CN110721692B - Gasoline adsorption desulfurization catalyst and preparation method and application thereof - Google Patents
Gasoline adsorption desulfurization catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN110721692B CN110721692B CN201810779827.5A CN201810779827A CN110721692B CN 110721692 B CN110721692 B CN 110721692B CN 201810779827 A CN201810779827 A CN 201810779827A CN 110721692 B CN110721692 B CN 110721692B
- Authority
- CN
- China
- Prior art keywords
- graphite rod
- catalyst
- gasoline
- hydrogenation active
- zno
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
Abstract
The present invention relates to a gasoline adsorption desulfurization catalyst, a preparation method and an application thereof, wherein the catalyst comprises, based on the dry basis weight of the catalyst, 5-25 wt% of hydrogenation active components, 25-60 wt% of ZnO, and 20-60 wt% of single-walled carbon nanotubes, wherein the hydrogenation active components are Ni and/or Co. The gasoline adsorption desulfurization catalyst has high desulfurization activity, and can deeply desulfurize industrial catalytic cracking gasoline under a mild condition.
Description
Technical Field
The disclosure relates to a gasoline adsorption desulfurization catalyst, a preparation method and application thereof.
Background
Sulfur-containing compounds in gasoline present a number of hazards: the sulfur oxides generated by combustion at high temperature can be converted into acid to corrode and damage engine parts, so that a three-way catalyst of an engine tail gas purification system generates irreversible poisoning, and NO in emissions X And CO X The content of SO is obviously increased and in addition, SO discharged into the atmosphere X Acid rain can also result. Therefore, many countries in the world have made strict regulations on the sulfur content of mogas by legislation. From 1 month and 1 day in 2017, the Chinese motor vehicle has comprehensively implemented the national fifth emission standard (the limit value of the sulfur content index is 10 mu g/g), and the more strict national sixth standard is also made. Therefore, the development of the gasoline deep desulfurization technology is imminent to produce gasoline with low sulfur content.
At present, the deep desulfurization technology of gasoline mainly comprises hydrodesulfurization, physical adsorption desulfurization, selective adsorption desulfurization, reaction adsorption desulfurization and the like. Hydrodesulfurization is a common desulfurization method, but in the process of gasoline hydrodesulfurization, olefin saturation is necessarily accompanied, so that the octane number is reduced; meanwhile, deep desulfurization by hydrogenation also results in greatly increased investment cost, more severe operating conditions and increased operating cost. The physical adsorption desulfurization process is simple, sulfides can be removed at normal temperature and normal pressure, and the adsorbent is easy to regenerate, but the adsorbent has poor selectivity on the sulfides and low sulfur capacity, and the deep desulfurization of gasoline is difficult to realize. The selective adsorption desulfurization condition is mild, the investment and operation cost is low, the desulfurization efficiency is high, but the sulfur capacity and the selectivity of the adsorbent are poor. The reactive adsorption desulfurization by using the Ni/ZnO adsorbent has the advantages of high desulfurization efficiency, small octane value loss, low hydrogen consumption and the like, and is a desulfurization process with a great development prospect. Current research on gasoline desulfurization catalysts is essentially going in two directions: one is to find new active ingredients and the other is to find new carriers.
Since the discovery of carbon nanotubes, the excellent properties have led to great research advances in a variety of applications. The carbon nano tube has very large specific surface area, and the maximum theoretical value can reach 8000m 2 (iv) g; the hollow structure of the carbon nano tube has special effect on sulfur in forms of hydrogen sulfide, methyl mercaptan, ethyl sulfide and the like; the carbon nano tube has special electronic property and is expected to have special adsorption effect on sulfur-containing compounds; the surface of the carbon nano tube can be loaded with different metals and oxides or filled with metal atoms, so that an active site with selective desulfurization is formed, and the desulfurization efficiency is expected to be multiplied.
Disclosure of Invention
The purpose of the present disclosure is to provide a gasoline adsorption desulfurization catalyst, a preparation method and an application thereof, wherein the gasoline adsorption desulfurization catalyst has high desulfurization activity, and can deeply desulfurize industrial catalytic cracking gasoline under a mild condition.
To achieve the above object, a first aspect of the present disclosure: the gasoline adsorption desulfurization catalyst comprises 5-25 wt% of hydrogenation active component, 25-60 wt% of ZnO and 20-60 wt% of single-walled carbon nanotube by taking the dry basis weight of the catalyst as a reference, wherein the hydrogenation active component is Ni and/or Co.
Optionally, the catalyst comprises 12-22 wt% of hydrogenation active component, 43-59 wt% of ZnO, and 24-45 wt% of single-walled carbon nanotubes based on the dry weight of the catalyst.
A second aspect of the disclosure: a method for preparing a gasoline adsorption desulfurization catalyst is provided, which comprises the following steps:
a. filling a mixed material containing a hydrogenation active component, znO and catalytic slurry oil into a graphite rod with a cavity, and then closing the graphite rod to obtain an anode graphite rod; the hydrogenation active component is Ni and/or Co;
b. and c, placing the anode graphite rod and the cathode graphite rod obtained in the step a in an arc discharge device, enabling the anode graphite rod and the cathode graphite rod to generate arc discharge in a helium or argon atmosphere, and collecting the gasoline adsorption desulfurization catalyst which is obtained in the arc discharge device and takes the single-walled carbon nanotube as a carrier after the anode graphite rod is consumed.
Optionally, in step a, based on the total weight of the mixed material, the content of the hydrogenation active component is 5 to 25 wt%, the content of ZnO is 20 to 60 wt%, and the content of the catalytic slurry oil is 20 to 55 wt%.
Optionally, in step a, based on the total weight of the mixed material, the content of the hydrogenation active component is 13 to 24 wt%, the content of ZnO is 45 to 60 wt%, and the content of the catalytic slurry oil is 22 to 42 wt%.
Optionally, in step a, the aromatic content of the catalytic slurry oil is 50 to 60 wt%.
Optionally, in step a, the hydrogenation active component is a simple substance of Ni and/or a simple substance of Co, and the particle size of the hydrogenation active component and the particle size of ZnO are 140 to 160 μm respectively.
Optionally, in step b, the arc discharge condition includes: the direct distance between the anode graphite rod and the cathode graphite rod is 2-4mm, the discharge voltage is 10-30V, the discharge current is 80-100A, and the absolute pressure is 0.03-0.05 MPa.
Optionally, the length of the graphite rod with the cavity is 60-80 mm, and the diameter of the graphite rod with the cavity is 7-10 mm; the cavity extends along the axial direction of the graphite rod, the axial length of the cavity is 40-60 mm, and the inner diameter of the cavity is 4-6 mm;
the cathode graphite rod is a solid graphite rod, the length of the solid graphite rod is 10-30 mm, and the diameter of the solid graphite rod is 8-20 mm.
A third aspect of the disclosure: there is provided a gasoline adsorption desulfurization catalyst prepared by the method of the second aspect of the present disclosure.
A fourth aspect of the present disclosure: there is provided the use of a catalyst according to the first or third aspect of the present disclosure in adsorptive desulfurization of gasoline.
According to the technical scheme, the gasoline adsorption desulfurization catalyst with the single-walled carbon nanotube as the carrier is prepared by taking the catalytic slurry oil as a carbon source for preparing the carbon nanotube, ni and/or Co as a hydrogenation active component and ZnO as an adsorption active component. The method provides an effective way for solving the processing and utilization problems of the catalytic slurry oil, and has the advantages of simple process, high carbon nano tube yield and uniform active component load. The gasoline adsorption desulfurization catalyst disclosed by the invention has the advantages of high desulfurization activity, low RON loss and the like, and can realize deep desulfurization of gasoline under mild reaction conditions.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure, but do not constitute a limitation of the disclosure. In the drawings:
FIG. 1 is a low-magnification TEM photograph of a gasoline adsorption desulfurization catalyst C3 prepared in example 3.
FIG. 2 is a high TEM photograph of the gasoline adsorption-desulfurization catalyst C3 prepared in example 3.
FIG. 3 is a high-magnification TEM photograph of the gasoline adsorption desulfurization catalyst C9 prepared in example 9.
Detailed Description
The following detailed description of the embodiments of the disclosure refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The first aspect of the disclosure: the gasoline adsorption desulfurization catalyst comprises 5-25 wt% of hydrogenation active component, 25-60 wt% of ZnO and 20-60 wt% of single-walled carbon nanotube by taking the dry basis weight of the catalyst as a reference, wherein the hydrogenation active component is Ni and/or Co. Preferably, the catalyst comprises 12-22 wt% of hydrogenation active component, 43-59 wt% of ZnO and 24-45 wt% of single-walled carbon nano-tube based on the dry weight of the catalyst.
The meaning of the single-walled carbon nanotubes (SWCNTs) is well known to those skilled in the art in light of the present disclosure, to which the present disclosure is not particularly limited. The gasoline adsorption desulfurization catalyst disclosed by the invention has the advantages of high desulfurization activity, low RON loss and the like, and can realize deep desulfurization of gasoline under mild reaction conditions.
In a second aspect of the present disclosure: a method for preparing a gasoline adsorption desulfurization catalyst is provided, which comprises the following steps:
a. filling a mixed material containing a hydrogenation active component, znO and catalytic slurry oil into a graphite rod with a cavity, and then sealing the graphite rod to obtain an anode graphite rod; the hydrogenation active component is Ni and/or Co;
b. and c, placing the anode graphite rod and the cathode graphite rod obtained in the step a in an arc discharge device, enabling the anode graphite rod and the cathode graphite rod to generate arc discharge in a helium or argon atmosphere, and collecting the gasoline adsorption desulfurization catalyst which is obtained in the arc discharge device and takes the single-walled carbon nanotube as a carrier after the anode graphite rod is consumed.
The method takes catalytic slurry oil as a carbon source for preparing the carbon nano tube, adopts Ni (nickel) and/or Co (cobalt) as a hydrogenation active component and ZnO (zinc oxide) as an adsorption active component, and prepares the gasoline adsorption desulfurization catalyst taking the single-walled carbon nano tube as a carrier. The method provides an effective way for solving the processing and utilization problems of the catalytic slurry oil, and has the advantages of simple process, high carbon nano tube yield and uniform active component load.
In order to achieve the desired effect, in step a, the content of the hydrogenation active component may be 5 to 25 wt%, preferably 13 to 24 wt%, based on the total weight of the mixture; the content of ZnO may be 20 to 60 wt%, preferably 45 to 60 wt%; the catalytic slurry oil may be present in an amount of 20 to 55 wt%, preferably 22 to 42 wt%.
The meaning of the catalytic slurry oil is well known to those skilled in the art in light of this disclosure and generally refers to the residue oil discharged from a catalytic cracking unit of a refinery. The catalytic slurry oil in a refinery has the processing and utilization problems due to the factors of poor reaction property, high solid particle content and the like, and can only be thrown out of a device. In the research of the inventor of the present disclosure, it is found that the aromatic hydrocarbon content in the catalytic slurry oil is high, and the catalytic slurry oil is an ideal component for preparing the carbon nano two-dimensional material. Specifically, in the step a, the aromatic hydrocarbon content of the catalytic slurry oil can be 50-60 wt%. The content of other components in the catalytic slurry oil is not particularly limited, and for example, it may contain 10 to 20 wt% of saturated hydrocarbon, 20 to 30 wt% of colloid, 2 to 8 wt% of asphaltene, and the like.
According to the disclosure, in the step a, the hydrogenation active component is a simple substance of Ni and/or a simple substance of Co. Furthermore, the hydrogenation active component can be powdery metal particles, and the particle diameters of the hydrogenation active component and ZnO can be respectively 140-160 μm, so that the hydrogenation active component and ZnO can be more uniformly loaded on the single-walled carbon nanotube without agglomeration, and the desulfurization activity of the catalyst is further improved.
The process of preparing carbon nanotubes using the arc discharge method according to the present disclosure may be conventional in the art. For example, after the anode graphite rod and the cathode graphite rod are placed in an arc discharge device, the arc discharge device can be purged by nitrogen firstly, and then the arc discharge device can be purged by helium or argon; then introducing helium or argon into the arc discharge device to reach the required absolute pressure; in order to further improve the purity of the single-walled carbon nanotube, cooling water can be introduced into the device after the steps; then starting a direct current power supply, and enabling the anode graphite rod and the cathode graphite rod to generate arc discharge under a certain condition; after the anode graphite rod is consumed, the power supply is turned off, the cooling water is stopped to be introduced, and the gasoline adsorption desulfurization catalyst taking the single-walled carbon nanotube as the carrier can be obtained in the electric arc discharge device (such as on the wall surface). Further, the step of purging the apparatus with nitrogen may be performed a plurality of times (e.g., 3-4 times), and the step of purging the apparatus with helium or argon may be performed 1 time, to exclude air from the arc discharge apparatus. The arc discharge device is not particularly limited by the present disclosure and may be various conventional apparatuses well known to those skilled in the art.
According to the present disclosure, in step b, the arc discharge condition may include: the direct distance between the anode graphite rod and the cathode graphite rod is 2-4mm, the discharge voltage is 10-30V, the discharge current is 80-100A, the absolute pressure is 0.03-0.05 MPa, and the discharge time can be 5-15 min.
Generally, according to the present disclosure, the anode graphite rod has a smaller diameter, while the cathode graphite rod has a larger diameter. Specifically, the length of the graphite rod with the cavity can be 60-80 mm, and the diameter can be 7-10 mm; the cavity extends along the axial direction of the graphite rod, the axial length of the cavity can be 40-60 mm, and the inner diameter can be 4-6 mm. The cathode graphite rod is a solid graphite rod, the length of the solid graphite rod can be 10-30 mm, and the diameter of the solid graphite rod can be 8-20 mm.
A third aspect of the disclosure: there is provided a gasoline adsorption desulfurization catalyst prepared by the method of the second aspect of the present disclosure.
A fourth aspect of the present disclosure: there is provided the use of a catalyst according to the first or third aspect of the present disclosure in adsorptive desulfurization of gasoline.
According to the present disclosure, the applying may include: and (3) carrying out contact reaction on industrial catalytic cracking gasoline and the gasoline adsorption desulfurization catalyst of the first aspect or the third aspect of the disclosure to obtain gasoline with low sulfur content. The conditions of the reaction may include: the reaction temperature is 200-450 ℃, the reaction pressure is 1-5MPa, and the weight hourly space velocity is 5-20h -1 The volume ratio of hydrogen to oil is 50-500. The sulfur content of the industrial catalytic cracking gasoline can be 300-1000 mu g/g. The reaction can be carried out in a fluidized bed reaction device, and the fluidized bed reaction device can realize continuous feeding and sampling operation. The catalyst disclosed by the invention can still maintain a high desulfurization rate (for example, more than 90 wt%) and a low RON loss (for example, less than 1.0) after a long reaction time (for example, 100 h); preferably, the sulfur content of the gasoline after reaction can reach the national gasoline standard V.
According to the disclosure, the sulfur-philic oxide (ZnO) on the gasoline adsorption desulfurization catalyst is gradually vulcanized and saturated after adsorbing sulfur element, the desulfurization capability is reduced, and at the moment, the adsorbed catalyst can recover the desulfurization activity after being subjected to a regeneration process of scorching (sulfur burning) and reduction, so that the catalyst can be reused. In general, the process of burning and reducing the catalyst may include the following steps: the catalyst is burnt at the burning temperature of 350-500 ℃, under normal pressure and in the air atmosphere with proper oxygen content; then reducing the burnt catalyst at the reduction temperature of 350-500 ℃ and under the hydrogen pressure of 1-3 MPa. After the catalyst disclosed by the invention is subjected to a regeneration process of scorching and reduction, the hydrogenation active components in the catalyst are reduced to a zero valence state. Thus, the application may further comprise: and regenerating the adsorbed catalyst obtained by separation after the contact reaction, and using the regenerated catalyst in the process of the contact reaction.
The following examples will further illustrate the methods provided by the present disclosure, but are not intended to limit the disclosure thereby.
The reagents used in the examples were analytical reagents unless otherwise indicated.
In the examples, the gasoline adsorption desulfurization catalyst was subjected to morphology analysis using a TEM (Transmission Electronic microscope) as a measuring instrument, and the measuring instrument was a Tecnai G2F 20 field emission transmission electron microscope manufactured by FEI corporation, USA.
In the examples, the contents of the hydrogenation active component, znO and single-walled carbon nanotubes of the gasoline adsorption desulfurization catalyst were measured by thermogravimetric analysis, and the test apparatus was a TGA/SDTA851e thermogravimetric analyzer manufactured by mettler toledo, switzerland.
The main body of the arc discharge device adopted in the embodiment is a stainless steel cylinder, and the accessory equipment comprises a direct current welding machine (A x 3-300-1 type), a vacuum pump and a water cooling pipeline.
The properties of the catalytic slurry oils used in the examples are shown in Table 1.
TABLE 1
Examples 1-6 are provided to illustrate the method of preparing a gasoline adsorption desulfurization catalyst provided by the present disclosure.
Example 1
Uniformly mixing Ni powder (with the particle size of 140-160 mu m), znO powder (with the particle size of 140-160 mu m) and catalytic slurry oil according to the proportion of 8 wt%, 45 wt% and 47 wt%, filling the mixture into a graphite rod (with the length of 70mm, the diameter of 8mm, the axial length of the cavity of 50mm and the inner diameter of the cavity of 5 mm) with a cavity, and then sealing the graphite rod to obtain the anode graphite rod. Placing the anode graphite rod and the cathode graphite rod (solid graphite rod, the diameter is 20mm, and the length is 30 mm) in an arc discharge plasma device, closing a cabin door of the device, starting a vacuum pump to vacuumize, purging the device with nitrogen for 3 times, and then purging the device with helium for 1 time. And introducing helium gas into the arc discharge device until the absolute pressure is 0.03-0.05 MPa, then opening circulating cooling water, switching on a direct current power supply, keeping the distance between the two electrodes between 2-4mm, continuously adjusting the voltage, keeping the arc stable, and finally keeping the working voltage of the arc plasma between 16-22V and the working current between 85-93A. During the arc discharge reaction, the absolute pressure of helium is maintained at 0.04-0.05 MPa. After the anode graphite rod is completely consumed, the power supply is turned off, the cooling water is stopped to be introduced, and the filamentous film-shaped substances on the wall of the device are collected to obtain the gasoline adsorption desulfurization catalyst which takes the single-walled carbon nanotube as the carrier and is prepared in the embodiment, the catalyst is marked as C1, and the contents of the hydrogenation active component, znO and the single-walled carbon nanotube are detected and listed in Table 2.
Example 2
Uniformly mixing Ni powder (with the particle size of 140-160 mu m), znO powder (with the particle size of 140-160 mu m) and catalytic slurry oil according to the proportion of 13 wt%, 45 wt% and 42 wt%, filling the mixture into a graphite rod (with the length of 70mm, the diameter of 8mm, the axial length of the cavity of 50mm and the inner diameter of the cavity of 5 mm) with a cavity, and then sealing the graphite rod to obtain the anode graphite rod. Placing the anode graphite rod and the cathode graphite rod (solid graphite rod, the diameter is 20mm, and the length is 30 mm) in an arc discharge plasma device, closing a cabin door of the device, starting a vacuum pump to vacuumize, purging the device with nitrogen for 3 times, and then purging the device with helium for 1 time. And introducing helium gas into the arc discharge device until the absolute pressure is 0.03-0.05 MPa, then opening circulating cooling water, switching on a direct current power supply, keeping the distance between the two electrodes between 2-4mm, continuously adjusting the voltage, keeping the arc stable, and finally keeping the working voltage of the arc plasma between 18-24V and the working current between 87-95A. During the arc discharge reaction, the absolute pressure of helium is maintained at 0.04-0.05 MPa. After the anode graphite rod is consumed, the power supply is turned off, the cooling water is stopped to be introduced, the silk film-shaped substances on the wall of the device are collected, the gasoline adsorption desulfurization catalyst which is prepared by the embodiment and takes the single-walled carbon nanotube as the carrier is obtained and marked as C2, and the contents of the hydrogenation active component, znO and the single-walled carbon nanotube are detected and listed in Table 2.
Example 3
Uniformly mixing Ni powder (with the particle size of 140-160 mu m), znO powder (with the particle size of 140-160 mu m) and catalytic slurry oil according to the proportion of 18 wt%, 45 wt% and 37 wt%, filling the mixture into a graphite rod (with the length of 70mm, the diameter of 8mm, the axial length of the cavity of 50mm and the inner diameter of the cavity of 5 mm) with a cavity, and then sealing the graphite rod to obtain the anode graphite rod. Placing the anode graphite rod and the cathode graphite rod (solid graphite rod with the diameter of 20mm and the length of 30 mm) in an arc discharge plasma device, closing a cabin door of the device, starting a vacuum pump to vacuumize, purging the device with nitrogen for 3 times, and then purging the device with helium for 1 time. And introducing helium gas into the arc discharge device until the absolute pressure is 0.03-0.05 MPa, then opening circulating cooling water, switching on a direct current power supply, keeping the distance between the two electrodes between 2-4mm, continuously adjusting the voltage, keeping the arc stable, and finally keeping the working voltage of the arc plasma between 15-22V and the working current between 87-93A. During the arc discharge reaction, the absolute pressure of helium is maintained at 0.04-0.05 MPa. After the anode graphite rod is completely consumed, the power supply is turned off, the cooling water is stopped to be introduced, and the filamentous film-shaped substances on the wall of the device are collected to obtain the gasoline adsorption desulfurization catalyst which takes the single-walled carbon nanotube as the carrier and is prepared in the embodiment, the catalyst is marked as C3, and the contents of the hydrogenation active component, znO and the single-walled carbon nanotube are detected and listed in Table 2. The TEM photographs of the catalyst C3 are shown in FIGS. 1-2, and it can be seen that Ni and ZnO particles are uniformly supported on the single-walled carbon nanotube.
Example 4
Uniformly mixing Ni powder (with the particle size of 140-160 mu m), znO powder (with the particle size of 140-160 mu m) and catalytic slurry oil according to the proportion of 24 wt%, 45 wt% and 31 wt%, filling the mixture into a graphite rod (with the length of 70mm, the diameter of 8mm, the axial length of the cavity of 50mm and the inner diameter of the cavity of 5 mm) with a cavity, and then sealing the graphite rod to obtain the anode graphite rod. Placing the anode graphite rod and the cathode graphite rod (solid graphite rod, the diameter is 20mm, and the length is 30 mm) in an arc discharge plasma device, closing a cabin door of the device, starting a vacuum pump to vacuumize, purging the device with nitrogen for 3 times, and then purging the device with helium for 1 time. And introducing helium gas into the arc discharge device until the absolute pressure is 0.03-0.05 MPa, then opening circulating cooling water, switching on a direct current power supply, keeping the distance between the two electrodes between 2-4mm, continuously adjusting the voltage, keeping the arc stable, and finally keeping the working voltage of the arc plasma between 14-23V and the working current between 85-94A. During the arc discharge reaction, the absolute pressure of helium is maintained at 0.04-0.05 MPa. After the anode graphite rod is consumed, the power supply is turned off, the cooling water is stopped to be introduced, the silk film-shaped substances on the wall of the device are collected, the gasoline adsorption desulfurization catalyst which is prepared by the embodiment and takes the single-walled carbon nanotube as the carrier is obtained and marked as C4, and the contents of the hydrogenation active component, znO and the single-walled carbon nanotube are detected and listed in Table 2.
Example 5
Uniformly mixing Ni powder (with the particle size of 140-160 mu m), znO powder (with the particle size of 140-160 mu m) and catalytic slurry oil according to the proportion of 18 wt%, 30 wt% and 52 wt%, filling the mixture into a graphite rod (with the length of 70mm, the diameter of 8mm, the axial length of the cavity of 50mm and the inner diameter of the cavity of 5 mm) with a cavity, and then sealing the graphite rod to obtain the anode graphite rod. Placing the anode graphite rod and the cathode graphite rod (solid graphite rod with the diameter of 20mm and the length of 30 mm) in an arc discharge plasma device, closing a cabin door of the device, starting a vacuum pump to vacuumize, purging the device with nitrogen for 3 times, and then purging the device with helium for 1 time. And then introducing helium gas into the arc discharge device until the absolute pressure is 0.03-0.05 MPa, then opening circulating cooling water, switching on a direct current power supply, keeping the distance between the two electrodes between 2-4mm, continuously adjusting the voltage, keeping the arc stable, and finally keeping the working voltage of the arc plasma between 15-23V and the working current between 87-93A. During the arc discharge reaction, the absolute pressure of helium is maintained at 0.04-0.05 MPa. After the anode graphite rod is completely consumed, the power supply is turned off, the cooling water is stopped to be introduced, and the filamentous film-shaped substances on the wall of the device are collected to obtain the gasoline adsorption desulfurization catalyst which takes the single-walled carbon nanotube as the carrier and is prepared in the embodiment, the catalyst is marked as C5, and the contents of the hydrogenation active component, znO and the single-walled carbon nanotube are detected and listed in Table 2.
Example 6
Uniformly mixing Ni powder (with the particle size of 140-160 mu m), znO powder (with the particle size of 140-160 mu m) and catalytic slurry oil according to the proportion of 18 wt%, 60 wt% and 22 wt%, filling the mixture into a graphite rod (with the length of 70mm, the diameter of 8mm, the axial length of the cavity of 50mm and the inner diameter of the cavity of 5 mm) with a cavity, and then sealing the graphite rod to obtain the anode graphite rod. Placing the anode graphite rod and the cathode graphite rod (solid graphite rod with the diameter of 20mm and the length of 30 mm) in an arc discharge plasma device, closing a cabin door of the device, starting a vacuum pump to vacuumize, purging the device with nitrogen for 3 times, and then purging the device with helium for 1 time. And introducing helium gas into the arc discharge device until the absolute pressure is 0.03-0.05 MPa, then opening circulating cooling water, switching on a direct current power supply, keeping the distance between the two electrodes between 2-4mm, continuously adjusting the voltage, keeping the arc stable, and finally keeping the working voltage of the arc plasma between 17-22V and the working current between 86-94A. During the arc discharge reaction, the absolute pressure of helium is maintained at 0.04-0.05 MPa. After the anode graphite rod is completely consumed, the power supply is turned off, the cooling water is stopped to be introduced, and the filamentous film-shaped substances on the wall of the device are collected to obtain the gasoline adsorption desulfurization catalyst which takes the single-walled carbon nanotube as the carrier and is prepared in the embodiment, the catalyst is marked as C6, and the contents of the hydrogenation active component, znO and the single-walled carbon nanotube are detected and listed in Table 2.
Example 7
A gasoline adsorption desulfurization catalyst was prepared according to the method of example 3, except that Co powder (particle size of 140 to 160 μm) was used in the same amount in place of Ni powder. The catalyst prepared in this example was designated as C7, and the contents of its hydrogenation active component, znO and single-walled carbon nanotubes were measured and listed in table 2.
Example 8
The gasoline adsorption desulfurization catalyst was prepared according to the method of example 3, except that Ni powder (particle size of 140 to 160 μm) and Co powder (particle size of 140 to 160 μm) in a weight ratio of 1: 9 wt% of Ni powder, 9 wt% of Co powder, 45 wt% of ZnO powder and 37 wt% of catalytic slurry oil. The catalyst prepared in this example was designated as C8, and the contents of its hydrogenation active component, znO and single-walled carbon nanotubes were measured and listed in table 2.
Example 9
A gasoline adsorption desulfurization catalyst was prepared according to the method of example 3, except that the particle size of Ni powder was 200 to 300 μm and the particle size of ZnO powder was 200 to 300 μm. The catalyst prepared in this example was designated as C9, and the contents of its hydrogenation active component, znO and single-walled carbon nanotubes were measured and listed in table 2. The TEM photograph of catalyst C9 is shown in fig. 3, and from a comparison of fig. 3 and fig. 2, it can be seen that the catalyst prepared in this example has larger Ni and ZnO particle diameters than example 3.
TABLE 2
Comparative example 1 is used to illustrate a method of preparing a gasoline adsorption desulfurization catalyst, which is different from the present disclosure.
Comparative example 1
The method is characterized in that Ni is used as a hydrogenation active component, znO is used as an adsorption active component, a single-walled carbon nanotube is used as a carrier, and the gasoline adsorption desulfurization catalyst is prepared by adopting an impregnation method, and comprises the following specific steps: adding 84g of nickel nitrate hexahydrate into 300 ml of water for dissolving to obtain an acidic aqueous solution; adding 43g of zinc oxide into the acidic aqueous solution, uniformly grinding, then adding 40g of single-walled carbon nanotubes, and continuously grinding uniformly to obtain a raw material mixture. And extruding the raw material mixture into strips, drying the strips at 120 ℃ for 1 hour, and roasting the strips in a muffle furnace at 550 ℃ for 1 hour to prepare the desulfurization catalyst of the comparative example, which is recorded as DC1.
Test examples
The catalysts prepared in examples 1 to 9 and comparative example 1 were subjected to hydrodesulfurization activity evaluation on a fluidized bed reaction apparatus.
The industrial catalytic cracking gasoline with 500 mug/g of sulfur content and 89 of RON is adopted, and the loading amount of the catalyst is 30mL. Industrial catalytic cracking gasoline, catalysts C1-C9 and DC1 are reacted at the temperature of 350 ℃, the reaction pressure of 3.0MPa and the weight hourly space velocity of 10h -1 And carrying out contact reaction under the hydrogen condition that the volume ratio of hydrogen to oil is 400, and sampling and analyzing after 100h of reaction. The evaluation results are shown in Table 3.
The method for measuring the total sulfur content in the oil sample is wavelength dispersion X-ray fluorescence spectrometry (GB/T11140-2008).
The sulfur removal rate was calculated according to the following formula:
η(％)＝(1-c 2 /c 1 )×100％，
wherein c is 1 Representing the sulfur content of the commercial catalytically cracked gasoline feedstock, c 2 Representing the sulfur content of the gasoline after the reaction.
The RON was determined by GB/T5487-2015.
The RON loss was calculated according to the following equation:
RON loss = RON of industrial catalytically cracked gasoline feedstock-RON of gasoline after reaction
TABLE 3
As can be seen from the data in Table 3, the gasoline adsorption desulfurization catalysts (C1-C9) of the present disclosure have higher desulfurization activity, significantly improved desulfurization rate compared to comparative example DC1 while reducing RON loss, and lower sulfur content of gasoline after reaction. As can be seen from the comparison between examples 1 to 6, when the content of the hydrogenation active component is 13 to 24 wt%, the content of ZnO is 45 to 60 wt%, and the content of the catalytic slurry oil is 22 to 42 wt%, based on the total weight of the mixed material, the desulfurization rate can be further improved.
The preferred embodiments of the present disclosure are described in detail above with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details in the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (5)
1. A method for preparing a gasoline adsorption desulfurization catalyst, which is characterized by comprising the following steps:
a. filling a mixed material containing a hydrogenation active component, znO and catalytic slurry oil into a graphite rod with a cavity, and then sealing the graphite rod to obtain an anode graphite rod; the hydrogenation active component is Ni and/or Co; based on the total weight of the mixed material, the content of the hydrogenation active component is 13-24 wt%, the content of ZnO is 45-60 wt%, and the content of the catalytic slurry oil is 22-42 wt%;
b. b, placing the anode graphite rod and the cathode graphite rod obtained in the step a in an arc discharge device, enabling the anode graphite rod and the cathode graphite rod to generate arc discharge in a helium or argon atmosphere, and collecting a gasoline adsorption desulfurization catalyst which is obtained in the arc discharge device and takes the single-walled carbon nanotube as a carrier after the anode graphite rod is consumed;
wherein the aromatic hydrocarbon content of the catalytic slurry oil is 50-60 wt%; the hydrogenation active component is a Ni simple substance and/or a Co simple substance, and the grain diameters of the hydrogenation active component and ZnO are respectively 140-160 mu m.
2. The method of claim 1, wherein in step b, the arc discharge conditions comprise: the direct distance between the anode graphite rod and the cathode graphite rod is 2-4mm, the discharge voltage is 10-30V, the discharge current is 80-100A, and the absolute pressure is 0.03-0.05 MPa.
3. The method according to claim 1, wherein the graphite rod having a cavity has a length of 60 to 80mm and a diameter of 7 to 10mm; the cavity extends along the axial direction of the graphite rod, the axial length of the cavity is 40-60 mm, and the inner diameter of the cavity is 4-6 mm;
the cathode graphite rod is a solid graphite rod, the length of the solid graphite rod is 10-30 mm, and the diameter of the solid graphite rod is 8-20 mm.
4. The gasoline adsorption desulfurization catalyst prepared by the method of any one of claims 1 to 3, wherein the catalyst comprises 12 to 22 wt% of hydrogenation active components, 43 to 59 wt% of ZnO and 24 to 45 wt% of single-walled carbon nanotubes based on the dry weight of the catalyst, and the hydrogenation active components are Ni and/or Co.
5. Use of the catalyst of claim 4 for adsorptive desulfurization of gasoline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810779827.5A CN110721692B (en) | 2018-07-16 | 2018-07-16 | Gasoline adsorption desulfurization catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810779827.5A CN110721692B (en) | 2018-07-16 | 2018-07-16 | Gasoline adsorption desulfurization catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110721692A CN110721692A (en) | 2020-01-24 |
| CN110721692B true CN110721692B (en) | 2023-01-13 |
Family
ID=69217329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810779827.5A Active CN110721692B (en) | 2018-07-16 | 2018-07-16 | Gasoline adsorption desulfurization catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110721692B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101102838A (en) * | 2004-11-17 | 2008-01-09 | 海珀里昂催化国际有限公司 | Method for preparing catalyst supports and supported catalysts from single walled carbon nanotubes |
| CN101607204A (en) * | 2009-06-03 | 2009-12-23 | 阜阳师范学院 | CNT is hydrodesulfurization, hydrodenitrogenation catalyst of carrier and preparation method thereof |
| CN102343276A (en) * | 2011-07-25 | 2012-02-08 | 中国石油大学(华东) | Catalyst for deep desulfuration and octane number increase for gasoline and preparation and application methods thereof |
| WO2013065007A1 (en) * | 2011-11-03 | 2013-05-10 | Indian Oil Corporation Ltd. | Nano structured adsorbent for removal of sulphur from diesel and gasoline like fuels and process for preparing the same |
| CN105772073A (en) * | 2016-03-29 | 2016-07-20 | 中国石油大学(华东) | Preparation method of coupling type sulfur-resistant diesel hydrogenation and desulfurizing catalyst |
| WO2017024421A1 (en) * | 2015-08-12 | 2017-02-16 | 华北电力大学（保定） | Multi-walled carbon nanotube catalyst, preparation method therefor and use thereof |
| WO2017093012A1 (en) * | 2015-12-02 | 2017-06-08 | Haldor Topsøe A/S | Regenerable sulfur adsorption and removal |
| CN108047495A (en) * | 2017-12-06 | 2018-05-18 | 山东大展纳米材料有限公司 | A kind of in-situ preparation method of carbon nanotubes and the superpower compounded mix of carbon black |
| CN110721699A (en) * | 2018-07-16 | 2020-01-24 | 中国石油化工股份有限公司 | Gasoline hydrodesulfurization catalyst and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5497049B2 (en) * | 2008-10-24 | 2014-05-21 | ナノシス・インク． | Electrochemical catalyst for fuel cell |
-
2018
- 2018-07-16 CN CN201810779827.5A patent/CN110721692B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101102838A (en) * | 2004-11-17 | 2008-01-09 | 海珀里昂催化国际有限公司 | Method for preparing catalyst supports and supported catalysts from single walled carbon nanotubes |
| CN101607204A (en) * | 2009-06-03 | 2009-12-23 | 阜阳师范学院 | CNT is hydrodesulfurization, hydrodenitrogenation catalyst of carrier and preparation method thereof |
| CN102343276A (en) * | 2011-07-25 | 2012-02-08 | 中国石油大学(华东) | Catalyst for deep desulfuration and octane number increase for gasoline and preparation and application methods thereof |
| WO2013065007A1 (en) * | 2011-11-03 | 2013-05-10 | Indian Oil Corporation Ltd. | Nano structured adsorbent for removal of sulphur from diesel and gasoline like fuels and process for preparing the same |
| WO2017024421A1 (en) * | 2015-08-12 | 2017-02-16 | 华北电力大学（保定） | Multi-walled carbon nanotube catalyst, preparation method therefor and use thereof |
| CN107107038A (en) * | 2015-08-12 | 2017-08-29 | 华北电力大学（保定） | A kind of multiple-wall carbon nanotube catalyst and its preparation method and application |
| WO2017093012A1 (en) * | 2015-12-02 | 2017-06-08 | Haldor Topsøe A/S | Regenerable sulfur adsorption and removal |
| CN105772073A (en) * | 2016-03-29 | 2016-07-20 | 中国石油大学(华东) | Preparation method of coupling type sulfur-resistant diesel hydrogenation and desulfurizing catalyst |
| CN108047495A (en) * | 2017-12-06 | 2018-05-18 | 山东大展纳米材料有限公司 | A kind of in-situ preparation method of carbon nanotubes and the superpower compounded mix of carbon black |
| CN110721699A (en) * | 2018-07-16 | 2020-01-24 | 中国石油化工股份有限公司 | Gasoline hydrodesulfurization catalyst and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| "Present Advancement in Production of Carbon Nanotubes and Their Derivatives from Industrial Waste with Promising Applications";Kerdnawee，K et al.;《KONA POWDER AND PARTICLE JOURNAL》;20160130(第34期);第29页2.2节 * |
| "催化裂化汽油S-Zorb反应吸附脱硫工艺吸附剂的研究";孟璇;《中国博士学位论文全文数据库 工程科技I辑》;20120815(第08期);文第96页第1-2段 * |
| "电弧等离子体法制备石油残渣基碳纳米管及其应用";徐凯;《中国博士学位论文全文数据库 工程科技I辑》;20180215(第02期);正文第1页第4段，第2页第2段，第3页第2段，第37-38页第3.3节，43页3.4.3节,第69页第3段，70页第2、4段，73页第5.5节，81页5.8.2节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110721692A (en) | 2020-01-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4472556B2 (en) | Hydrocarbon hydrotreating catalyst, process for producing the same, and hydrotreating process for hydrocarbon oil | |
| CN102485332B (en) | Distillate oil hydrogenation deacidification catalyst containing molecular sieve, its preparation and application | |
| TWI558455B (en) | Hydrodemetallization and hydrodesulphurization catalysts, and use in a single formulation in a concatenated process | |
| CA2907604C (en) | Hydrodesulfurization catalyst for diesel oil and hydrotreating method for diesel oil | |
| Badoga et al. | Effect of synthesis technique on the activity of CoNiMo tri-metallic catalyst for hydrotreating of heavy gas oil | |
| CA1068251A (en) | Process for improved carbon supported hydrodesulfurization catalysts | |
| CN102343249A (en) | Hydrocarbon oil desulphurization adsorbent, its preparation method and its application | |
| WO2009105749A2 (en) | Catalyst to attain low sulfur gasoline | |
| Shi et al. | Preparation and evaluation of hydrotreating catalysts based on activated carbon derived from oil sand petroleum coke | |
| CN103861595A (en) | Residual oil hydrogenation catalyst as well as preparation method and application thereof | |
| JP4864106B2 (en) | Method for producing hydrocarbon oil hydrotreating catalyst | |
| CN101259420A (en) | Hydrogenation catalysts and its manufacturing method and use | |
| JP4519719B2 (en) | Method for producing hydrotreating catalyst for hydrocarbon oil, and hydrotreating method for hydrocarbon oil | |
| CN110721692B (en) | Gasoline adsorption desulfurization catalyst and preparation method and application thereof | |
| CN110721699B (en) | Gasoline hydrodesulfurization catalyst and preparation method and application thereof | |
| Iwamoto et al. | Effect of cobalt on the sulfiding temperature of CoOMoO3/Al2O3 studied by temperature programmed sulfiding | |
| CN110882700B (en) | Preparation method of gasoline hydrodesulfurization catalyst, gasoline hydrodesulfurization catalyst and application thereof | |
| CN116408104A (en) | Adsorption desulfurization catalyst and preparation method and application thereof | |
| JP2711871B2 (en) | Method for producing hydrotreating catalyst from hydrogel | |
| CN105536857B (en) | A kind of preparation method of hydrocracking catalyst | |
| CN105749987A (en) | Hydrogenation catalyst and pretreatment method and application thereof | |
| TWI611015B (en) | Hydrodesufurization catalyst for hydrocarbon oil | |
| JP2006306974A (en) | Catalyst for hydrotreating hydrocarbon oil, method for producing the same and method for hydrotreating hydrocarbon oil | |
| Aryee et al. | Synthesis and Characterization of NiMo Catalysts Supported on Fine Carbon Particles for Hydrotreating: Effects of Metal Loadings in Catalyst Formulation | |
| CN115555001B (en) | Alkyne-rich carbon four-selective hydrogenation catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |