CN113171778B - Deep purification desulfurizer for coke oven gas and preparation method and application thereof - Google Patents
Deep purification desulfurizer for coke oven gas and preparation method and application thereof Download PDFInfo
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- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/882—Molybdenum and cobalt
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
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Abstract
The invention relates to a deep purification desulfurizer for coke oven gas and a preparation method and application thereof. The desulfurizer of the invention loads active components Co and Mo on the surface of a titanium dioxide nanotube according to a certain proportion, wherein the active components account for 6-11 wt% of the total mass of the desulfurizer and the balance is the titanium dioxide nanotube. The desulfurizer is suitable for the dry fine desulfurization process of the coke oven gas after primary desulfurization and fine desulfurization, and the optimal application conditions are that the sulfur content in the feed gas is not higher than 20ppm 2 The volume ratio of CO is 5:1, the technological parameters are that the reaction temperature is 200-250 ℃, the reaction pressure is 0.5-3 MPa, and the airspeed is 3800-6000 h ‑1 . By adopting the deep purification desulfurizer for the coke oven gas, the desulfurization rate can reach more than 99.7% and the sulfur residual quantity is lower than 0.1ppm by controlling process parameters.
Description
Technical Field
The invention belongs to the technical field of gas hydrodesulfurization catalysis, and particularly relates to a deep purification desulfurizer for coke oven gas applied to dry desulfurization as well as a preparation method and application thereof.
Background
In coal resource reserves in Shanxi province, 55% of coking coal, 27% of power coal and 18% of anthracite coal are used, and the coal resource endowment characteristics determine that the coking industry as the traditional pillar industry occupies a significant position in the industrial structure of Shanxi province. As a byproduct of the coking industry, the byproduct of Shanxi province is as high as 400 hundred million m each year in recent years 3 Coke oven gas.
The main component of the coke oven gas is H 2 、CH 4 CO and CO 2 It is a good chemical raw material and high-calorific-value fuel. However, the impurities (such as sulfur, tar, benzene, naphthalene, ammonia, and HCN) contained in the oil are various and complex in composition, which seriously affects the application range. Especially, sulfur in various forms is a fatal factor for the poisoning and deactivation of the catalyst in the subsequent application process. Therefore, when coke oven gas is used as a raw material of synthesis gas, the total sulfur content is required to be less than 0.1ppm, even as low as tens of ppb, in order to avoid sulfur poisoning of the catalyst during the synthesis process. At present, the coke oven gas desulfurization process of iron-molybdenum pre-hydrogenation → iron-molybdenum hydrogenation → zinc oxide absorption → nickel-molybdenum hydrogenation → zinc oxide absorption is widely adopted in industrial production, and the main technical problems exist: (1) the high operating temperatures of iron-molybdenum and nickel-molybdenum-aluminum based hydrogenation catalysts (about 350 ℃) lead to methanation, carbon build-up, even in COS and CS 2 In the presence of side reactions such as thiol and thioether; (2) under the action of trace oxygen in the coke oven gas, sulfate is generated on the surface of the iron-molybdenum pre-hydrogenation catalyst to cover an active center, so that the catalytic activity is reduced and the service life is shortened; (3) the traditional zinc oxide desulfurizer can generate COS while absorbing hydrogen sulfide, thereby generating a sulfur release phenomenon and reducing the desulfurization effect. The problems lead to frequent replacement of the catalyst in coke oven gas deep processing enterprises and increase the economic transportation of the enterprisesThe running cost, especially in the bad weather period of the coking industry, makes the survival of enterprises face a severe examination.
In addition, when the coke oven gas is used as return gas, sulfur in the coke oven gas can be transferred into flue gas, so that the atmospheric environmental pollution is caused. The atmospheric pollution emission limit specified in the national Standard "emission Standard of pollutants for coking chemical industry (GB 16171-2012)" is that sulfur dioxide in flue gas does not exceed 50mg/Nm 3 The high control area is lower than 30mg/Nm 3 . However, the wet desulfurization technology widely adopted by coking enterprises at present has poor organic sulfur removal effect and is difficult to meet the existing requirements. In order to achieve the standard emission, part of enterprises are forced to add a secondary wet desulphurization device or a coke oven flue gas desulphurization device, so that the process is complicated, and the operation cost is increased.
Disclosure of Invention
Aims to solve the problem that a desulfurization catalyst is easy to react with COS and CS in the processes of primary desulfurization and fine desulfurization in the prior art 2 The invention aims to provide a novel titanium-based organic sulfur hydrodesulfurization agent, a preparation method and application thereof, and solves the technical problems of reduction of catalytic activity, shortened service life and poor desulfurization effect caused by side reaction or sulfate generation by the action of trace oxygen.
The technical scheme adopted by the invention is as follows.
The desulfurizer for deeply purifying the coke oven gas is characterized in that active components Co and Mo are loaded on the surface of a titanium dioxide nanotube, wherein the molar ratio of the active components Co to Mo is 1:5-1:7, the active components Co and Mo are expressed in the form of oxides, the content of the active components accounts for 6-11 wt% of the total mass of the desulfurizer, and the balance is the titanium dioxide nanotube.
In the deep purification desulfurizer for coke oven gas, the specific surface area is preferably 40-60 m 2 ·g -1 Pore volume of 0.2-0.4 cm 3 ·g -1 And the diameter of the titanium dioxide nanotube is 17-30 nm.
The preparation method of the desulfurizing agent for deeply purifying the coke oven gas comprises the following steps:
1) Mixing glycerol, ethanol and diethyl ether according to a certain volume ratio to obtain a mixed solution,then adding proper amount of TiOSO 4 ·2H 2 Adding O into the mixed solution, performing ultrasonic stirring for 12-40 h at room temperature to obtain a white suspension A, then transferring the white suspension A into a high-pressure reaction kettle, reacting for 15-30 h at 140-180 ℃, cooling the reactant to room temperature after the reaction is finished, filtering to obtain a precipitate, washing the precipitate with absolute ethyl alcohol to neutrality, then placing the washed precipitate to neutrality in a drying oven, and drying for 1-4 h at 30-50 ℃ to obtain a titanium dioxide nanotube intermediate;
2) Adding a certain amount of 10mol/L NaOH solution into the titanium dioxide nanotube intermediate obtained in the step 1), uniformly mixing to obtain a white suspension B, transferring the white suspension B into a high-pressure reaction kettle, adding a certain amount of mixed solution of cobalt nitrate solution and molybdenum nitrate solution, wherein the molar ratio of Co to Mo is 1:5-1:7, and reacting for 15-25 h at the temperature of 150-200 ℃;
3) And after the reaction is finished, carrying out acid washing treatment for 24h by using 0.1mol/L hydrochloric acid, filtering, washing the solid filter residue to be neutral by using deionized water, then placing the solid filter residue into an oven, carrying out gradient temperature rise drying at 80 ℃ and 120 ℃ for 18h, and finally roasting the obtained material at 400-600 ℃ for 2-4 h to obtain the coke oven gas deep purification desulfurizer with Co and Mo active components uniformly dispersed on the surface of the titanium dioxide nanotube.
Further, in the above preparation method, the volume ratio of glycerol, ethanol and diethyl ether is 1.
Further, in the above preparation method, in step 1), the reaction temperature is 150 to 170 ℃ and the reaction time is 23 to 25 hours, preferably the reaction temperature is 160 ℃ and the reaction time is 24 hours.
Further, in the preparation method, in the step 2), the reaction temperature is 165-185 ℃ and the reaction time is 19-21 h, preferably the reaction temperature is 170 ℃ and the reaction time is 20h.
The deep purification desulfurizer for the coke oven gas is suitable for being applied to the dry fine desulfurization process of the coke oven gas after primary desulfurization and fine desulfurization, and a fixed bed reactor is preferably selected as a reactor; the content of sulfur in the raw material gas of the coke oven is not higher than 20ppm 2 The volume ratio of CO was adjusted to 5:1.
Preferably, the desulfurizing agent is first sulfurized before being applied, and the treating method is to use the desulfurizing agent in the volume ratio of H 2 ：CS 2 =97:3 for 4 to 6 hours under the condition of the mixed gas atmosphere and the temperature of 320 to 380 ℃.
Further, the preferable process conditions for the application of the desulfurizing agent are as follows: the reaction temperature is 200-250 ℃, the reaction pressure is 0.5-3 MPa, and the airspeed is 3800-6000 h -1 。
Compared with the prior art, the deep purification desulfurizer for coke oven gas and the preparation method thereof provided by the invention have the following advantages or obvious technical progress:
firstly, the deep purification desulfurizer for coke oven gas provided by the invention preferably adopts a specific surface area of 40-60 m 2 ·g -1 Pore volume of 0.2-0.4 cm 3 ·g -1 The titanium dioxide nanotube with the aperture of 17-30 nm is beneficial to improving the loading capacity of the active component, the active component is an aqueous solution of cobalt nitrate and molybdenum nitrate in the preparation process of the desulfurizer, the aqueous solution is easy to decompose in the roasting process, and the generated gas can improve the dispersion degree of the active component and prevent the active component from agglomerating, so that the catalytic activity of the catalyst is enhanced.
Secondly, the desulfurizer for deeply purifying the coke oven gas, provided by the invention, adopts the titanium dioxide nanotube as the carrier, and is more gamma-Al than the existing desulfurizer industrially used 2 O 3 Carrier, optimum operation temperature is 200-250 deg.C, lower than gamma-Al 2 O 3 The optimum operating temperature of the desulfurizer which is a carrier is 300-400 ℃. In the actual production, when the operation temperature is higher than 300 ℃, the catalyst can generate methanation side reaction, and the temperature of the catalyst bed layer is increased to promote the phenomena of olefin polymerization and coking. Therefore, the desulfurizer provided by the invention avoids application at a higher operating temperature, and has excellent low-temperature activity and coking resistance.
Finally, in a further preferred technical scheme, the desulfurizing agent is subjected to vulcanization treatment before application, so that elemental sulfur can be combined into a catalyst crystal structure, and the sulfur resistance of the catalyst is improved.
Detailed Description
The following describes the specific technical contents of the present invention in detail by way of specific examples.
Example 1
1) Glycerol, ethanol and diethyl ether are mixed according to a volume ratio of 1 4 ·2H 2 Adding O into 10mL of the mixed solution, performing ultrasonic stirring for 30 hours at room temperature to obtain a white suspension A, transferring the white suspension A into a high-pressure reaction kettle, reacting for 24 hours at 160 ℃, cooling the reactant to room temperature after the reaction is finished, filtering to obtain a precipitate, washing the precipitate with absolute ethyl alcohol to be neutral, placing the washed neutral precipitate in a drying oven, and drying for 2 hours at 40 ℃ to obtain a titanium dioxide nanotube intermediate.
2) Adding 150mL of NaOH solution with the concentration of 10mol/L into 10g of the titanium dioxide nanotube intermediate obtained in the step 1), uniformly mixing to obtain white suspension B, transferring the white suspension B into a 100mL high-pressure reaction kettle, adding a proper amount of mixed solution of cobalt nitrate solution and molybdenum nitrate solution with the molar ratio of Co to Mo of 1:5-1:7, and reacting for 20 hours at the temperature of 170 ℃.
3) After the reaction is finished, carrying out acid washing treatment for 24h by using a proper amount of hydrochloric acid with the concentration of 0.1mol/L, filtering, washing solid filter residue to be neutral by using deionized water, then placing the solid filter residue into a drying oven, drying for 14h at 80 ℃, then rapidly heating to 120 ℃, continuing to dry for 4h, and finally roasting the obtained material for 3h at 450 ℃ to obtain the coke oven gas deep purification desulfurizer with Co and Mo active components uniformly dispersed on the surface of the titanium dioxide nanotube, wherein the desulfurizer comprises the following components: expressed in the form of oxide, the content of active components accounts for 10.98wt% of the total mass of the desulfurizer, and the balance is titanium dioxide nanotubes.
Example 2
1) Mixing glycerol, ethanol and diethyl ether according to a volume ratio of 1Then 2.0g of TiOSO 4 ·2H 2 Adding O into 10mL of the mixed solution, performing ultrasonic stirring for 15h at room temperature to obtain a white suspension A, then transferring the white suspension A into a high-pressure reaction kettle, reacting for 16h at 180 ℃, cooling the reactant to room temperature after the reaction is finished, filtering to obtain a precipitate, washing the precipitate with absolute ethyl alcohol to be neutral, then placing the washed neutral precipitate into a drying oven, and drying for 3h at 30 ℃ to obtain a titanium dioxide nanotube intermediate.
2) Adding a certain amount of 10mol/L NaOH solution into the titanium dioxide nanotube intermediate obtained in the step 1), uniformly mixing to obtain a white suspension B, transferring the white suspension B into a 100mL high-pressure reaction kettle, adding a proper amount of mixed solution of cobalt nitrate solution and molybdenum nitrate solution, wherein the molar ratio of Co to Mo is 1:5-1:7, and reacting at the temperature of 150 ℃ for 24 hours;
3) After the reaction is finished, washing the solid filter residue with 0.1mol/L hydrochloric acid for 24h, filtering, washing the solid filter residue with deionized water until the solid filter residue is neutral, placing the solid filter residue into an oven, drying the solid filter residue for 14h at 80 ℃, rapidly heating the solid filter residue to 120 ℃, continuing to dry the solid filter residue for 4h, and finally roasting the obtained material for 4h at 400 ℃ to obtain the coke oven gas deep purification desulfurizer with Co and Mo active components uniformly dispersed on the surface of the titanium dioxide nanotube, wherein the desulfurizer comprises the following components: expressed in the form of oxide, the content of active components accounts for 6.17wt% of the total mass of the desulfurizer, and the balance is titanium dioxide nanotubes.
Example 3
1) Glycerol, ethanol and diethyl ether are mixed according to a volume ratio of 1 4 ·2H 2 Adding O into 10mL of the mixed solution, performing ultrasonic stirring for 40h at room temperature to obtain a white suspension A, then transferring the white suspension A into a high-pressure reaction kettle, reacting for 24h at 160 ℃, cooling the reaction product to room temperature after the reaction is finished, filtering to obtain a precipitate, washing the precipitate with absolute ethyl alcohol to be neutral, then placing the washed neutral precipitate into a drying oven, and drying for 1h at 50 ℃ to obtain a titanium dioxide nanotube intermediate.
2) Adding a certain amount of 10mol/L NaOH solution into the titanium dioxide nanotube intermediate obtained in the step 1), uniformly mixing to obtain a white suspension B, transferring the white suspension B into a 100mL high-pressure reaction kettle, adding a proper amount of mixed solution of cobalt nitrate solution and molybdenum nitrate solution, wherein the molar ratio of Co to Mo is 1:5-1:7, and reacting at the temperature of 200 ℃ for 18 hours;
3) After the reaction is finished, washing the solid filter residue with 0.1mol/L hydrochloric acid for 24 hours, filtering, washing the solid filter residue with deionized water until the solid filter residue is neutral, placing the solid filter residue into an oven, drying the solid filter residue for 14 hours at 80 ℃, rapidly heating the solid filter residue to 120 ℃, continuing to dry the solid filter residue for 4 hours, and finally roasting the obtained material for 2 hours at 550 ℃ to obtain the coke oven gas deep purification desulfurizer with Co and Mo active components uniformly dispersed on the surface of the titanium dioxide nanotube, wherein the desulfurizer comprises the following components: expressed in the form of oxide, the content of active components accounts for 8.46wt% of the total mass of the desulfurizer, and the balance is titanium dioxide nanotubes.
Example 4
1) Glycerol, ethanol and diethyl ether are mixed according to a volume ratio of 1 4 ·2H 2 Adding O into 10mL of the mixed solution, performing ultrasonic stirring at room temperature for 20 hours to obtain a white suspension A, then transferring the white suspension A into a high-pressure reaction kettle, reacting at 180 ℃ for 16 hours, cooling the reaction product to room temperature after the reaction is finished, filtering to obtain a precipitate, washing the precipitate with absolute ethyl alcohol to be neutral, then washing the precipitate to be neutral, placing the precipitate in a drying oven, and drying at 40 ℃ for 3 hours to obtain a titanium dioxide nanotube intermediate;
2) Adding a certain amount of 10mol/L NaOH solution into the titanium dioxide nanotube intermediate obtained in the step 1), uniformly mixing to obtain a white suspension B, transferring the white suspension B into a 100mL high-pressure reaction kettle, adding a certain amount of mixed solution of cobalt nitrate solution and molybdenum nitrate solution, wherein the molar ratio of Co to Mo is 1:5-1:7, and reacting at the temperature of 180 ℃ for 24 hours;
3) After the reaction is finished, washing the solid filter residue with 0.1mol/L hydrochloric acid for 24h, filtering, washing the solid filter residue with deionized water to be neutral, placing the solid filter residue into an oven, drying the solid filter residue for 14h at 80 ℃, rapidly heating the solid filter residue to 120 ℃, continuing to dry the solid filter residue for 4h, and finally roasting the obtained material for 3h at 550 ℃ to obtain the coke oven gas deep purification desulfurizer with Co and Mo active components uniformly dispersed on the surface of the titanium dioxide nanotube, wherein the desulfurizer comprises the following components: expressed in the form of oxide, the content of active components accounts for 7.52wt% of the total mass of the desulfurizer, and the balance is titanium dioxide nanotubes.
In the desulfurizing agent for deep purification of coke oven gas described in examples 1 to 4, the specific surface area of the titanium dioxide nanotube as the carrier is 40 to 60m 2 ·g -1 Pore volume of 0.2-0.4 cm 3 ·g -1 And the average pore diameter is 17-30 nm. The evaluation method and evaluation conditions of the activity of the desulfurizing agent are as follows: a certain amount of the desulfurizing agent prepared in examples 1 to 4 was used in a fixed bed reactor for evaluation of catalytic performance under the following conditions: a. catalyst loading 1ml, then in H 2 ：CS 2 =97:3, vulcanizing for 4 to 6 hours under the condition that the mixed gas atmosphere and the temperature are 320 to 380 ℃; b. after the pre-sulfurization is finished, the reaction temperature is 200-250 ℃, the reaction pressure is 0.5-3 MPa, and the airspeed is 3800-6000 h -1 Under the specified conditions, 2ulC is injected into the raw material gas 4 H 4 S, the reaction was completed, and the conversion was measured, and the results are shown in Table 1.
TABLE 1
The evaluation results in table 1 show that by controlling the process parameters, the desulfurization rate of the deep purification desulfurizer for coke oven gas provided by the invention can reach more than 99.7%, and the maximum sulfur residual amount is not more than 0.1ppm, which indicates that the desulfurizer provided by the invention has excellent low-temperature activity and coking resistance.
Claims (8)
1. The coke oven gas deep purification desulfurizer is characterized in that active components Co and Mo are loaded on the surface of a titanium dioxide nanotube, wherein the molar ratio of the active components Co to Mo is 1:5-1:7, expressed in the form of oxide, the content of the active components accounts for 6-11 wt% of the total mass of the desulfurizer, and the balance is the titanium dioxide nanotube; the specific surface area of the titanium dioxide nanotube is 40-60 m 2 ·g −1 A hole, aThe volume is 0.2-0.4 cm 3 ·g −1 The aperture is 17-30 nm;
the preparation method of the desulfurizing agent for deeply purifying the coke oven gas comprises the following steps:
1) Mixing glycerol, ethanol and diethyl ether according to a certain volume ratio to obtain a mixed solution, and then adding a proper amount of TiOSO 4 ·2H 2 Adding O into the mixed solution, performing ultrasonic stirring for 12-40 h at room temperature to obtain a white suspension A, then transferring the white suspension A into a high-pressure reaction kettle, reacting for 15-30 h at 140-180 ℃, cooling the reactant to room temperature after the reaction is finished, filtering to obtain a precipitate, washing the precipitate with absolute ethyl alcohol to neutrality, then placing the washed precipitate to neutrality in a drying oven, and drying for 1-4 h at 30-50 ℃ to obtain a titanium dioxide nanotube intermediate;
2) Adding a certain amount of 10mol/L NaOH solution into the titanium dioxide nanotube intermediate obtained in the step 1), uniformly mixing to obtain a white suspension B, transferring the white suspension B into a high-pressure reaction kettle, adding a certain amount of mixed solution of cobalt nitrate solution and molybdenum nitrate solution, wherein the molar ratio of Co to Mo is 1:5-1:7, and reacting for 15-25 h at the temperature of 150-200 ℃;
3) And after the reaction is finished, carrying out acid washing treatment for 24h by using 0.1mol/L hydrochloric acid, filtering, washing the solid filter residue to be neutral by using deionized water, then placing the solid filter residue into an oven, carrying out gradient temperature rise drying at 80 ℃ and 120 ℃ for 18h, and finally roasting the obtained material at 400-600 ℃ for 2-4 h to obtain the coke oven gas deep purification desulfurizer with Co and Mo active components uniformly dispersed on the surface of the titanium dioxide nanotube.
2. The desulfurizing agent for deeply purifying coke oven gas according to claim 1, wherein in the step 1), the volume ratio of glycerol to ethanol to diethyl ether is 1.
3. The desulfurizing agent for deeply purifying coke oven gas according to claim 1, wherein in the step 1), the reaction temperature is 150-170 ℃ and the reaction time is 23-25 h.
4. The desulfurizing agent for deeply purifying coke oven gas according to claim 1, wherein in the step 2), the reaction temperature is 165-185 ℃ and the reaction time is 19-21 h.
5. The application of the desulfurizing agent for deeply purifying coke oven gas as defined in any one of claims 1 to 4 in a fixed bed reactor is characterized by being applied to a dry fine desulfurization process of coke oven gas after primary desulfurization and fine desulfurization.
6. The application of the desulfurizing agent for deeply purifying coke oven gas in the fixed bed reactor as claimed in claim 5, wherein the desulfurizing agent is first subjected to a vulcanization treatment before being applied, and the treatment method is to use the desulfurizing agent in a volume ratio of H 2 ：CS 2 =97:3 for 4 to 6 hours under the condition of the mixed gas atmosphere and the temperature of 320 to 380 ℃.
7. The application of the desulfurizing agent for deeply purifying coke oven gas in the fixed bed reactor as claimed in claim 5, wherein the sulfur content in the coke oven gas is in the range of 0.1ppm to 20ppm 2 The volume ratio of CO was 5:1.
8. The application of the desulfurizing agent for deeply purifying coke oven gas in the fixed bed reactor according to claim 5 is characterized in that the application conditions are as follows: the reaction temperature is 200-250 ℃, the reaction pressure is 0.5-3 MPa, the airspeed is 3800-6000 h -1 。
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| "Highly active CoMoS phase on titania nanotubes as new hydrodesulfurization catalysts";J.A. Toledo-Antonio et al.;《Applied Catalysis B: Environmental》;20090327;第90卷;第213页摘要部分，第214页第2.3节 * |
| J.A. Toledo-Antonio et al.."Highly active CoMoS phase on titania nanotubes as new hydrodesulfurization catalysts".《Applied Catalysis B: Environmental》.2009,第90卷第213-223页. * |
| TiO_2纳米管的制备及应用研究进展;肖虹等;《材料导报》;20150210(第03期);第34-38页 * |
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