CN110694678A - Phenol hydrodeoxygenation catalyst, preparation method and application - Google Patents

Phenol hydrodeoxygenation catalyst, preparation method and application Download PDF

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CN110694678A
CN110694678A CN201910957162.7A CN201910957162A CN110694678A CN 110694678 A CN110694678 A CN 110694678A CN 201910957162 A CN201910957162 A CN 201910957162A CN 110694678 A CN110694678 A CN 110694678A
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catalyst
sba
hydrodeoxygenation
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陈冠益
刘菊平
李湘萍
刘彬
王传斌
殷晗
颜蓓蓓
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Tianjin University
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    • 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
    • B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
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    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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    • 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
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/0333—Iron group metals or copper
    • 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
    • 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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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

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Abstract

The invention relates to a phenol hydrodeoxygenation catalyst, a preparation method and application thereof; the structural formula of the catalyst is Ni/Al-SBA-15/HZSM-5. Firstly, three-stage polymer P123 is taken as a template agent, added into deionized water, and stirred by magnetic force to prepare Al (NO)3)3·9H2Dissolving O and tetraethyl silicate (TEOS) in deionized water, introducing hot circulating water for reaction, and placing the mixture into an oven for crystallization; finally, washing with deionized water, drying, and then placing into a muffle furnace at 550 ℃ to calcine the template agent at high temperature to obtain white powder Al-SBA-15; mixing the obtained Al-SBA-15 and HZSM-5 catalyst according to the proportion of 1:1, uniformly mixing, loading 6-16% of nickel metal, and calcining at the high temperature of 550 ℃ to obtain a catalyst; the catalyst is used for hydrodeoxygenation refining of eugenol, the conversion rate of eugenol reaches about 100.0%, and the naphthene has 99.50% of selectivity.

Description

Phenol hydrodeoxygenation catalyst, preparation method and application
Technical Field
The invention belongs to the technical field of biomass derivative catalytic conversion, and relates to a preparation method of a catalyst in liquid fuel preparation by one-step catalytic hydrodeoxygenation of downstream product eugenol derived from lignin.
Background
The lignin is used as a main component of biomass, is a main byproduct in the ethanol production industry and the paper industry by hydrolysis and fermentation of lignocellulose biomass, is not fully utilized, and becomes an environmental pollutant, thus bringing great pressure to the environment. Bio-oil is a complex mixture of biomass that is pyrolyzed, gasified and rapidly condensed under non-thermodynamic equilibrium conditions, and is considered to be one of the best alternative liquid fuels in renewable energy sources at present. The currently internationally accepted technology for preparing the bio-oil from the biomass is biomass fast pyrolysis and direct liquefaction, but the obtained bio-oil has high oxygen content (35-40 wt%), poor chemical stability and high corrosivity, is immiscible with hydrocarbon fuels, cannot be directly used as a transportation fuel, and needs subsequent deoxidation and refining. Therefore, the research on the removal of oxygen element in the bio-oil is the core research content in the refining process of the bio-oil. The oxygen-containing substances in the biological oil mainly comprise acids, phenols, aldehydes, esters, alcohols, ketones, ethers and the like. Among them, phenols are a very important class of oxygen-containing substances, and since phenolic hydroxyl groups are directly connected to benzene rings, direct removal of oxygen elements in phenols becomes the greatest challenge in bio-oil refining.
The complex composition and many disadvantages of bio-oil make it necessary to refine it for use. Among many bio-oil refining methods, catalytic hydrodeoxygenation of bio-oil is one of the more effective methods. In a catalytic hydrodeoxygenation system, the active site of the used catalyst, the type of the carrier loaded by the catalyst and the experimental temperature and pressure all have obvious influence on the catalytic hydrogenation effect. The types of catalysts for hydrodeoxygenation of phenolic compounds are many. Wherein the catalyst adopted in the initial hydrodeoxygenation reaction of the bio-oil is CoMo/NiMo sulfide gamma-Al used for refining petroleum products2O3A catalyst.The loss of sulfur in the reaction is easy to cause product pollution, and the interaction of sulfide and oxygen leads to structural change to deactivate the catalyst, so the catalyst is not suitable for the hydrodeoxygenation reaction of the bio-oil. The traditional zeolite molecular sieves have too small pore diameters to meet the requirements of some reactions, so that molecular sieve catalytic materials with larger pore diameters are urgently needed. Supported catalysts with noble metals as active species (e.g. Pt/C, Pt-Sn/CNFs, Pd, Ru, Rh/SiO)2-Al2O3Etc.), although the catalytic activity is high, the high cost limits its application. In recent years, a supported catalyst using a transition metal Ni as an active species shows excellent catalytic performance in HDO reaction, and is an important direction in the research field of bio-oil hydrodeoxygenation catalysts.
In the currently reported research works, the research on model compounds as objects is more, and the research on real lignin degradation products as raw materials is less. Although the model compound has certain representativeness, the phenolic compound is easy to polymerize to generate a macromolecular organic polymer, thereby causing carbon deposition on the surface of the catalyst. In fact, in the process of hydro-upgrading biomass-based oxygenates, the hydrogenation reaction of the oxygenates and the polymerization reaction are in parallel competition relationship. However, the rate of the polymerization reaction is generally far greater than that of the hydrogenation reaction, so the hydrogenation modification process is often accompanied by the occurrence of polymerization and coking phenomena, which leads to the rapid deactivation of the catalyst. This is an important reason that the prior biomass hydrodeoxygenation refining is difficult to make breakthrough progress. At present, neither traditional sulfided catalysts nor noble metal catalysts have been tested for long runs. Meanwhile, the hydrodeoxygenation reaction of the oxygen-containing compound is generally carried out in various ways, and various intermediate products are generated. The mesoporous molecular sieve SBA-15 has a two-dimensional hexagonal through hole structure and high stability, and Al-SBA-15 obtained by Al modification in the invention has high hydrothermal stability, good pore size and acid-base solution stability. HZSM-5 is a microporous zeolite molecular sieve with high silica-alumina ratio, and shows excellent catalytic efficiency in many organic catalytic reactions. Therefore, the Al-SBA-15 and HZSM-5 are compounded by the prior art, so that the invention has better acidic activity and pore-size structure. In order to overcome the defects that the catalyst is easy to inactivate and has poor catalytic effect, the invention designs and synthesizes a novel bifunctional hydrodeoxygenation acidic catalyst Ni/Al-SBA-15/HZSM-5 which has a unique micro-mesoporous structure and has good hydrodeoxygenation effect on a phenol product obtained by depolymerizing lignin, and high-grade hydrocarbon fuel oil can be obtained through one-step reaction.
Disclosure of Invention
The main purpose of the present invention is to solve the problems of the prior art, and the present invention provides a novel bifunctional hydrodeoxygenation catalyst, which utilizes a typical model compound eugenol (C) after biomass depolymerization10H12O2) As a reactant, the method for preparing the hydrocarbon fuel by one-step hydrodeoxygenation solves the problems of high oxygen content and the like of the existing bio-oil, and converts the bio-oil into a liquid fuel with stable properties.
The invention is realized by the following technical scheme:
a phenol hydrodeoxygenation catalyst has a structural formula of Ni/Al-SBA-15/HZSM-5.
A preparation method of a phenol hydrodeoxygenation catalyst comprises the following steps:
(1) firstly, three-stage polymer P123 is taken as a template agent, added into deionized water, and stirred by magnetic force to prepare Al (NO)3)3·9H2Dissolving O and tetraethyl silicate (TEOS) in deionized water, introducing hot circulating water to react for 20-24 h, and putting the mixture into an oven for crystallization; finally, washing with deionized water, drying at 50-90 ℃, and then placing into a muffle furnace at 550 ℃ to calcine a template agent at high temperature to obtain white powder Al-SBA-15;
(2) mixing the obtained Al-SBA-15 and HZSM-5 catalyst according to the proportion of 1:1, uniformly mixing, loading 6-16% of nickel metal, and calcining at the high temperature of 550 ℃ to obtain the Ni/Al-SBA-15/HZSM-5 catalyst.
The mass ratio of the template agent to the deionized water in the step 1) is 0.005-0.2: 1.
al (NO) in the step 1)3)3·9H2The molar ratio of O to tetraethyl silicate (TEOS) is 0.01-0.2: 1.
and (2) magnetically stirring for 12-20 h in the step 1).
And (3) putting the mixture into an oven for crystallization 2d in the step 1).
And (3) calcining for 4 hours in a muffle furnace in the step 1).
The catalyst of the invention is used for the hydrodeoxygenation reaction of phenols.
In the hydrodeoxygenation reaction of the biomass depolymerization product eugenol, the reaction temperature is 200-300 ℃, the reaction time is 1-3 h, and the reaction pressure is 1-3 Mpa; the adding mass ratio of the raw material eugenol to the catalyst is 5-20: 1.
as shown in FIG. 1, the bio-oil model compound eugenol (C)10H12O2) Under the action of a novel micro-mesoporous nickel-based catalyst Ni/Al-SBA-15/HZSM-5, a catalytic hydrodeoxygenation experiment is carried out to finally obtain the C7-C10 alkane liquid fuel. The reaction result shows that the eugenol is subjected to hydrodeoxygenation refining by using the novel Ni/Al-SBA-15/HZSM-5 catalyst with the micro-mesoporous structure, the conversion rate of the eugenol reaches about 100.0 percent, and the cycloparaffin has the selectivity of 99.50 percent.
The invention has the beneficial effects that: the invention adopts the cheap micro-mesoporous bifunctional nickel-based catalyst to carry out hydrodeoxygenation reaction on the phenolic compound obtained by depolymerization of lignin under certain conditions, thereby improving the thermal stability of the light phenolic compound.
Drawings
FIG. 1 is a schematic diagram of the hydrodeoxygenation experimental results of eugenol in bio-oil under Ni/Al-SBA-15/HZSM-5 catalyst
Detailed Description
A preparation method of the phenol hydrodeoxygenation catalyst comprises the following steps: a preferred specific method for preparing the catalyst comprises the steps of:
(1) synthesizing Al-SBA-15: three-stage polymer (P123) is used as a template agent, and the mass ratio of the template agent to deionized water is 0.01-0.1:1, stirring Al (NO) under magnetic force3)3·9H2Dissolving O and tetraethyl silicate (TEOS) in deionized water according to the mixing ratio of 0.05-0.1: 1 by mol, magnetically stirring for 12-20 h, introducing hot circulating water for reacting for 20-24 h, and placing the mixture into an oven for crystallization for 2 d. And finally, after suction filtration and drying, putting the mixture into a muffle furnace to calcine and remove the template agent, thereby obtaining a white powdery product.
(2) Preparation of Ni/Al-SBA-15/HZSM-5: the mass ratio of the synthesized Al-SBA-15 to the HZSM-5 purchased in the market is 1:1, uniformly mixing, and then loading 10-16% of Ni by adopting an isometric impregnation method; 5mL of absolute ethyl alcohol is added to dissolve nickel nitrate, the mixture is slowly dripped by a one-time dropper, and the mixture is stirred by a glass rod until the color is uniform. Sealing with sealing film, soaking at room temperature, oven drying at 60 deg.C overnight, and roasting in muffle furnace at 550 deg.C for 2 hr.
And (3) testing the activity of the catalyst: all catalysts were reduced for 4 hours at 550 ℃ with a hydrogen flow of 100mL/min, then 3 ℃/min to 550 ℃.50 mL of n-dodecane solvent and 1g of eugenol solution are respectively added into a 100mL high-pressure reaction kettle, and H is utilized2Adjusting the system pressure, wherein the reaction temperature is 260 ℃, the reaction pressure is 2MPa, the reaction time is 2h, the input amount of the Ni/Al-SBA-15/HZSM-5 catalyst is 0.2-0.5 g, and the adding ratio of the raw material eugenol to the catalyst is 5-20: 1.
in order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The following catalyst preparation examples:
example 1: (1) Al-SBA-15 is prepared by synthesis, three-stage polymer (P123) is used as a template agent, and the mass ratio of the template agent to deionized water is 0.01: 1, stirring Al (NO) under magnetic force3)3·9H2O and tetraethyl silicate (TEOS) as 0.05: 1 mol ratio is dissolved in deionized water and stirred by magnetic forceAnd (3) 12h, introducing hot circulating water for reaction for 20h, and placing the mixture into an oven for crystallization for 2 d. And finally, after suction filtration and drying, putting the mixture into a muffle furnace to be calcined for 4 hours at 550 ℃ to remove the template agent, thus obtaining a white powdery product. (2) Synthesizing and preparing Ni/Al-SBA-15/HZSM-5, wherein the prepared Al-SBA-15 and HZSM-5 purchased in the market are mixed according to the proportion of 1:1, uniformly mixing, standing overnight, then weighing 10% of nickel nitrate hexahydrate, putting the mixture into a small beaker, adding 5mL of absolute ethyl alcohol to dissolve the nickel nitrate, slowly dripping the mixture by using a one-time dropper, and stirring the mixture by using a glass rod until the mixture shows a uniform color. Sealing with a sealing film, soaking at room temperature, drying in an oven overnight, and roasting in a muffle furnace at 550 deg.C for 2 h.
Example 2: (1) Al-SBA-15 is prepared by synthesis, three-stage polymer (P123) is used as a template agent, and the mass ratio of the template agent to deionized water is 0.05: 1, stirring Al (NO) under magnetic force3)3·9H2O and tetraethyl silicate (TEOS) as per 0.08: dissolving the mixture ratio of 1 in deionized water, magnetically stirring for 12h, introducing hot circulating water for reaction for 22h, and placing the mixture into an oven for crystallization for 2 d. And finally, after suction filtration and drying, putting the mixture into a muffle furnace to be calcined for 4 hours at 550 ℃ to remove the template agent, thus obtaining a white powdery product. (2) Synthesizing and preparing Ni/Al-SBA-15/HZSM-5, wherein the prepared Al-SBA-15 and HZSM-5 purchased in the market are mixed according to the proportion of 1:1, uniformly mixing, standing overnight, then weighing 13% of nickel nitrate hexahydrate, putting the mixture into a small beaker, adding 5mL of absolute ethyl alcohol to dissolve the nickel nitrate, slowly dripping the mixture by using a one-time dropper, and stirring the mixture by using a glass rod until the mixture shows a uniform color. Sealing with a sealing film, soaking at room temperature, drying in an oven overnight, and roasting in a muffle furnace at 550 deg.C for 2 h.
Example 3: (1) Al-SBA-15 is prepared by synthesis, three-stage polymer (P123) is used as a template agent, and the mass ratio of the template agent to deionized water is 0.1:1, stirring Al (NO) under magnetic force3)3·9H2O and tetraethyl silicate (TEOS) as 0.1: dissolving the mixture ratio of 1 in deionized water, magnetically stirring for 12h, introducing hot circulating water for reacting for 24h, and placing the mixture into an oven for crystallization for 2 d. And finally, after suction filtration and drying, putting the mixture into a muffle furnace to be calcined for 4 hours at 550 ℃ to remove the template agent, thus obtaining a white powdery product. (2) Synthesizing and preparing Ni/Al-SBA-15/HZSM-5, and mixing the prepared Al-SBA-15 with the commercially available Al-SBA-15The commercial HZSM-5 was prepared in a ratio of 1:1, uniformly mixing, standing overnight, then weighing 16% of nickel nitrate hexahydrate, putting the mixture into a small beaker, adding 5mL of absolute ethyl alcohol to dissolve the nickel nitrate, slowly dripping the mixture by using a one-time dropper, and stirring the mixture by using a glass rod until the mixture shows a uniform color. Sealing with a sealing film, soaking at room temperature, drying in an oven overnight, and roasting in a muffle furnace at 550 deg.C for 2 h. The basic physical characteristics of the catalyst obtained are shown in table 1:
TABLE 1 structural and functional Properties of different acidic catalysts
Figure BDA0002227721590000041
The structural properties of different catalysts prepared by using the above cases are mainly described in table 1, and under different experimental preparation conditions, according to later-stage catalytic activity, Si/Al is 25-44; the load rate of Ni is 18-24%; total specific surface area (A)BET) 292-554 m2g-1(ii) a Total pore volume (V)p) In the range of 0.158 to 0.584cm3g-1(ii) a The mesopore volume is 0.241-0.277 cm3g-1(ii) a The pore volume of the micropores is 0.087-0.107 cm3g-1(ii) a The total acid amount is 0.196-0.210 mmol/g. The catalytic activity of the catalyst prepared under the three conditions is relatively good.
Catalysts were used in the phenolic hydrodeoxygenation examples:
the prepared examples 1-3 were used for the phenol hydrodeoxygenation reaction: as shown in Table 2, example 4 is the result of the reaction using example 1, example 5 is the result of the reaction using example 2, and example 6 is the result of the reaction using example 3.
Example 4: carrying out the biological oil phenol hydrodeoxygenation reaction in a high-pressure reaction kettle, and adjusting the reaction temperature of a system to be 200 ℃; the reaction time is 1 h; the reaction pressure is 1 Mpa; the adding mass ratio of the raw material eugenol to the catalyst is 5: 1.
example 5: carrying out the biological oil phenol hydrodeoxygenation reaction in a high-pressure reaction kettle, and adjusting the reaction temperature of a system to be 250 ℃; the reaction time is 2 h; the reaction pressure is 2 Mpa; the adding mass ratio of the raw material eugenol to the catalyst is 10: 1.
example 6: carrying out the biological oil phenol hydrodeoxygenation reaction in a high-pressure reaction kettle, and adjusting the reaction temperature of a system to 300 ℃; the reaction time is 3 h; the reaction pressure is 3 Mpa; the adding mass ratio of the raw material eugenol to the catalyst is 20: 1.
the catalyst needs to be reduced before reaction, and the calcined catalyst is taken and kept for 2 hours at 550 ℃ by using mixed gas of hydrogen and nitrogen in a tubular furnace at the flow rate of 100mL/min and the flow rate of 3 ℃/min. The high-pressure reaction kettle is filled with eugenol solution and H is utilized2Regulating system pressure, reaction temperature and reaction time, and regulating the input amount of the acidic catalyst and the eugenol. All liquid phase products were analyzed by GC-MS (Agilent 7890A/5975C) using p-phenol (Aladdin, 99.7%) as an internal standard. The instrument was equipped with a capillary column (HP-5, 30 m.times.250 m.times.0.25 m) and a Flame Ionization Detector (FID). The results of the experiment are shown in table 2.
TABLE 2 results of acid catalysts for phenol hydrodeoxygenation experiments
Figure BDA0002227721590000051
As can be seen from table 2, the conversion of eugenol by the acid catalyst was 100.00%, and in examples 4, 5 and 6, the hydrocarbon yields were 94.00%, 95.50% and 99.50%. In example 5, example 6 and example 7, it can be seen that eugenol can be efficiently converted into alkane, the reaction effect is good, the hydrocarbon yield is high and reaches 94.0%, and the generated oxygen-containing compounds are few. The result shows that the prepared Ni/Al-SBA-15/HZSM-5 catalyst with the novel micro-mesoporous structure has high selectivity on alkane generated by hydrodeoxygenation of eugenol.
While the above detailed description of the preparation method of a phenol hydrodeoxygenation catalyst provided by the present invention has been provided, the above examples are only for the purpose of helping understanding the technical scheme of the present invention and the core idea thereof, and it should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims (9)

1. A phenol hydrodeoxygenation catalyst has a structural formula of Ni/Al-SBA-15/HZSM-5.
2. A preparation method of a phenol hydrodeoxygenation catalyst comprises the following steps:
(1) firstly, three-stage polymer P123 is taken as a template agent, added into deionized water, and stirred by magnetic force to prepare Al (NO)3)3·9H2Dissolving O and tetraethyl silicate (TEOS) in deionized water, introducing hot circulating water to react for 20-24 h, and putting the mixture into an oven for crystallization; finally, washing with deionized water, drying at 50-90 ℃, and then placing into a muffle furnace at 550 ℃ to calcine a template agent at high temperature to obtain white powder Al-SBA-15;
(2) mixing the obtained Al-SBA-15 and HZSM-5 catalyst according to the proportion of 1:1, uniformly mixing, loading 6-16% of nickel metal, and calcining at the high temperature of 550 ℃ to obtain the Ni/Al-SBA-15/HZSM-5 catalyst.
3. The method as set forth in claim 2, characterized in that the mass ratio of the template agent to the deionized water in the step 1) is 0.005-0.2: 1.
4. the method as set forth in claim 2, wherein Al (NO) in the step 1)3)3·9H2The molar ratio of O to tetraethyl silicate (TEOS) is 0.01-0.2: 1.
5. the method as claimed in claim 2, wherein the magnetic stirring in step 1) is carried out for 12-20 hours.
6. The method as set forth in claim 2, wherein the step 1) is performed by crystallization in an oven for 2 d.
7. The method as set forth in claim 2, characterized in that the high-temperature calcination in the muffle furnace is carried out for 4 hours in the step 1).
8. Use of the catalyst of claim 1 for hydrodeoxygenation of phenols.
9. The application of claim 7, wherein the catalyst is used for hydrodeoxygenation reaction of eugenol which is a biomass depolymerization product, the reaction temperature is 200-300 ℃, the reaction time is 1-3 h, and the reaction pressure is 1-3 Mpa; the adding mass ratio of the raw material eugenol to the catalyst is 5-20: 1.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104056650A (en) * 2013-03-21 2014-09-24 中国科学院青岛生物能源与过程研究所 Nickel group-supported catalyst and preparation method and application thereof
CN104549476A (en) * 2015-01-12 2015-04-29 天津大学 Nickel metal loaded micro-mesoporous molecular sieve catalyst precursor and preparation method and application of nickel metal loaded micro-mesoporous molecular sieve catalyst precursor
CN105238423A (en) * 2015-11-03 2016-01-13 北京工商大学 Method for preparing furan compound through selective pyrolysis of bagasse
CN106492808A (en) * 2016-09-06 2017-03-15 中国科学院广州能源研究所 A kind of catalyst of catalysis Syringa oblata Lindl. phenol hydrogenation deoxidation reaction and preparation method
CN110117499A (en) * 2019-04-10 2019-08-13 中国科学技术大学 A method of alkane is prepared by oxygen-containing organic compound hydrogenation deoxidation
CN110257097A (en) * 2019-07-15 2019-09-20 中国林业科学研究院林产化学工业研究所 A kind of method of microwave-assisted lignin hydrogenolysis preparation bio oil

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104056650A (en) * 2013-03-21 2014-09-24 中国科学院青岛生物能源与过程研究所 Nickel group-supported catalyst and preparation method and application thereof
CN104549476A (en) * 2015-01-12 2015-04-29 天津大学 Nickel metal loaded micro-mesoporous molecular sieve catalyst precursor and preparation method and application of nickel metal loaded micro-mesoporous molecular sieve catalyst precursor
CN105238423A (en) * 2015-11-03 2016-01-13 北京工商大学 Method for preparing furan compound through selective pyrolysis of bagasse
CN106492808A (en) * 2016-09-06 2017-03-15 中国科学院广州能源研究所 A kind of catalyst of catalysis Syringa oblata Lindl. phenol hydrogenation deoxidation reaction and preparation method
CN110117499A (en) * 2019-04-10 2019-08-13 中国科学技术大学 A method of alkane is prepared by oxygen-containing organic compound hydrogenation deoxidation
CN110257097A (en) * 2019-07-15 2019-09-20 中国林业科学研究院林产化学工业研究所 A kind of method of microwave-assisted lignin hydrogenolysis preparation bio oil

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
XIANGPING LIA ET.AL: ""Hydrodeoxygenation of lignin-derived phenols to produce hydrocarbons over Ni/Al-SBA-15 prepared with different impregnants"", 《FUEL》 *
YUJING WENG ET.AL: ""Jet-Fuel Range Hydrocarbons from Biomass-Derived Sorbitol over Ni-HZSM-5/SBA-15 Catalyst"", 《CATALYSTS》 *

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