CN114602511B - Reduced transition metal sulfide catalyst for catalytic hydrogenation of polycyclic aromatic hydrocarbon compounds and preparation method thereof - Google Patents

Reduced transition metal sulfide catalyst for catalytic hydrogenation of polycyclic aromatic hydrocarbon compounds and preparation method thereof Download PDF

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CN114602511B
CN114602511B CN202011409106.9A CN202011409106A CN114602511B CN 114602511 B CN114602511 B CN 114602511B CN 202011409106 A CN202011409106 A CN 202011409106A CN 114602511 B CN114602511 B CN 114602511B
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transition metal
sulfide
aromatic hydrocarbon
polycyclic aromatic
metal sulfide
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CN114602511A (en
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田志坚
杨成功
王冬娥
王从新
刘浩
王琳
杨林
王学林
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Dalian Institute of Chemical Physics of CAS
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    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
    • C07C5/11—Partial hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
    • C07C2603/26—Phenanthrenes; Hydrogenated phenanthrenes
    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a reduced transition metal sulfide catalyst for catalytic hydrogenation of polycyclic aromatic hydrocarbon compounds and a preparation method thereof, belonging to the technical field of catalytic hydrogenation and nano materials. The invention comprises the following steps: fully and mechanically mixing transition metal sulfide (molybdenum sulfide, tungsten sulfide and the like) and a reducing agent (sodium borohydride, lithium aluminum hydride and the like) by grinding and the like; regulating and controlling the types and the proportion of the sulfide and the reducing agent; placing the mixture in heating equipment purged by inert atmosphere or directly exposing transition metal sulfide to reducing atmosphere (hydrogen), controlling the reaction temperature to be 300-900 ℃ and the reaction time to be 2-12 hours; and cooling, washing and drying after the reaction is finished to obtain the reduced transition metal sulfide catalyst. The preparation process of the invention is simple, and is easy for large-scale industrial application, and the sulfur atoms on the surface of the reduced transition metal sulfide partially escape to generate sulfur vacancies, thereby improving the catalytic hydrogenation activity.

Description

Reduced transition metal sulfide catalyst for catalytic hydrogenation of polycyclic aromatic hydrocarbon compounds and preparation method thereof
Technical Field
The invention relates to a reduced transition metal sulfide catalytic material, a preparation method thereof and application thereof in hydrogenation reaction of polycyclic aromatic hydrocarbon compounds, belonging to the technical field of catalytic hydrogenation and nano materials.
Background introduction
Transition metal sulfides, particularly molybdenum sulfide and tungsten sulfide, have been widely studied as high-efficiency catalysts in catalytic hydrogenation and electrocatalytic hydrogen evolution reactions in recent years. Experimental and theoretical studies have shown that limited active sites and poor conductivity in transition metal sulfides limit their potential catalytic capabilities (Journal of the American Chemical Society,2013,135,47, 17881-17888). Literature (Nature Energy,2017,17127) studies found that S vacancies on the basal planes are catalytically active sites, with vacancy states around the fermi level allowing hydrogen to bind directly to the exposed metal atoms.
The document (Nature Materials,2016,15, 48-53) exposes molybdenum sulfide to Ar plasma, and controls exposure time and radio frequency power, thereby realizing controllable removal of S atoms on the surface of the molybdenum sulfide, constructing a large number of sulfur vacancies on the surface of a catalyst, preparing reduced molybdenum sulfide, and remarkably improving the catalytic activity of the molybdenum sulfide in the electrocatalytic hydrogen evolution reaction. However, this method uses plasma, requires precise equipment, multiple steps, and is not suitable for large-scale synthesis because the synthesis method is expensive.
The literature (Nature Communications,2017,8, 15113) applies molybdenum sulfide to an electrode, and reduces the molybdenum sulfide on the electrode by applying an electric potential, thereby realizing the formation of surface sulfur vacancies. The catalyst is used for electrocatalytic hydrogen evolution reaction and has good activity and stability. The method needs an external power supply, is complex to operate, and the product is not easy to separate. The literature (Journal of the American Chemical Society,2016,138,51, 16632-16638) prepares molybdenum sulfide catalysts rich in sulfur vacancies by reducing the pretreated molybdenum sulfide in 5% hydrogen (argon as the balance) at 350 ℃ for 2 hours. The method uses a large amount of hydrogen at high temperature, has potential safety hazard and is not suitable for large-scale synthesis and application.
The literature (Angewandte Chemie International Edition,2019,58 2 Obtaining MoS rich in S vacancy 2 A material. The method is in MoS 2 The basal plane of the catalyst produces a large number of S vacancies, and the reduction degree is adjusted by adjusting the amount of Zn powder, so that the catalyst has relatively good catalytic activity and stability in the electrocatalytic Hydrogen Evolution (HER) reaction. The methodThe reduction type molybdenum sulfide prepared by the method is doped with Zn atoms, and the product is not easy to separate.
The above studies indicate that removal of surface S atoms can create a large number of exposed sulfur vacancies. However, the above method is not only complicated in operation and high in instrument requirement, but also expensive. Therefore, there is an urgent need for an economical and effective strategy to construct sulfur vacancies on the surface of transition metal sulfides. According to the invention, a solid precursor is treated at high temperature in an inert atmosphere to prepare the reduced transition metal sulfide catalyst, during the synthesis process, the reducing agents such as sodium borohydride or lithium aluminum hydride are decomposed at high temperature to release hydrogen, and S atoms on the surface of the transition metal sulfide escape in the high-temperature reducing atmosphere to obtain the reduced transition metal sulfide with a sulfur vacancy.
Disclosure of Invention
The invention aims to provide a method for synthesizing reduced transition metal sulfide by gas-solid phase aiming at the problem of large-scale preparation of reduced transition metal sulfide. And the catalyst is used in the reaction of hydrogenation of polycyclic aromatic hydrocarbon compounds.
The invention adopts the following technology to realize the purpose:
1: molybdenum sulfide or tungsten sulfide and a reducing agent are mechanically and uniformly mixed by grinding or ball milling, and the amount of the sulfide and the reducing agent is adjusted to ensure that the molar ratio of the reducing agent to the transition metal sulfide in the formed mixture is 0.01.
2: transferring the mixture into a quartz tube or a crucible, respectively placing the quartz tube or the crucible filled with the mixture into a tube furnace or a muffle furnace, and introducing inert gases such as argon or helium, wherein the purging speed is 20-100 ml/min; purging for 20-40 min to replace air in the tubular furnace or muffle furnace, heating the tubular furnace or crucible to 300-900 deg.c, and reacting for 2-12 hr.
3: and after the heating reaction is finished, cooling the obtained sample to room temperature, taking out the sample, washing away the unreacted reducing agent by using deionized water, drying the sample at the temperature of more than 40 ℃ for more than 4 hours by adopting a conventional drying method, and collecting a solid product to obtain the reduced molybdenum sulfide or reduced tungsten sulfide catalyst.
In the step 1, the transition metal is one or two of molybdenum sulfide or tungsten sulfide. The reducing agent is one of sodium borohydride, lithium aluminum hydride and the like.
In the step 1, the molar ratio of the mixture reducing agent to the transition metal is preferably 0.5.
In the step 2, the reaction temperature is preferably 300 to 800 ℃, and the reaction time is preferably 3 to 10 hours.
The invention can be used as a catalyst for polycyclic aromatic hydrocarbon hydrogenation reaction, uses polycyclic aromatic hydrocarbon organic solution and hydrogen as raw materials, the temperature is 200-500 ℃, the pressure is 4-15MPa, disperses reduction type molybdenum sulfide or reduction type tungsten sulfide into the organic solution, and reacts for 2-6 hours to obtain one or more polycyclic aromatic hydrocarbon hydrogenation products; the reaction temperature is preferably 250 to 450 ℃, the reaction time is preferably 3 to 5 hours, and the reaction pressure is preferably 5 to 10MPa.
Compared with the prior art, the invention has the following advantages and effects:
1) The reduction type transition metal sulfide catalyst synthesized by the invention has good catalytic hydrogenation activity when being used in phenanthrene hydrogenation reaction, under the optimal reaction condition, the highest hydrogenation conversion rate of phenanthrene on the reduction type molybdenum sulfide catalyst can reach 92%, and the highest hydrogenation conversion rate of phenanthrene on the reduction type tungsten sulfide catalyst can reach 88%, and the catalytic activity is obviously improved compared with that of unreduced molybdenum sulfide and tungsten sulfide.
2) The gas-solid method adopted by the invention has simple preparation process and easy industrial large-scale application, partial escape of sulfur atoms on the surface of the reduced transition metal sulfide generates sulfur vacancies, improves the catalytic hydrogenation activity, and has good application prospect in the catalytic hydrogenation reaction of polycyclic aromatic hydrocarbon
Detailed Description
The following examples further illustrate the present invention without limiting the scope of the invention.
Example 1
Adding 10mmol of molybdenum sulfide, 5And (3) sufficiently grinding mmol of lithium aluminum hydride, and uniformly mixing, wherein the ratio of the reducing agent to molybdenum sulfide is 0.5. The mixture was transferred to a tube furnace and treated with helium at 300 ℃ for 6 hours at a flow rate of 20 ml/min. Naturally cooling to room temperature, washing the reacted powder with deionized water, vacuum drying at 70 ℃ overnight, and collecting the reduced MoS 2 And (3) sampling.
Example 2
Fully grinding 10mmol of molybdenum sulfide and 10mmol of sodium borohydride, and uniformly mixing, wherein the ratio of the reducing agent to the molybdenum sulfide is 1. The mixture was transferred to a tube furnace and treated with helium at a flow rate of 20ml/min at 800 ℃ for 10 hours. Naturally cooling to room temperature, washing the reacted powder with deionized water, vacuum drying at 70 ℃ overnight, and collecting the reduced MoS 2 And (3) sampling.
Example 3
Fully grinding 5mmol of molybdenum sulfide, 5mmol of tungsten sulfide and 15mmol of sodium borohydride, and uniformly mixing, wherein the ratio of the reducing agent to the sulfide is 1.5. The mixture was transferred to a tube furnace and treated with helium at a flow rate of 20ml/min at 800 ℃ for 10 hours. Naturally cooling to room temperature, washing the reacted powder with deionized water, drying at 70 ℃ overnight, and collecting the reduced MoS 2 And WS 2 The mixed sample of (1).
Example 4
Fully grinding 10mmol of tungsten sulfide and 15mmol of lithium aluminum hydride, and uniformly mixing, wherein the ratio of the reducing agent to the tungsten sulfide is 1.5. The mixture was transferred to a tube furnace and treated with helium at 400 ℃ for 5 hours at a flow rate of 20 ml/min. Naturally cooling to room temperature, washing the reacted powder with deionized water, vacuum drying at 70 deg.c overnight, and collecting the reduced WS 2 And (4) sampling.
Example 5
Fully grinding 10mmol of tungsten sulfide and 10mmol of sodium borohydride, and uniformly mixing, wherein the ratio of the reducing agent to the tungsten sulfide is 1. The mixture was transferred to a tube furnace and treated with helium at a flow rate of 20ml/min at 500 ℃ for 4 hours. Naturally cooling to room temperature, washing the reacted powder with deionized water, vacuum drying at 70 ℃ overnight, and collecting the reduced WS 2 And (4) sampling.
Example 6
Fully grinding 10mmol of tungsten sulfide and 5mmol of sodium borohydride, and uniformly mixing, wherein the ratio of the reducing agent to the molybdenum sulfide is 0.5. The mixture was transferred to a tube furnace and treated with helium at 800 ℃ for 10 hours at a flow rate of 20 ml/min. Naturally cooling to room temperature, washing the reacted powder with deionized water, vacuum drying at 70 deg.c overnight, and collecting the reduced WS 2 Sample (I)
Example 7
The products prepared in examples 1-6 were used as catalysts to evaluate the performance of phenanthrene hydrogenation catalysts, and molybdenum sulfide and tungsten sulfide were used for comparison, respectively, and the procedure was as follows: in a 100ml suspension bed microreactor (Parr kettle reactor) 30 g of tridecane are added as solvent, together with 3 g of phenanthrene and 0.075 g of the preparation catalyst. The air in the kettle is replaced by 0.5-1.0MPa hydrogen for five times. Closing the air inlet valve and the air release valve, and filling hydrogen to 5-10 Mpa. Starting the condensed water and stirring, adjusting the rotating speed to 300 revolutions per minute, the reaction temperature to 250-450 ℃ and the reaction time to 3-5 hours. After the reaction was completed, the raw material and the hydrogenation product were quantified by gas chromatography equipped with an FID detector.
The results of the phenanthrene catalytic hydrogenation evaluation are shown in Table 1.
TABLE 1 phenanthrene catalytic hydrogenation evaluation results
Figure BDA0002817224650000041
The present invention is further described in detail with reference to Table 1 below. The result of the phenanthrene catalytic hydrogenation reaction comprises product selectivity and phenanthrene conversion rate, and the hydrogenation products are dihydrophenanthrene (PH 2), tetrahydrophenanthrene (PH 4), octahydrophenanthrene (PH 8) and perhydrophenanthrene (PH 14).
The reduced molybdenum sulfide and the reduced tungsten sulfide are used in a phenanthrene suspension bed hydrogenation reaction, the maximum conversion rate of phenanthrene on the reduced molybdenum sulfide is 92 percent, and the conversion rate is 4.6 times that of commercial molybdenum sulfide; the maximum conversion of phenanthrene to reduced tungsten sulfide was 88%, which is 5.2 times that of commercial tungsten sulfide (see table 1).
The above-described embodiments are merely preferred conditions for carrying out the present invention, and are not limited to the embodiments. All equivalents, related parameter optimizations, etc. that are the same as the principles of the present invention are intended to be within the scope of the present invention.

Claims (11)

1. A method for polycyclic aromatic hydrocarbon compound catalytic hydrogenation reaction is characterized in that: the method adopts a reduced transition metal sulfide catalyst to catalyze the hydrogenation of polycyclic aromatic hydrocarbons; the preparation process of the reduced transition metal sulfide catalyst comprises the following steps:
1) Mechanically mixing a transition metal sulfide and a reducing agent, wherein the molar ratio of the reducing agent to the transition metal sulfide in the mixture is 0.01 to 1;
the transition metal sulfide is one or two of molybdenum sulfide and tungsten sulfide;
2) Processing the mixture at 300 to 900 ℃ for 2 to 12 hours; and after the high-temperature treatment is finished, washing, drying and collecting a solid product to obtain the reduction type molybdenum sulfide and/or reduction type tungsten sulfide catalyst.
2. The method of claim 1, wherein:
the polycyclic aromatic hydrocarbon hydrogenation product is obtained by taking polycyclic aromatic hydrocarbon organic solution and hydrogen as raw materials, reacting for 2 to 6 hours under the catalytic action of a reduction type molybdenum sulfide or tungsten sulfide catalyst at the temperature of 200-500 ℃ and the pressure of 4-15 MPa.
3. The method of claim 1, wherein: the mechanical mixing mode is one or two of grinding and ball milling; the high-temperature treatment equipment is a tubular furnace or a muffle furnace.
4. The method of claim 1, wherein: the reducing agent is one or two of sodium borohydride and lithium aluminum hydride.
5. The method according to claim 1 or 4, characterized in that: the molar ratio of the mixture reducing agent to the transition metal in the step 1) is 0.5 to 1.
6. The method of claim 1, wherein: the reaction temperature in the step 2) is 300 to 800 ℃.
7. The method of claim 1, wherein: the reaction time in the step 2) is 3 to 10 hours.
8. The method of claim 2, wherein: the polycyclic aromatic hydrocarbon organic solution is an organic solution of a polycyclic aromatic hydrocarbon compound, or one or more of polycyclic aromatic hydrocarbon-containing coal tar and diesel fuel; the polycyclic aromatic hydrocarbon is one or more than two of bicyclic, tricyclic, tetracyclic, pentacyclic, hexacyclic or heptacyclic aromatic hydrocarbon compounds.
9. The method of claim 8, wherein: the polycyclic aromatic hydrocarbon is phenanthrene and/or anthracene.
10. The method of claim 1, wherein: the reaction temperature is 250 to 450 ℃; the reaction pressure is 5-10MPa.
11. The method according to claim 1 or 10, characterized in that: the reaction time in the step 3) is 3 to 5 hours.
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