CN111151239A - Attapulgite-loaded vanadium oxidation desulfurization catalyst and preparation method and application thereof - Google Patents
Attapulgite-loaded vanadium oxidation desulfurization catalyst and preparation method and application thereof Download PDFInfo
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 64
- 230000023556 desulfurization Effects 0.000 title claims abstract description 64
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 63
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 63
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 50
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- 238000000034 method Methods 0.000 claims description 22
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 17
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- 150000003568 thioethers Chemical class 0.000 description 2
- JGYOEDXSKNEVDJ-UHFFFAOYSA-N 2-hydroperoxy-2-methylpropane;octane Chemical compound CC(C)(C)OO.CCCCCCCC JGYOEDXSKNEVDJ-UHFFFAOYSA-N 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
-
- B01J35/615—
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
- C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates
Abstract
The invention relates to an attapulgite loaded vanadium oxidation desulfurization catalyst and a preparation method and application thereof, wherein the catalyst takes physically modified attapulgite as a carrier and vanadium as an active component; the preparation method comprises mixing attapulgite with dispersant, homogenizing, ultrasonic dispersing, grading, solid-liquid separating, press filtering, dehydrating, oven drying, and pulverizing to obtain physically modified attapulgite; then preparing a vanadium source solution, dipping the physically modified attapulgite in the vanadium source solution, and drying and roasting to obtain the attapulgite-loaded vanadium oxidation desulfurization catalyst; the attapulgite loaded vanadium oxidation desulfurization catalyst can be applied to the field of deep desulfurization of fuel oil. Compared with the prior art, the catalyst has the advantages of simple preparation method, convenient operation, low cost, high catalytic efficiency, long cycle life and the like, and has wide industrial application prospect.
Description
Technical Field
The invention belongs to the field of deep desulfurization of fuel oil, and relates to a catalyst taking clay as a carrier, a preparation method and application thereof, in particular to an attapulgite-loaded vanadium oxidation desulfurization catalyst, a preparation method and application thereof, and specifically relates to a fuel oil oxidation desulfurization catalyst taking physically modified attapulgite as a carrier, a preparation method thereof and application thereof in the field of deep desulfurization of fuel oil.
Background
With the development of society, people use more and more vehicles in travel, and organic sulfur substances contained in fuel oil used by vehicles release a large amount of nitrogen oxides and sulfides after combustion, which is an important reason for causing environmental pollution. The national five standards have clearly defined that the sulfur content in the fuel is below 10ppm, so the development of ultra-low sulfur fuel is not technically feasible. At present, the fuel oil desulfurization technology commonly used at home and abroad can be generally divided into two routes of hydrodesulfurization and non-hydrodesulfurization, wherein the non-hydrodesulfurization is commonly carried out by oxidative desulfurization, adsorption desulfurization, biological desulfurization and the like. Hydrodesulfurization is the earliest and mature technology, but the hydrodesulfurization needs high temperature, high pressure, pure hydrogen and other factors, so that the cost is high, and the hydrodesulfurization hardly has an effect on large sulfide molecules; oxidative desulfurization in non-hydrodesulfurization technologies has the advantages of mild operating conditions, capability of efficiently removing macromolecular sulfides such as Dibenzothiophene (DBT) and derivatives, no consumption of hydrogen, and the like, and thus has attracted extensive attention. Oxidative desulfurization systems are generally classified into two types: the oxidant is mixed with a polar solvent and then placed in the oil phase to form a biphasic system. In this system, there is a mass transfer limitation, resulting in that ODS reaction is too slow to be suitable for industrial production. Compared to the two-phase oxidation system, the single-phase system uses an oil-soluble oxidizing agent. The oxidant and the sulfide can be sufficiently contacted compared to a two-phase oxidation system. Transition metal oxides are widely used for oxidative desulfurization due to their good redox properties. Simple metal oxides are relatively easy to agglomerate and metal ions are easy to lose in the reaction process, so the metal oxides are generally loaded on a carrier as active ingredients. A commonly used carrier is Al2O3、SiO2、TiO2Or molecular sieves, and the like, and the catalysts are often high in cost and difficult to recycle, so that a new cheap, efficient and recyclable carrier material needs to be researched.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an attapulgite loaded vanadium oxidation desulfurization catalyst, a preparation method and application thereof, which are used for solving the problems of high catalyst cost, low catalytic efficiency and incapability of recycling in the existing dibenzothiophene oxidation desulfurization system.
The purpose of the invention can be realized by the following technical scheme:
an attapulgite loaded vanadium oxidation desulfurization catalyst takes physically modified attapulgite as a carrier and vanadium as an active component.
Further, the specific surface area of the physically modified attapulgite is 100-150m2/g。
The preparation method of the attapulgite supported vanadium oxidation desulfurization catalyst comprises the following steps:
1) mixing the attapulgite with a dispersing agent, and sequentially carrying out homogenization, ultrasonic dispersion, grading, solid-liquid separation, filter pressing, dehydration, drying and grinding treatment to obtain the physically modified attapulgite;
2) preparing a vanadium source solution, soaking the physically modified attapulgite in the vanadium source solution, and then drying and roasting to obtain the attapulgite-loaded vanadium oxidation desulfurization catalyst.
Further, in the step 1), the dispersing agent is isopropanol solution, and suspension liquid with the mass concentration of 0.01-0.02g/ml is prepared.
Further, in the step 1), the particle size of the obtained classification product is 1.5-2.5 μm in the classification process.
Further, in the step 2), in the vanadium source solution, a vanadium source is ammonium metavanadate, and the mass concentration of the vanadium source solution is 1-9 wt%.
Further, in the step 2), the dipping temperature is 75-85 ℃ and the dipping time is 1.5-3h in the dipping process.
Further, in the step 2), the roasting temperature is 450-550 ℃ and the roasting time is 3-6h in the roasting process.
The attapulgite loaded vanadium oxidation desulfurization catalyst can be applied to the field of deep desulfurization of fuel oil.
Further, the attapulgite supported vanadium oxidation desulfurization catalyst is used for catalyzing oxidation desulfurization reaction of dibenzothiophene.
Compared with the prior art, the invention has the following characteristics:
1) the catalyst has high catalytic efficiency: the catalyst is applied to an oxidation desulfurization experiment of dibenzothiophene-octane simulation oil with the S content of 200ppm, under the condition of 60 ℃ and normal pressure, the removal efficiency of DBT reaches more than 99.9% within 30min by taking tert-butyl hydroperoxide as an oxidant;
2) the catalyst has long cycle life: the catalyst is applied to an oxidation desulfurization experiment of dibenzothiophene-octane simulation oil with the S content of 200ppm, and after the reaction is finished, the catalyst is centrifuged, dried at low temperature and recovered, and then subjected to a cycle life experiment, and the result shows that the desulfurization efficiency of the catalyst is basically kept unchanged after the catalyst is repeatedly used for 5 times;
3) the preparation process of the catalyst is simple: the catalyst of the invention has the advantages of simple preparation method, easy operation, low cost and wide industrial application prospect.
Drawings
FIG. 1 is an XRD pattern of the catalyst prepared from the physically modified attapulgite and ammonium metavanadate precursor solutions of different concentrations in example 7;
FIG. 2 is a Transmission Electron Microscope (TEM) chromatogram of the catalyst prepared from the physically modified attapulgite and ammonium metavanadate precursor solutions with different concentrations in example 7;
FIG. 3 is a graph comparing the oxidative desulfurization rates of dibenzothiophenes over different catalysts in example 8;
FIG. 4 is a graph comparing the oxidative desulfurization rates of dibenzothiophenes over different loadings of catalyst in example 8;
FIG. 5 is a graph showing the comparison of the oxidative desulfurization rates of dibenzothiophene with V/nano-ATP (2%) at different reaction temperatures in example 9;
FIG. 6 is a graph showing the results of the cyclic catalysis experiment for V/nano-ATP (2%) in example 10.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1:
in the embodiment, physically modified attapulgite is used as a carrier, 2 wt% ammonium metavanadate precursor solution is used as a vanadium source to prepare the catalyst, and the catalyst is used for the catalytic oxidation reaction of DBT, and the specific process is as follows:
1) preparing a physically modified attapulgite carrier: mixing attapulgite raw soil serving as a raw material with isopropanol serving as a dispersing agent, preparing suspension liquid with the mass concentration of 0.014g/ml, homogenizing, performing ultrasonic dispersion treatment, classifying by 5 grades in sequence until the 2-micron particle size fraction of the attapulgite accounts for more than 90%, performing solid-liquid separation, and performing filter pressing, dehydration, drying and grinding treatment to obtain the physically modified attapulgite;
2) preparation of the catalyst: taking 0.2g of physically modified attapulgite, mixing with 2.5g of 2 wt% ammonium metavanadate precursor solution, stirring for 2h under the condition of a water bath at 80 ℃, and then sequentially centrifuging, drying and roasting to obtain a catalyst, which is recorded as V/nano-ATP (2%), wherein the roasting temperature in the roasting process is 500 ℃, the roasting time is 4h, and the roasting atmosphere is oxygen;
3) DBT oxidative desulfurization experiments: 5g of dibenzothiophene-octane simulation oil with the sulfur content of 200ppm, 40mg of catalyst and 40mg of 30 wt% of tert-butyl hydroperoxide-octane solution are sequentially added into a closed container with magnetic stirring as an oxidant, then the mixture is magnetically stirred for 60min at the temperature of 60 ℃ for reaction, samples are taken at the moments of 5min, 10min, 20min, 30min and 60min respectively, the content of dibenzothiophene in the sample simulation oil is detected by adopting a GC-FPD (gas chromatography-flat panel display), and the desulfurization rate of the sample simulation oil is calculated.
Wherein, the oxidant in the reaction system is extracted by octane before being added, so the reaction system belongs to a homogeneous system.
Example 2:
in the embodiment, the physically modified attapulgite is used as a carrier, 4 wt% of ammonium metavanadate precursor solution is used as a vanadium source, and the catalyst is prepared and used for the catalytic oxidation reaction of DBT.
Wherein, in the preparation process of the catalyst, the concentration of the ammonium metavanadate precursor solution is 4 wt%, the prepared catalyst is marked as V/nano-ATP (4%), and the rest process is the same as that of example 1.
Example 3:
in the embodiment, the physically modified attapulgite is used as a carrier, 8 wt% of ammonium metavanadate precursor solution is used as a vanadium source, and the catalyst is prepared and used for the catalytic oxidation reaction of DBT.
Wherein, in the preparation process of the catalyst, the concentration of the ammonium metavanadate precursor solution is 8 wt%, the prepared catalyst is marked as V/nano-ATP (8%), and the rest processes are the same as in example 1.
Example 4:
in the embodiment, the physically modified attapulgite is used as the catalyst, and the catalyst is used for the catalytic oxidation reaction of DBT. Wherein, the preparation process of the physically modified attapulgite carrier and the DBT oxidation desulfurization experiment process are the same as those in the example 1.
Example 5:
in this embodiment, vanadium pentoxide is used as a catalyst, and the catalyst is used for a catalytic oxidation reaction of DBT, and the specific process is as follows:
1) preparation of the catalyst: 2.5g of 4 wt% ammonium metavanadate solution are dried in an oven at 100 ℃, and then calcined for 4 hours at 500 ℃ in an oxygen atmosphere to prepare a catalyst which is marked as V2O5；
2) The DBT oxidative desulfurization experiments were the same as in example 1.
Example 6:
in the embodiment, unmodified attapulgite is used as a carrier, 4 wt% of ammonium metavanadate precursor solution is used as a vanadium source, and the catalyst is prepared and used for the catalytic oxidation reaction of DBT.
Wherein the concentration of the ammonium metavanadate precursor solution used in the preparation of the catalyst was 4 wt%, and the prepared catalyst was denoted as V-ATP (4%), and the rest of the procedure was the same as in example 1.
Example 7:
this example examines the effect of loading on the catalyst crystal structure.
XRD and TEM characterization of V/nano-ATP (2%) in example 1, V/nano-ATP (4%) in example 2, and V/nano-ATP (8%) in example 3 were performed, respectively, and the results are shown in FIG. 1 and FIG. 2.
As shown in FIG. 1, it is a XRD pattern of the catalyst obtained by immersing the physically modified attapulgite in ammonium metavanadate precursor solutions with different concentrations. As can be seen from the figure, V was successfully calcined at 500 ℃ in an oxygen atmosphere2O5At 2% precursor solution concentration, there is no apparent V2O5Diffraction peaks, demonstrating no bulk of V2O5Agglomeration is favorable for the catalysis of the catalyst.
As shown in fig. 2, it is a transmission electron microscope image of the catalyst obtained by immersing the physically modified attapulgite in ammonium metavanadate precursor solutions with different concentrations. As can be seen from the figure, the equal volume immersion method allows V2O5Uniformly distributed on the surface of the carrier, and the high resolution results are 0.251, 0.212, 0.338nm and V2O5The lattice spacings in the { 211 }, { 102 }, and { 110 } planes are the same, further demonstrating that V is the same2O5And (4) generating.
Example 8:
this example examines the effect of the supported amount on the DBT oxidative desulfurization efficiency of the catalyst, i.e., examines the DBT oxidative desulfurization rate at different times for each of the catalysts in examples 1 to 6, and the results are shown in fig. 3 and 4.
As shown in FIG. 3, pure nano-ATP has no significant desulfurization effect, while pure V2O5The desulfurization rate after 30 minutes was only 78% due to agglomeration in the solution and dissolution of metal ions. When the unmodified attapulgite is used as a carrier, the catalyst obtained by impregnating the ammonium metavanadate precursor solution with the mass fraction of 4 percent can achieve 78 percent of catalytic effect after 30 minutes, but when V is used as the carrier2O5After the nano-ATP is loaded to form the heterogeneous catalyst, the catalytic efficiency is greatly improved, and the desulfurization effect can reach 97 percent in 30 minutes.
As shown in FIG. 4, the attapulgite after physical modification has good catalytic effect when being used as a carrier to load vanadium pentoxide, and can achieve about 99.92% of desulfurization effect (V/nano-ATP (2%)) within about 30min, and the loading amount of the vanadium pentoxide has obvious influence on the catalytic result, and the catalytic effect is the best when the precursor solution has a concentration of 2 wt%.
Example 9:
this example investigates the effect of catalytic reaction temperature on DBT oxidative desulfurization efficiency: the experiment procedure of DBT oxidative desulfurization was the same as that of example 1, except that V/nano-ATP (2%) in example 1 was used as a catalyst, and the experiment results were shown in FIG. 5, wherein the experiments were carried out at three temperatures of 40 deg.C, 60 deg.C and 80 deg.C, respectively.
As shown in FIG. 5, it can be seen that the effect of different temperatures on the oxidative desulfurization efficiency in this example is that the reaction process is adversely affected when the temperature is decreased (40 ℃), the catalytic efficiency is rapidly increased when the temperature is increased to 60 ℃, and further increase of the temperature (80 ℃) has no significant effect on the catalytic effect, and from the economic viewpoint, 60 ℃ is most suitable for the catalytic temperature.
Example 10:
in this example, the catalyst cycle life was examined, and the results are shown in FIG. 6, using V/nano-ATP (2%) as the catalyst prepared in example 1.
As shown in fig. 6, which is a result of the cycle experiment of the catalyst in this example, it can be seen that the performance of the catalyst is relatively stable, and the catalytic efficiency is not substantially reduced after 5 times of cycle use.
Example 11:
the attapulgite supported vanadium oxidation desulfurization catalyst is prepared by the following steps:
1) the attapulgite is mixed with isopropanol serving as a dispersant to prepare suspension liquid with the mass concentration of 0.01g/mL, and then the suspension liquid is subjected to homogenization, ultrasonic dispersion, classification, solid-liquid separation, filter pressing, dehydration, drying and grinding in sequence to obtain the material with the specific surface area of 100-150m2Physically modified attapulgite in the same manner as in example 1;
2) preparing 1 wt% ammonium metavanadate solution, soaking the physically modified attapulgite in the vanadium source solution for 3h at 75 ℃, and then drying and roasting to obtain the attapulgite-loaded vanadium oxidation desulfurization catalyst.
Wherein, in the step 1), the particle size of the obtained grading product is 1.5-2.5 μm in the grading process.
In the step 2), the roasting temperature in the roasting process is 450 ℃, the roasting time is 6h, and the roasting atmosphere is oxygen.
Example 12:
the attapulgite supported vanadium oxidation desulfurization catalyst is prepared by the following steps:
1) the attapulgite is mixed with isopropanol serving as a dispersant to prepare suspension liquid with the mass concentration of 0.015g/mL, and then the suspension liquid is subjected to homogenization, ultrasonic dispersion, classification, solid-liquid separation, filter pressing, dehydration, drying and grinding in sequence to obtain the material with the specific surface area of 100-150m2Physically modified attapulgite in the same manner as in example 1;
2) preparing 9 wt% ammonium metavanadate solution, soaking the physically modified attapulgite in the vanadium source solution at 85 ℃ for 1.5h, and then drying and roasting to obtain the attapulgite-supported vanadium oxidation desulfurization catalyst.
Wherein, in the step 1), the particle size of the obtained grading product is 1.5-2.5 μm in the grading process.
In the step 2), the roasting temperature in the roasting process is 550 ℃, the roasting time is 3 hours, and the roasting atmosphere is oxygen.
Example 13:
the attapulgite supported vanadium oxidation desulfurization catalyst is prepared by the following steps:
1) the attapulgite is mixed with isopropanol serving as a dispersant to prepare suspension liquid with the mass concentration of 0.02g/mL, and then the suspension liquid is subjected to homogenization, ultrasonic dispersion, 5-stage classification, solid-liquid separation, filter pressing, dehydration, drying and powder grinding in sequence to obtain the material with the specific surface area of 100-150m2Physically modified attapulgite in the same manner as in example 1;
2) preparing 2 wt% of ammonium metavanadate solution, soaking the physically modified attapulgite in the vanadium source solution for 2 hours at the temperature of 80 ℃, and then drying and roasting to obtain the attapulgite-loaded vanadium oxidation desulfurization catalyst.
Wherein, in the step 1), the particle size of the obtained grading product is 1.5-2.5 μm in the grading process.
In the step 2), the roasting temperature in the roasting process is 500 ℃, the roasting time is 5 hours, and the roasting atmosphere is oxygen.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The catalyst is characterized in that the catalyst takes physically modified attapulgite as a carrier and vanadium as an active component.
2. The catalyst as claimed in claim 1, wherein the specific surface area of the physically modified attapulgite is 100-150m2/g。
3. The preparation method of the attapulgite-supported vanadium oxidation desulfurization catalyst according to claim 1 or 2, characterized by comprising the following steps:
1) mixing the attapulgite with a dispersing agent, and sequentially carrying out homogenization, ultrasonic dispersion, grading, solid-liquid separation, filter pressing, dehydration, drying and grinding treatment to obtain the physically modified attapulgite;
2) preparing a vanadium source solution, soaking the physically modified attapulgite in the vanadium source solution, and then drying and roasting to obtain the attapulgite-loaded vanadium oxidation desulfurization catalyst.
4. The preparation method of the attapulgite-supported vanadium oxidation desulfurization catalyst according to claim 3, characterized in that in step 1), the dispersant is isopropanol.
5. The method for preparing the attapulgite-supported vanadium oxidation desulfurization catalyst according to claim 3, characterized in that in the step 1), the particle size of the obtained classification product is 1.5-2.5 μm in the classification process.
6. The preparation method of the attapulgite-supported vanadium oxidation desulfurization catalyst according to claim 3, characterized in that in the step 2), the vanadium source solution contains ammonium metavanadate, and the mass concentration of the vanadium source solution is 1-9 wt%.
7. The preparation method of the attapulgite-supported vanadium oxidation desulfurization catalyst according to claim 3, characterized in that in the step 2), the impregnation temperature is 75-85 ℃ and the impregnation time is 1.5-3 h.
8. The method for preparing the attapulgite-supported vanadium oxidation desulfurization catalyst as claimed in claim 3, wherein in the step 2), the calcination temperature is 450-550 ℃ and the calcination time is 3-6 h.
9. The application of the attapulgite supported vanadium oxidation desulfurization catalyst as claimed in claim 1 or 2, characterized in that the attapulgite supported vanadium oxidation desulfurization catalyst is applied in the field of deep desulfurization of fuel oil.
10. The application of the attapulgite supported vanadium oxidation desulfurization catalyst according to claim 9, characterized in that the attapulgite supported vanadium oxidation desulfurization catalyst is used for catalyzing the oxidation desulfurization reaction of dibenzothiophene.
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