CN105251524B - Biomass liquefied oil catalytic cracking dehydrogenation catalyst - Google Patents
Biomass liquefied oil catalytic cracking dehydrogenation catalyst Download PDFInfo
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- CN105251524B CN105251524B CN201510672840.7A CN201510672840A CN105251524B CN 105251524 B CN105251524 B CN 105251524B CN 201510672840 A CN201510672840 A CN 201510672840A CN 105251524 B CN105251524 B CN 105251524B
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Abstract
A kind of biomass liquefied oil catalytic cracking dehydrogenation catalyst, belongs to catalyst field.It is characterized in that it is made up of the composition of following masses percentage：11.00 15.45% Ni, 17.12 24.67% ZrO2With 59.88 71.88% zeolite.The catalyst is prepared using infusion process, and its preparation process includes：(1) dealuminated zeolite is prepared；(2) ZrO is prepared2/ dealuminated zeolite；(3) NiO/ZrO is prepared2/ dealuminated zeolite；(4) NiO/ZrO obtained in step (3)2/ dealuminated zeolite is biomass liquefied oil catalytic cracking dehydrogenation catalyst, and before bio-oil catalytic cracking reaction is carried out, the catalyst should be placed in 700 DEG C of hydrogen and reduce 3 hours.Catalyst provided by the present invention, there is preferable DNA vaccine and anticoking capability, in biomass liquefied oil catalytic cracking deoxygenation, under the conditions of normal pressure, 500 DEG C, biomass liquefied oil DNA vaccine reaches 38.87%.Its preparation method is simple to operate, and used raw material economics is easy to get.
Description
Technical field
The present invention relates to a kind of catalyst, more particularly to a kind of biomass liquefied oil catalytic cracking dehydrogenation catalyst, belong to
Catalyst field.
Background technology
With the increasingly depleted being continuously increased with oil of energy demand, seek a kind of new energy of alternative traditional fuel
The inevitable requirement for solving energy shortage, maintaining social development is turned into.Biomass energy is regenerative resource, wide material sources, including：
Timber and forest industry discarded object, agricultural wastes, water plant, city and industrial organic wastes, animal wastes etc..Its is excellent
Point is that sulphur, nitrogen content are low, and environmental pollution is small in process；Organic matter is changed into fuel and reduces public hazards, is following energy
Chief component in source structure.But the depth of biomass utilization is inadequate, and industrialized condition is immature, especially in profound profit
Larger space with aspect be present.It is that biomass energy deep processing should wherein by biomass liquefying product (bio-oil) upgrading refining
One of approach.Due to the complicated component of biomass liquefying product, there are the compounds such as alcohols, ethers, acids, hydro carbons, phenols,
The problems such as oxygen content is high, calorific value is low, moisture and acid number are higher, is not suitable as engine fuel and chemical products is straight
Connect utilization.Have high oxidation, unstability, sticky, corrosivity, strong hygroscopicity and chemical composition complicated for bio-oil
The features such as property, traditional petroleum fuel is directly substituted to be very limited with it, therefore, it is necessary to refined, improved to it
Its quality is to reach fuel oil requirement.
At present, bio-oil process for purification can be divided into physics method for refining and chemical refining method.Physics is refined mainly to be passed through
The means such as solvent, emulsification are added to complete, although its calorific value can be improved, are restricted using field.Chemical refining mainly collects
In in catalytic hydrogenation, catalytic pyrolysis, catalytic esterification etc., no matter be to urge using any chemical refining method, its key technology
The exploitation of agent pair.The oil quality that catalytic hydrogenation obtains is higher, but because equipment requirement is high, abrasion is big, and technical requirements are high, whole
Costly, while the blocking of the inactivation of catalyst and reactor restricts the development of this technology to individual process.Catalytic cracking process
Bio-oil is cracked under the conditions of existing for catalyst, oxygen is deviate from the form of CO2, H2O or CO.The process reaction
Condition is gentleer, it is not necessary to is hydrogenated with, consersion unit requires that no catalytic hydrogenation is strict, thus has very big development potentiality, together
When catalytic pyrolysis refined raw material oil yield it is relatively low, coking rate is high, and catalyst life is short, therefore how to improve process catalysis
Activity, selectivity and the anticoking capability of agent, turn into the crucial and anxious bottleneck to be broken through of tackling key problem.
The content of the invention
The invention provides a kind of biomass liquefied oil catalytic cracking dehydrogenation catalyst.Biomass liquefied oil in the present invention
Catalytic cracking dehydrogenation catalyst is prepared using infusion process, and under the conditions of normal pressure, 500 DEG C, biomass liquefied oil DNA vaccine reaches
To 38.87%, while catalyst has preferable anticoking capability.
The concrete scheme that the present invention uses for：
Biomass liquefied oil catalytic cracking dehydrogenation catalyst of the present invention, by following masses percentage into packet
Into：11.00-15.45% Ni, 17.12-24.67% ZrO2With 59.88-71.88% zeolite.
Wherein, described zeolite is dealuminated zeolite.
Described biomass liquefied oil catalytic cracking dehydrogenation catalyst is prepared using infusion process, and preparation process includes：
(1) dealuminated zeolite is prepared, natural zeolite is together added in water heating kettle with distilled water, water heating kettle good seal is put into dry
In dry case, under the conditions of 150 DEG C, constant temperature processing 5h, by the Zeolite dehydration after hydro-thermal process, and 1mol/L HCL stirring leachings are added
After steeping 1-3 hours, wash, filter, cross 200 mesh sieves after drying and select particle, obtain dealuminated zeolite.Wherein, natural zeolite and distillation
The mass ratio of water is preferably 1:2.
(2) ZrO is prepared2/ dealuminated zeolite, the dealuminated zeolite obtained in step (1), is put into beaker and adds 200ml's
Distilled water, Zr (NO are added in the beaker equipped with dealuminated zeolite3)4·5H2O, 100 DEG C of constant temperature stirrings, dissolves, evaporation, will after drying
Product smashes, and is put into Muffle furnace after setting 550 DEG C of calcining 5h, obtains ZrO2/ dealuminated zeolite.
(3) NiO/ZrO is prepared2/ dealuminated zeolite, the ZrO obtained in step (2)2/ dealuminated zeolite is immersed in nickel nitrate solution,
100 DEG C of constant temperature stirrings, evaporation, after drying, it is put into Muffle furnace and 550 DEG C of calcining 4h is set；Obtain NiO/ZrO2/ dealuminated zeolite.
(4) NiO/ZrO obtained in step (3)2/ dealuminated zeolite is biomass liquefied oil catalytic cracking deoxidation catalysis
Agent, before bio-oil catalytic cracking reaction is carried out, the catalyst should be placed in 700 DEG C of hydrogen and reduce 3 hours.
Heretofore described biomass liquefied oil catalytic cracking dehydrogenation catalyst is carrying out bio-oil Catalytic Cracking Unit of Measure
At once, reaction temperature sets 600 DEG C, and micro pump is fed with 0.03ml/min speed, and temperature of vaporization chamber is 500 DEG C, with N2For
Carrier gas is best mode.
It is an advantage of the invention that：
1st, catalyst provided by the present invention, there is preferable DNA vaccine and anticoking capability, urged in biomass liquefied oil
Change in cracking deoxygenation, under the conditions of normal pressure, 500 DEG C, biomass liquefied oil DNA vaccine reaches 38.87%.
2nd, method for preparing catalyst provided by the present invention is simple to operate, and used raw material economics is easy to get.
Embodiment
Embodiment 1
It is further detailed with reference to specific embodiment
(1) it is 1 by natural zeolite 5g and distilled water mass ratio:2, water heating kettle is together added, water heating kettle good seal is put into
In drying box, under the conditions of 150 DEG C, constant temperature processing 5h.By the Zeolite dehydration after hydro-thermal process, and 1mol/L HCL are added, stirred
Mix, wash, filter, cross 200 mesh sieves after drying and select particle, obtain dealuminated zeolite.
(2) the dealuminated zeolite 2g obtained in step (1), 14g 25% (mass percent) Zr (NO are put into3)4·
5H2In O solution, 100 DEG C of constant temperature stirrings, dissolve, evaporation, smash product after drying, be put into Muffle furnace and set 550 DEG C
After calcining 5h, ZrO is obtained2/ dealuminated zeolite.
(3) ZrO obtained into step (2)2/ dealuminated zeolite is totally immersed into 12ml 25% nickel nitrate solution, and 100
The stirring of DEG C constant temperature, evaporation, after drying, it is put into Muffle furnace and 550 DEG C of calcining 4h is set；Obtain NiO/ZrO2/ dealuminated zeolite；
(4) by the NiO/ZrO2/ dealuminated zeolites catalyst obtained in step (3) before bio-oil catalytic cracking reaction,
It is in situ after 700 DEG C of hydrogen reducings 3 hours, reaction temperature sets 600 DEG C, and micro pump is fed with 0.03ml/min speed, vapour
It is 500 DEG C to change room temperature, N2For carrier gas.
NiO/ZrO2The performance of/dealuminated zeolite catalyst is as shown in the table：
| Performance title | Performance indications |
| Specific surface area m2/g | 67.44 |
| Pore volume cc/g | 5.22 |
| Average pore size nm | 8.07 |
Claims (2)
1. a kind of biomass liquefied oil catalytic cracking dehydrogenation catalyst, it is characterized in that, it is made up of the composition of following masses percentage：
11.00-15.45% Ni, 17.12-24.67% ZrO2With 59.88-71.88% zeolite；Wherein, described zeolite is
Dealuminated zeolite；
The preparation process of described catalyst includes：
(1) dealuminated zeolite is prepared, natural zeolite is together added in water heating kettle with distilled water, and water heating kettle good seal is put into drying box
In, under the conditions of 150 DEG C, constant temperature processing 5h, by the Zeolite dehydration after hydro-thermal process, and add 1mol/L HCl stirring immersions 1-
After 3 hours, wash, filter, cross 200 mesh sieves after drying and select particle, obtain dealuminated zeolite；
(2) ZrO is prepared2/ dealuminated zeolite：The dealuminated zeolite obtained in step (1), it is put into beaker and adds 200mL distillation
Water, Zr (NO are added in the beaker equipped with dealuminated zeolite3)4 · 5H2O, 100 DEG C of constant temperature stirrings, dissolves, evaporation, will after drying
Product smashes, and is put into Muffle furnace after setting 550 DEG C of calcining 5h, obtains ZrO2/ dealuminated zeolite；
(3) NiO/ ZrO are prepared2/ dealuminated zeolite：The ZrO obtained in step (2)2/ dealuminated zeolite is immersed in nickel nitrate solution,
100 DEG C of constant temperature stirrings, evaporation, after drying, it is put into Muffle furnace and 550 DEG C of calcining 4h is set；Obtain NiO/ZrO2/ dealuminated zeolite；
(4) NiO/ZrO obtained in step (3)2/ dealuminated zeolite is biomass liquefied oil catalytic cracking dehydrogenation catalyst, is being entered
Before row bio-oil catalytic cracking reaction, the catalyst should be placed in 700 DEG C of hydrogen and reduce 3 hours.
2. biomass liquefied oil catalytic cracking dehydrogenation catalyst according to claim 1, it is characterized in that, described step
(1) mass ratio of natural zeolite and distilled water is 1 in:2.
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| CN201510672840.7A CN105251524B (en) | 2015-10-15 | 2015-10-15 | Biomass liquefied oil catalytic cracking dehydrogenation catalyst |
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| CN201510672840.7A CN105251524B (en) | 2015-10-15 | 2015-10-15 | Biomass liquefied oil catalytic cracking dehydrogenation catalyst |
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| CN105251524B true CN105251524B (en) | 2017-12-08 |
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| CN113070096B (en) * | 2021-03-22 | 2022-07-12 | 西安交通大学 | Biomass oxidative cracking catalyst based on modified H-Beta molecular sieve, and preparation method and application thereof |
| CN113617343A (en) * | 2021-08-31 | 2021-11-09 | 福州大学 | Biomass oil deoxidation catalyst and preparation method and application thereof |
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| FR2582665B1 (en) * | 1985-06-04 | 1988-08-05 | Inst Francais Du Petrole | CATALYTIC CRACKING PROCESS |
| WO2010035748A1 (en) * | 2008-09-25 | 2010-04-01 | セントラル硝子株式会社 | Process for producing 1,3,3,3-tetrafluoropropene |
| US8063258B2 (en) * | 2009-05-22 | 2011-11-22 | Kior Inc. | Catalytic hydropyrolysis of organophillic biomass |
| JP5525786B2 (en) * | 2009-08-31 | 2014-06-18 | Ｊｘ日鉱日石エネルギー株式会社 | Aviation fuel oil base material production method and aviation fuel oil composition production method |
| CN102719317B (en) * | 2012-07-12 | 2013-11-27 | 湖南未名创林生物能源有限公司 | Method for preparing biological aviation fuel by using litsea cubeba kernel oil |
| CN102773117A (en) * | 2012-08-21 | 2012-11-14 | 中国海洋石油总公司 | Medium-oil-type hydrocracking catalyst and preparation method thereof |
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