turn includes the following steps:
S1, dilutes load weighted waterglass by deionized water, prepares silicic acid gel solution;
S2, joins magnesium sulfate solution in silicic acid gel solution, stirred tank stirs, and is stirred to till magnesium sulfate molecule is attracted to the surface of silicic acid gel core, obtains both mixed solutions;
S3, adds ammoniacal liquor in the mixed solution obtained in S2, and magnesium sulfate is precipitated with the form of magnesium hydroxide, and the magnesium hydroxide of generation can be attached to the silica surface of porous, forms emulsion;
S4, the emulsion obtained in S3 is stirred 16-24h, and put into crystallizing kettle, crystallizing kettle is placed in baking oven, and solution is crystallization 12-16h in crystallizing kettle, can form silica-magnesia cocrystallization thing precursor liquid;
S5, is dissolved in zirconia in hydrofluoric acid, obtains saturated zirconium fluoride solution, joins in the precursor liquid obtained in S4 by the zirconium fluoride solution configured, and stirs 16-24h, obtains new mixed solution;
S6, add ammoniacal liquor in the mixed solution obtained in S5, zirconium fluoride is precipitated with the form of zirconium hydroxide, stirring 6-8h is carried out to this mixed liquor, after having stirred, this mixed liquor is put in crystallizing kettle, then crystallizing kettle is placed in baking oven at 180 DEG C of temperature, cures 24-48h continuously;
S7, mixed liquor in crystallizing kettle in S6 is taken out, to put in mixed liquor by load weighted carclazyte carrier in advance, again mixed liquor is carried out supersonic oscillations 12h after stirring 6h, then the mixed liquor after vibration is put into crystallizing kettle, and adding ammoniacal liquor in advance to crystallizing kettle, last crystallizing kettle is continuous crystallization 24h at 200 DEG C, obtains loaded catalyst emulsion;
S8, the emulsion obtained in crystallizing kettle in S7 is filtered, repeatedly cleans by deionized water, until solution is aobvious neutral, then solution is sent into spray dryer by feed pump and carry out drying and moulding, obtain the spheric granules of the cocrystallization thing of silica-magnesia-zirconium dioxide.
Compared with prior art, the embodiment of the present invention at least has the following advantages:
The nano-composite catalyst of cracking lignin of the present invention can reduce the charcoal of living beings in thermal cracking processes and the growing amount of tar, improves the yield of bio oil active principle; Improve the processing route of bio oil simultaneously, reduce bio oil difficulty of processing, only need directly to obtain high-quality biological oil product by single step reaction.
After catalyst preparing completes, in fluid bed, catalyse pyrolysis experiment is carried out to this catalyst, and contrast with the pure Pyrolysis Experiment not containing catalyst.Result shows, the bio oil productive rate 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 not containing the bio oil productive rate obtained by pure pyrolysis only 31.7% of catalyst, pyrolysis carbon left is up to 54.6%, and biological flue gas amount is 13.7%
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, and following examples are descriptive, is not determinate, can not limit protection scope of the present invention with this.
A kind of nano-composite catalyst of cracking lignin, take carclazyte as carrier, silica-magnesia cocrystallization thing is had at carclazyte supported on carriers, on silica-magnesia cocrystallization thing, load has zirconium dioxide, described silica-magnesia cocrystallization thing accounts for the 10-15% of carrier quality, and zirconium dioxide accounts for the 0.5-1% of carrier quality.
The specific area of described carclazyte carrier is 200-400m
2/ g, particle diameter is 100-140 order, and moisture is lower than 12%.
A preparation method for the nano-composite catalyst of cracking lignin, in turn includes the following steps:
S1, dilutes load weighted waterglass by deionized water, prepares silicic acid gel solution;
S2, joins magnesium sulfate solution in silicic acid gel solution, stirred tank stirs, and is stirred to till magnesium sulfate molecule is attracted to the surface of silicic acid gel core, obtains both mixed solutions;
S3, adds ammoniacal liquor in the mixed solution obtained in S2, and magnesium sulfate is precipitated with the form of magnesium hydroxide, and the magnesium hydroxide of generation can be attached to the silica surface of porous, forms emulsion;
S4, the emulsion obtained in S3 is stirred 16-24h, and put into crystallizing kettle, crystallizing kettle is placed in baking oven, and solution is crystallization 12-16h in crystallizing kettle, can form silica-magnesia cocrystallization thing precursor liquid;
S5, is dissolved in zirconia in hydrofluoric acid, obtains saturated zirconium fluoride solution, joins in the precursor liquid obtained in S4 by the zirconium fluoride solution configured, and stirs 16-24h, obtains new mixed solution;
S6, add ammoniacal liquor in the mixed solution obtained in S5, zirconium fluoride is precipitated with the form of zirconium hydroxide, stirring 6-8h is carried out to this mixed liquor, after having stirred, this mixed liquor is put in crystallizing kettle, then crystallizing kettle is placed in baking oven at 180 DEG C of temperature, cures 24-48h continuously;
S7, mixed liquor in crystallizing kettle in S6 is taken out, to put in mixed liquor by load weighted carclazyte carrier in advance, again mixed liquor is carried out supersonic oscillations 12h after stirring 6h, then the mixed liquor after vibration is put into crystallizing kettle, and adding ammoniacal liquor in advance to crystallizing kettle, last crystallizing kettle is continuous crystallization 24h at 200 DEG C, obtains loaded catalyst emulsion;
S8, the emulsion obtained in crystallizing kettle in S7 is filtered, repeatedly cleans by deionized water, until solution is aobvious neutral, then solution is sent into spray dryer by feed pump and carry out drying and moulding, obtain the spheric granules of the cocrystallization thing of silica-magnesia-zirconium dioxide.
After catalyst preparing completes, in fluid bed, catalyse pyrolysis experiment is carried out to this catalyst, and contrast with the pure Pyrolysis Experiment not containing catalyst.Result shows, the bio oil productive rate 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 not containing the bio oil productive rate obtained by pure pyrolysis only 31.7% of catalyst, pyrolysis carbon left is up to 54.6%, and biological flue gas amount is 13.7%.
The above; be only the present invention's preferably detailed description of the invention, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (4)
1. the nano-composite catalyst of a cracking lignin, it is characterized in that, take carclazyte as carrier, silica-magnesia cocrystallization thing is had at carclazyte supported on carriers, on silica-magnesia cocrystallization thing, load has zirconium dioxide, described silica-magnesia cocrystallization thing accounts for the 10-15% of carrier quality, and zirconium dioxide accounts for the 0.5-1% of carrier quality.
2. the nano-composite catalyst of cracking lignin according to claim 1, is characterized in that, the specific area of described carclazyte carrier is 200-400m
2/ g, particle diameter is 95-200 order, and moisture is lower than 12%.
3. the nano-composite catalyst of cracking lignin according to claim 2, is characterized in that, the particle diameter of described carclazyte carrier is 100-140 order.
4. a preparation method for the nano-composite catalyst of cracking lignin, is characterized in that, in turn includes the following steps:
S1, dilutes load weighted waterglass by deionized water, prepares silicic acid gel solution;
S2, joins magnesium sulfate solution in silicic acid gel solution, stirred tank stirs, and is stirred to till magnesium sulfate molecule is attracted to the surface of silicic acid gel core, obtains both mixed solutions;
S3, adds ammoniacal liquor in the mixed solution obtained in S2, and magnesium sulfate is precipitated with the form of magnesium hydroxide, and the magnesium hydroxide of generation can be attached to the silica surface of porous, forms emulsion;
S4, the emulsion obtained in S3 is stirred 16-24h, and put into crystallizing kettle, crystallizing kettle is placed in baking oven, and solution is crystallization 12-16h in crystallizing kettle, can form silica-magnesia cocrystallization thing precursor liquid;
S5, is dissolved in zirconia in hydrofluoric acid, obtains saturated zirconium fluoride solution, joins in the precursor liquid obtained in S4 by the zirconium fluoride solution configured, and stirs 16-24h, obtains new mixed solution;
S6, add ammoniacal liquor in the mixed solution obtained in S5, zirconium fluoride is precipitated with the form of zirconium hydroxide, stirring 6-8h is carried out to this mixed liquor, after having stirred, this mixed liquor is put in crystallizing kettle, then crystallizing kettle is placed in baking oven at 180 DEG C of temperature, cures 24-48h continuously;
S7, mixed liquor in crystallizing kettle in S6 is taken out, to put in mixed liquor by load weighted carclazyte carrier in advance, again mixed liquor is carried out supersonic oscillations 12h after stirring 6h, then the mixed liquor after vibration is put into crystallizing kettle, and adding ammoniacal liquor in advance to crystallizing kettle, last crystallizing kettle is continuous crystallization 24h at 200 DEG C, obtains loaded catalyst emulsion;
S8, the emulsion obtained in crystallizing kettle in S7 is filtered, repeatedly cleans by deionized water, until solution is aobvious neutral, then solution is sent into spray dryer by feed pump and carry out drying and moulding, obtain the spheric granules of the cocrystallization thing of silica-magnesia-zirconium dioxide.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115212912A (en) * | 2022-07-04 | 2022-10-21 | 中节能工程技术研究院有限公司 | Molecular sieve catalyst, preparation method and application thereof |
Citations (5)
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| 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 |
| CN101824330A (en) * | 2010-04-30 | 2010-09-08 | 中国科学技术大学 | Catalytic thermal cracking method for lignin |
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| 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 |
| US20140121419A1 (en) * | 2012-10-31 | 2014-05-01 | Shell Oil Company | Methods and systems for processing lignin during hydrothermal digestion of cellulosic biomass solids |
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Patent Citations (5)
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| 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 |
| CN101824330A (en) * | 2010-04-30 | 2010-09-08 | 中国科学技术大学 | Catalytic thermal cracking method for 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 |
| US20140121419A1 (en) * | 2012-10-31 | 2014-05-01 | Shell Oil Company | Methods and systems for processing lignin during hydrothermal digestion of cellulosic biomass solids |
Non-Patent Citations (1)
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| QIANG LU ET.AL: ""Catalytic Upgrading of Biomass Fast Pyrolysis Vapors Using Ordered Mesoporous ZrO2, TiO2 and SiO2"", 《ENERGY PROCEDIA》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115212912A (en) * | 2022-07-04 | 2022-10-21 | 中节能工程技术研究院有限公司 | Molecular sieve catalyst, preparation method and application thereof |
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Inventor after: Yin Hui Inventor before: Zhang Xiaoxiong |
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Effective date of registration: 20170627 Address after: 100193, Haidian District northeast Zhongguancun Beijing Software Park incubator 1 building B block 3, layer 1305, Beijing Applicant after: Beijing Hesheng Xinyuan Technology Co. Ltd. Address before: 100080 Beijing, Haidian District, northeast Wang Zhongguancun Software Park, building B, floor 3, block, level 1301 Applicant before: BEIJING HUABIAO LVYOU TECHNOLOGY DEVELOPMENT CO., LTD. |
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