CN108855115B - Coating catalyst, preparation method and application - Google Patents
Coating catalyst, preparation method and application 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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- B01J23/88—Molybdenum
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0222—Compounds of Mn, Re
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
- B01J20/0244—Compounds of Zn
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
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- 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
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
A coating catalyst is characterized by comprising three parts of a hydrodesulfurization active component, a sulfur adsorbent and a carrier, wherein the mass fraction of the hydrodesulfurization active component is 2.0-20.0wt%, the mass fraction of the sulfur adsorbent is 30.0-80.0wt%, and the balance is the carrier. The invention has the advantages of no need of reduction or pre-vulcanization treatment, simple and convenient use of the catalyst and low start-up cost; the sulfur capacity is higher than that of the common adsorption desulfurization catalyst by more than 10 percent.
Description
Technical Field
The invention relates to a reaction adsorption desulfurization catalyst and a preparation method thereof, in particular to a coating catalyst for reaction adsorption desulfurization and a preparation method and application thereof.
Technical Field
The organic sulfur in the fuel oil can cause great harm to the environment after being combusted, and strict laws and regulations are set by countries in the world to limit the sulfur content in the fuel oil. In recent years, in order to deal with increasingly worsened environment, the national gasoline quality standard completely implements the national fourth standard, and the sulfur content of oil products is reduced from less than 150ppm of the national third standard to less than 50ppm and is reduced by 67%. In Beijing, Shanghai and Jiangsu provinces, Suzhou and Wuxi provinces, Guangzhou and Shenzhen provinces in Guangdong, the quality standard of gasoline reaches the national fifth standard, and the sulfur content of oil products is reduced to less than 10ppm from less than 50ppm of the national fourth standard and then reduced by 80 percent.
China's gasoline mainly comes from catalytic cracking, and the catalytic cracking gasoline has high sulfur content and can be used only after being desulfurized. At present, two methods of fuel oil desulfurization are hydrofining and adsorption desulfurization, but hydrofining consumes a large amount of hydrogen, is high in cost, can saturate olefins and reduces the octane number of gasoline. For diesel fuel, hydrofinishing can improve cetane number, but hydrogen consumption costs are too high. Therefore, a deep desulfurization method with relatively small hydrogen consumption is needed, and the production cost is reduced.
The Kangfei petroleum company develops an S-Zorb adsorption desulfurization technology, and the technology has the temperature of 243--1Adsorbing desulfurization under the conditions of hydrogen and fluidization, and then regenerating the adsorbent by an oxygen-enriched regeneration method, wherein the adsorbent mainly comprises an active component nickel oxide and an adsorbent zinc oxide. The company has improved this technique again in US7182918B 2. The catalyst is less active and requires frequent regeneration in order to increase its strength and reduce aromatics loss.
CN1048418, CN1151333 disclose a novel composition containing zinc oxide, silica, colloidal oxides and promoters, the pore volume and specific surface area being increased by adding pore formers to the colloid, but the catalyst prepared by this method is less strong.
CN1130253C and US6150300 disclose a particulate adsorbent composition comprising a mixture of zinc oxide, silica, alumina, reduced nickel or cobalt, prepared by first preparing zinc oxide with alumina and silica into a particulate support and then loading the nickel, and a method of using the catalyst. The process is complicated, the strength of the catalyst is seriously reduced after the carrier is loaded with nickel through roasting, and pulverization is easily caused.
The prior catalyst taking zinc oxide as an adsorbent has the problems of small sulfur capacity, frequent regeneration of the catalyst and the like. Therefore, there is a need to develop a new type of adsorption desulfurization catalyst to improve these properties to meet the production requirements.
Disclosure of Invention
Aiming at the problems that the prior reaction adsorption desulfurization catalyst has small sulfur capacity, the desulfurization activity is obviously reduced in the middle and later stages of the reaction, the catalyst is frequently regenerated and the like, the invention aims to provide a coated catalyst with a coating structure for improving the sulfur capacity and the desulfurization performance in the middle and later stages of the reaction, and a preparation method and application thereof.
The catalyst comprises three parts of hydrodesulfurization active components, sulfur adsorbent and carrier, wherein the mass fraction of the hydrodesulfurization active components is 2.0-20.0wt%, the mass fraction of the sulfur adsorbent is 30.0-80.0wt%, and the balance is the carrier.
The hydrodesulfurization active component consists of two parts of AB: the molar ratio of B is 0.1-10, A is at least one of nickel oxide and cobalt oxide, B is at least one of molybdenum oxide and tungsten oxide.
The sulfur adsorbent is at least one of zinc oxide, manganese oxide, iron oxide and calcium oxide, and the carrier is at least one of silicon oxide, aluminum oxide and molecular sieve.
The catalyst of the invention has two coatings A and B, obtains a specific layered structure by a special dipping method, and the specific preparation method comprises the following steps:
(1) uniformly kneading the sulfur adsorbent or the precursor thereof, the carrier or the precursor thereof and the promoter, extruding and molding;
(2) drying the sample obtained in the step (1), increasing the temperature from room temperature to 150 ℃ at the heating rate of 10-20 ℃/min during drying, and drying for 6-24h at the temperature;
(3) roasting the sample obtained in the step (2) at the temperature of 400-600 ℃ for 3-12 h;
(4) preparing the precursor of the component B into a solution with the concentration of 0.05-1 mol/L;
(5) adding the solution obtained in the step (4) into the sample obtained in the step (3) for soaking for 2-20h, filtering and drying the sample, increasing the temperature from room temperature to 150 ℃ at the heating rate of 10-20 ℃/min, and drying for 6-24h at the temperature;
(6) roasting the sample obtained in the step (5) at the temperature of 400-600 ℃ for 3-12 h;
7) preparing the precursor of the component A into a solution with the concentration of 0.05-1 mol/L;
(8) adding the solution obtained in the step (7) into the sample obtained in the step (6) for soaking for 2-20h, filtering and drying the sample, increasing the temperature from room temperature to 150 ℃ at the heating rate of 10-20 ℃/min during drying, and drying for 6-24h at the temperature;
(9) and (4) roasting the sample obtained in the step (8) at the temperature of 400-600 ℃ for 3-12h to obtain the required catalyst.
Wherein, the sulfur adsorbent precursor in the step (1) is hydroxide or carbonate of the sulfur adsorbent. The carrier precursor is hydroxide of the carrier. The accelerant is sesbania powder or soluble starch, and the adding amount is 0.5-10wt% of the sulfur adsorbent.
The precursor of the component B is ammonium salt of the component B;
and (7) the precursor of the component A is nitrate of the component A.
The catalyst of the invention is suitable for the desulfurization treatment of sulfur-containing chemical raw materials, wherein the raw materials comprise gas and liquid forms. The catalyst is particularly suitable for reaction adsorption desulfurization of liquid oil products, and has the characteristics of no need of activation modes such as reduction or prevulcanization, simplifying pretreatment flow, shortening start-up time and saving catalyst use cost. The reaction temperature is raised to 200-500 ℃, then the materials are directly fed and reacted, the reaction pressure is 0.1-10.0MPa, the mass space velocity of the fuel oil is 0.2-5.0h-1，H2The volume ratio of oil/oil is 10-600.
THE ADVANTAGES OF THE PRESENT INVENTION
The invention provides a coating structure reaction adsorption desulfurization catalyst, which has the advantages that: the catalyst does not need reduction or pre-vulcanization treatment, is simple and convenient to use, and has low start-up cost; the sulfur capacity is higher than that of the common adsorption desulfurization catalyst by more than 10 percent.
Detailed Description
The invention is further illustrated, but not limited, by the following examples. The sulfur content of the raw material in the inventive example was 500 ppm.
Example 1:
preparing a catalyst: 1) 30g of zinc oxide, 50g of manganese oxide, 18g of aluminum oxide and 0.04g of soluble starch are uniformly mixed, kneaded into dough and extruded into strips. 2) The resulting sample was slowly raised from room temperature to 100 ℃ at a ramp rate of 10 ℃/min, and dried at this temperature for 6 h. 3) Baking at 400 ℃ for 3h to obtain a strip sample. 4) 2.23g of ammonium heptamolybdate was added to deionized water to make the volume of the solution 80ml, and the molybdenum concentration in the solution was 0.149 mol/L. 5) The resulting solution was added to the strip sample and immersed for 2h, the sample was filtered and dried, slowly increasing from room temperature to 110 ℃ at a ramp rate of 12 ℃/min, and dried at this temperature for 6 h. 6) The resulting sample was calcined at 400 ℃ for 3 h. 7) 0.70g of nickel nitrate is taken to prepare a solution with the concentration of 0.05 mol/L. 8) Adding the solution obtained in the step 7) into the sample obtained in the step 6), soaking for 2h, filtering and drying the sample, and slowly increasing the temperature from room temperature to 100 ℃ at the heating rate of 15 ℃/min during drying, and drying for 6h at the temperature. 9) Roasting the sample obtained in the step 8) at 400 ℃ for 3h to obtain the required catalyst.
The obtained catalyst is crushed into 20-40 meshes, 2.0g of catalyst is loaded in a fixed bed reactor, and the catalyst is directly fed and reacted after being heated to 200 ℃. The reaction pressure is 0.1MPa, the mass airspeed of the fuel oil is 0.2h-1，H2The/oil volume ratio was 10. The catalyst composition is shown in Table 1, and the reaction conditions and results are shown in Table 2.
Example 2
Preparing a catalyst: 1) 20g of calcium oxide, 14.9g of ferric hydroxide, 25g of alumina, 75g of soluble silica sol with the silicon dioxide content of 33 percent and 3g of sesbania powder are uniformly mixed and extruded to form strips. 2) The sample was slowly raised from room temperature to 150 ℃ at a ramp rate of 20 ℃/min, and dried at this temperature for 24 h. 3) Baking at 600 ℃ for 12h to obtain a strip sample. 4) 19.46g of ammonium metatungstate was taken, and deionized water was added to make the volume of the solution 45ml, and the tungsten concentration in the solution was 1.21 mol/L. 5) The resulting solution was added to the strip sample and immersed for 20h, the sample was filtered and dried, while slowly increasing the temperature from room temperature to 150 ℃ at a heating rate of 10 ℃/min, and dried at that temperature for 24 h. 6) The resulting sample was calcined at 600 ℃ for 12 h. 7) 6.31g of cobalt nitrate is taken to prepare a solution with the concentration of 1 mol/L. Adding the solution obtained in the step 7) into the sample obtained in the step 6), soaking for 20h, filtering and drying the sample, slowly increasing the temperature from room temperature to 150 ℃ at the heating rate of 20 ℃/min, and drying for 24h at the temperature. 9) Roasting the sample obtained in the step 8) at 600 ℃ for 12h to obtain the required catalyst.
The obtained catalyst is crushed into 20-40 meshes, 2.0g of catalyst is loaded in a fixed bed reactor, and the catalyst is directly fed and reacted after being heated to 500 ℃. The reaction pressure is 5.0MPa, and the mass airspeed of the fuel oil is 5.0h-1，H2The volume/oil ratio was 600. The catalyst composition is shown in Table 1, and the reaction conditions and results are shown in Table 2.
Example 3
Preparing a catalyst: 1) 20g of calcium oxide, 10g of ferric oxide, 30.8g of zinc carbonate, 20g of alumina, 30g of soluble silica sol with the silicon dioxide content of 33 percent, 10g of SBA15 molecular sieve and 5g of sesbania powder are uniformly mixed and extruded into strips. 2) The resulting sample was slowly raised from room temperature to 140 ℃ at a ramp rate of 18 ℃/min, and dried at this temperature for 12 h. 3) Baking at 400 ℃ for 6h to obtain a strip sample. 4) 4.28g of ammonium metatungstate was taken, and deionized water was added to make the volume of the solution 65ml, and the tungsten concentration in the solution was 0.33 mol/L. 5) The resulting solution was added to the strip sample and immersed for 10h, the sample was filtered and dried, while slowly increasing from room temperature to 120 ℃ at a ramp rate of 11 ℃/min, and dried at this temperature for 12 h. 6) The resulting sample was calcined at 400 ℃ for 6 h. 7) 13.62g of nickel nitrate and 8.77g of cobalt nitrate are taken to prepare a solution with the concentration of 0.8 mol/L. 8) Adding the solution obtained in the step 7) into the sample obtained in the step 6), soaking for 10h, filtering and drying the sample, and slowly increasing the temperature from room temperature to 120 ℃ at a heating rate of 13 ℃/min during drying, and drying at the temperature for 12 h. 9) Roasting the sample obtained in the step 8) at 400 ℃ for 6h to obtain the required catalyst.
The obtained catalyst is crushed into 20-40 meshes, 2.0g of catalyst is loaded in a fixed bed reactor, and the catalyst is directly fed and reacted after being heated to 400 ℃. The reaction pressure is 3.0MPa, and the mass airspeed of the fuel oil is 4.0h-1，H2The oil/volume ratio was 300. The catalyst composition is shown in Table 1, and the reaction conditions and results are shown in Table 2.
Example 4
Preparing a catalyst: 1) and (2) uniformly mixing 20g of manganese oxide, 10g of calcium oxide, 50g of zinc oxide, 5g of alumina, 5g of ZSM5 molecular sieve and 4g of sesbania powder, and extruding into strips. 2) The resulting sample was slowly raised from room temperature to 130 ℃ at a ramp rate of 16 ℃/min, and dried at this temperature for 10 h. 3) Baking at 450 deg.C for 8h to obtain strip sample. 4) 2.67g of ammonium metatungstate and 3.07g of ammonium molybdate are taken and added into deionized water to ensure that the volume of the solution is 85ml, and the total concentration of molybdenum and tungsten in the solution is 0.28 mol/L. 5) The resulting solution was added to the strip sample and immersed for 8h, the sample was filtered and dried, slowly increasing from room temperature to 110 ℃ at a ramp rate of 14 ℃/min, and dried at this temperature for 8 h. 6) The resulting sample was calcined at 450 ℃ for 8 h. 7) 19.45g of nickel nitrate is taken to prepare a solution with the concentration of 0.7 mol/L. 8) Adding the solution obtained in the step 7) into the sample obtained in the step 6), soaking for 8h, filtering and drying the sample, and slowly increasing the temperature from room temperature to 110 ℃ at a heating rate of 10 ℃/min during drying, and drying for 8h at the temperature. 9) Roasting the sample obtained in the step 8) at 450 ℃ for 8h to obtain the required catalyst.
The obtained catalyst is crushed into 20-40 meshes, 2.0g of catalyst is loaded in a fixed bed reactor, and the catalyst is directly fed and reacted after being heated to 450 ℃. The reaction pressure is 10.0MPa, and the mass airspeed of the fuel oil is 3.0h-1，H2The oil/volume ratio was 200. The catalyst composition is shown in Table 1, and the reaction conditions and results are shown in Table 2.
Example 5
Preparing a catalyst: 1) and (3) uniformly mixing 20g of manganese oxide, 10g of calcium oxide, 45g of zinc oxide, 5g of aluminum oxide and 3g of sesbania powder, and extruding into strips. 2) The resulting sample was slowly raised from room temperature to 130 ℃ at a ramp rate of 16 ℃/min, and dried at this temperature for 10 h. 3) Baking at 450 deg.C for 8h to obtain strip sample. 4) 2.67g of ammonium metatungstate and 3.07g of ammonium molybdate are taken and added into deionized water to ensure that the volume of the solution is 85ml, and the total concentration of molybdenum and tungsten in the solution is 0.28 mol/L. 5) The resulting solution was added to the strip sample and immersed for 5h, the sample was filtered and dried, slowly increasing from room temperature to 120 ℃ at a ramp rate of 16 ℃/min, and dried at this temperature for 9 h. 6) The resulting sample was calcined at 440 ℃ for 11 h. 7) 19.45g of nickel nitrate is taken to prepare a solution with the concentration of 0.7 mol/L. 8) Adding the solution obtained in the step 7) into the sample obtained in the step 6), soaking for 7h, filtering and drying the sample, and slowly increasing the temperature from room temperature to 140 ℃ at the heating rate of 17 ℃/min during drying, and drying for 7h at the temperature. 9) Roasting the sample obtained in the step 8) at 410 ℃ for 8h to obtain the required catalyst.
The catalyst is crushed into 20-40 meshes, 2.0g of the catalyst is loaded in a fixed bed reactor, and the catalyst is directly fed and reacted after being heated to 250 ℃. The reaction pressure is 7.0MPa, and the mass airspeed of the fuel oil is 2.0h-1，H2The volume ratio/oil is 100. The reaction conditions and results are shown in Table 2.
Example 6
Preparing a catalyst: 1) and taking 10g of manganese oxide, 18g of calcium oxide, 24.4g of zinc hydroxide, 10g of ferrous oxide, 20g of aluminum oxide, 10g of silicon oxide and 1g of starch, uniformly mixing, extruding and forming. 2) The resulting sample was slowly raised from room temperature to 110 ℃ at a ramp rate of 13 ℃/min, and dried at this temperature for 5 h. 3) Baking at 450 deg.C for 3h to obtain strip sample. 4) 5.35g of ammonium metatungstate and 2.45g of ammonium molybdate are taken and added into deionized water to ensure that the volume of the solution is 100ml, and the total concentration of molybdenum and tungsten in the solution is 0.355 mol/L. 5) The resulting solution was added to the strip sample and immersed for 4h, the sample was filtered and dried, while slowly increasing from room temperature to 130 ℃ at a ramp rate of 14 ℃/min, and dried at this temperature for 10 h. 6) The resulting sample was calcined at 420 ℃ for 10 h. 7) 13.63g of nickel nitrate is taken to prepare a solution with the concentration of 0.2 mol/L. 8) Adding the solution obtained in the step 7) into the sample obtained in the step 6), soaking for 6h, filtering and drying the sample, and slowly increasing the temperature from room temperature to 120 ℃ at a heating rate of 14 ℃/min during drying, and drying for 8h at the temperature. 9) Roasting the sample obtained in the step 8) at 400 ℃ for 5 hours to obtain the required catalyst.
The catalyst is crushed into 20-40 meshes, 2.0g of the catalyst is loaded in a fixed bed reactor, and the catalyst is directly fed and reacted after being heated to 280 ℃. The reaction pressure is 2.0MPa, and the mass airspeed of the fuel oil is 2.0h-1，H2The volume ratio/oil is 100. The reaction conditions and results are shown in Table 2.
Example 7
Preparing a catalyst: 1) and (2) uniformly mixing 20g of zinc oxide, 40g of calcium oxide, 25g of MCM-41 molecular sieve and 2g of soluble starch, kneading into dough, extruding into strips and forming. 2) The resulting sample was slowly raised from room temperature to 110 ℃ at a ramp rate of 11 ℃/min, and dried at this temperature for 8 h. 3) Baking at 420 ℃ for 5h to obtain a strip sample. 4) 10.69g of ammonium metatungstate was taken, and deionized water was added to make the volume of the solution 90ml, and the concentration of tungsten in the solution was 0.28 mol/L. 5) The resulting solution was added to the strip sample and immersed for 3h, the sample was filtered and dried, slowly increasing from room temperature to 130 ℃ at a ramp rate of 16 ℃/min, and dried at this temperature for 7 h. 6) The resulting sample was calcined at 400 ℃ for 6 h. 7) 19.46g of nickel nitrate is taken to prepare a solution with the concentration of 0.9 mol/L. 8) Adding the solution obtained in the step 7) into the sample obtained in the step 6), soaking for 4h, filtering and drying the sample, and slowly increasing the temperature from room temperature to 140 ℃ at a heating rate of 14 ℃/min during drying, and drying for 6h at the temperature. 9) Roasting the sample obtained in the step 8) at 410 ℃ for 5 hours to obtain the required catalyst.
The catalyst is crushed into 20-40 meshes, 2.0g of the catalyst is loaded in a fixed bed reactor, and the catalyst is directly fed and reacted after being heated to 300 ℃. The reaction pressure is 2.0MPa, and the mass airspeed of the fuel oil is 2.0h-1，H2The volume ratio/oil is 100. The reaction conditions and results are shown in Table 2.
Example 8
Preparing a catalyst: 1) taking 40g of zinc oxide, 30g of calcium oxide, 15g of silicon dioxide and 1.6g of soluble starch, uniformly mixing, kneading into dough, extruding into strips and forming. 2) The resulting sample was slowly raised from room temperature to 140 ℃ at a ramp rate of 15 ℃/min, and dried at this temperature for 5 h. 3) Baking at 400 ℃ for 11h to obtain a strip sample. 4) 9.81g of ammonium metatungstate was taken, and deionized water was added to make the volume of the solution 70ml, and the tungsten concentration in the solution was 0.79 mol/L. 5) The resulting solution was added to the strip sample and immersed for 4h, the sample was filtered and dried, while slowly increasing from room temperature to 140 ℃ at a ramp rate of 13 ℃/min, and dried at this temperature for 9 h. 6) The resulting sample was calcined at 400 ℃ for 8 h. 7) 24.55g of nickel nitrate is taken to prepare a solution with the concentration of 0.5 mol/L. 8) Adding the solution obtained in the step 7) into the sample obtained in the step 6), soaking for 6h, filtering and drying the sample, and slowly increasing the temperature from room temperature to 120 ℃ at the heating rate of 12 ℃/min during drying, and drying for 6h at the temperature. 9) Roasting the sample obtained in the step 8) at 430 ℃ for 6h to obtain the required catalyst.
The catalyst is crushed into 20-40 meshes, 2.0g of the catalyst is loaded in a fixed bed reactor, and the temperature is raised to 320 ℃ for direct feeding reaction. The reaction pressure is 2.0MPa, and the mass airspeed of the fuel oil is 2.0h-1，H2The volume ratio/oil is 100. The reaction conditions and results are shown in Table 2.
Comparative example 1
Comparative catalyst preparation: 1) and uniformly mixing 20g of manganese oxide, 10g of calcium oxide, 55g of zinc oxide, 5g of alumina, 15g of soluble silica sol with the silica content of 33%, 5g of ZSM5 molecular sieve and 2g of sesbania powder. Kneading into dough, extruding into strips and forming. 2) The resulting sample was slowly raised from room temperature to 110 ℃ at a ramp rate of 10 ℃/min, and dried at this temperature for 10 h. 3) Baking at 450 deg.C for 8h to obtain strip sample. 4) 19.45g of nickel nitrate is taken to prepare a solution with the concentration of 0.7 mol/L. Adding the solution obtained in the step 3) into the sample obtained in the step 4), soaking for 8h, filtering and drying the sample, slowly increasing the temperature from room temperature to 110 ℃ at a heating rate of 10 ℃/min, and drying for 8h at the temperature. 5) Roasting the sample obtained in the step 4) at 450 ℃ for 8h to obtain the required catalyst.
The obtained catalyst is crushed into 20-40 meshes, 2.0g of catalyst is loaded in a fixed bed reactor, and the catalyst is directly fed and reacted after being heated to 450 ℃. The reaction pressure is 10.0MPa, and the mass airspeed of the fuel oil is 3.0h-1，H2The oil/volume ratio was 200. The catalyst composition is shown in Table 1, and the reaction conditions and results are shown in Table 2. In comparison with example 4, example 4 has a 15% higher sulfur capacity than comparative example 1.
Comparative example 2
Comparative catalyst preparation: 1) and (2) uniformly mixing 20g of manganese oxide, 10g of calcium oxide, 45g of zinc oxide, 5g of aluminum oxide, 10g of ferrous oxide and 3g of sesbania powder. Kneading into dough, extruding into strips and forming. 2) The resulting sample was slowly raised from room temperature to 120 ℃ at a ramp rate of 15 ℃/min, and dried at this temperature for 15 h. 3) Roasting at 440 ℃ for 8h to obtain a strip sample. 4) 38.91g of nickel nitrate is taken to prepare a solution with the concentration of 0.5 mol/L. Adding the solution obtained in the step 3) into the sample obtained in the step 4), soaking for 6h, filtering and drying the sample, slowly increasing the temperature from room temperature to 120 ℃ at a heating rate of 10 ℃/min, and drying for 7h at the temperature. 5) Roasting the sample obtained in the step 4) at 430 ℃ for 9h to obtain the required catalyst.
Crushing the catalyst of comparative example 2 into 20-40 meshes, loading 2.0g of the catalyst into a fixed bed reactor, heating to 250 ℃, and directly feeding for reaction. The reaction pressure is 7.0MPa, and the mass airspeed of the fuel oil is 2.0h-1，H2The volume ratio/oil is 100. The reaction conditions and results are shown in Table 2. Comparative example 2 is similar in composition to the catalyst of example 5, whereas example 5 has a 23% higher sulfur capacity than comparative example 2.
Comparative example 3
Comparative catalyst preparation: 1) and uniformly mixing 10g of manganese oxide, 18g of calcium oxide, 24.4g of zinc hydroxide, 10g of aluminum oxide, 10g of ferrous oxide and 5g of sesbania powder. Kneading into dough, extruding into strips and forming. 2) The resulting sample was slowly raised from room temperature to 130 ℃ at a ramp rate of 10 ℃/min, and dried at this temperature for 12 h. 3) Baking at 420 ℃ for 8h to obtain a strip sample. 4) 50.58g of nickel nitrate is taken to prepare a solution with the concentration of 0.6 mol/L. Adding the solution obtained in the step 3) into the sample obtained in the step 4), soaking for 8h, filtering and drying the sample, slowly increasing the temperature from room temperature to 120 ℃ at the heating rate of 15 ℃/min, and drying for 8h at the temperature. 5) Roasting the sample obtained in the step 4) at 450 ℃ for 9h to obtain the required catalyst.
Crushing the catalyst of the comparative example 3 into 20-40 meshes, putting 2.0g of the catalyst into a fixed bed reactor, heating to 280 ℃, and directly feeding for reaction. The reaction pressure is 2.0MPa, and the mass airspeed of the fuel oil is 2.0h-1，H2The volume ratio/oil is 100. The reaction conditions and results are shown in Table 2. Comparative example 3 is similar in composition to the catalyst of example 6, whereas example 6 has a 17% higher sulfur capacity than comparative example 3.
Comparative example 4
Comparative catalyst preparation: 1) 40g of calcium oxide, 20g of zinc oxide, 25g of MCM-41 and 8g of sesbania powder are uniformly mixed. Kneading into dough, extruding into strips and forming. 2) The resulting sample was slowly raised from room temperature to 150 ℃ at a ramp rate of 15 ℃/min, and dried at this temperature for 11 h. 3) Baking at 410 deg.C for 8h to obtain strip sample. 4) 58.39g of nickel nitrate was taken to prepare a solution with a concentration of 0.7 mol/L. Adding the solution obtained in the step 3) into the sample obtained in the step 4), soaking for 8h, filtering and drying the sample, and slowly increasing the temperature from room temperature to 140 ℃ at a heating rate of 14 ℃/min during drying, and drying for 8h at the temperature. 5) Roasting the sample obtained in the step 4) at 450 ℃ for 9h to obtain the required catalyst.
Crushing the catalyst of comparative example 4 into 20-40 meshes, loading 2.0g of the catalyst into a fixed bed reactor, heating to 300 ℃, and directly feeding for reaction. The reaction pressure is 2.0MPa, and the mass airspeed of the fuel oil is 2.0h-1，H2The volume ratio/oil is 100. The reaction conditions and results are shown in Table 2.Comparative example 4 is similar in composition to the catalyst of example 7, whereas example 7 has a 12% higher sulfur capacity than comparative example 4.
Comparative example 5
Comparative catalyst preparation: 1) 30g of calcium oxide, 40g of zinc oxide, 15g of silicon oxide and 2.5g of sesbania powder are mixed uniformly. Kneading into dough, extruding into strips and forming. 2) The resulting sample was slowly raised from room temperature to 110 ℃ at a ramp rate of 11 ℃/min, and dried at this temperature for 15 h. 3) Baking at 400 ℃ for 8h to obtain a strip sample. 4) 58.39g of nickel nitrate was taken to prepare a solution with a concentration of 0.7 mol/L. Adding the solution obtained in the step 3) into the sample obtained in the step 4), soaking for 8h, filtering and drying the sample, and slowly increasing the temperature from room temperature to 140 ℃ at the temperature rising rate of 15 ℃/min during drying, and drying for 8h at the temperature. 5) Roasting the sample obtained in the step 4) at 400 ℃ for 10h to obtain the required catalyst.
Crushing the catalyst of the comparative example 5 into 20-40 meshes, putting 2.0g of the catalyst into a fixed bed reactor, heating to 320 ℃, and directly feeding for reaction. The reaction pressure is 2.0MPa, and the mass airspeed of the fuel oil is 2.0h-1，H2The volume ratio/oil is 100. The reaction conditions and results are shown in Table 2. Comparative example 5 is similar in composition to the catalyst of example 8, whereas example 8 has 11% higher sulfur capacity than comparative example 5.
TABLE 1 catalyst composition
| Examples | |
| 1 | 0.18%Ni-1.82%Mo-30%ZnO-50%MnO2-18%Al2O3 |
| 2 | 1.8%Co2O3-18.2%WO3-20%CaO-10%FeO-25%Al2O3-25%SiO2 |
| 3 | 3.5%NiO-2.5%Co2O3-5.0%WO3-20%CaO-10%FeO-20%ZnO-20%Al2O3-10%SiO2-10%SBA15 |
| 4 | 5.0%NiO-2.5%MoO3-2.5%WO3-20%MnO2-10%CaO-50%ZnO-5%Al2O3-5%ZSM5 |
| 5 | 5.0%NiO-2.5%MoO3-2.5%WO3/20%MnO2-10%CaO-45%ZnO-10%FeO/5%Al2O3 |
| 6 | 3.5%NiO-2.0%MoO3-2.5%Co2O3-5.0%WO3/18%CaO-10%FeO-20%ZnO-10%MnO/20%Al2O3-10%SiO2 |
| 7 | 5%NiO-10%WO3/20%ZnO-40%CaO/25%MCM-41 |
| 8 | 7%CO-8%MoO3/40%ZnO-30%CaO/15%SiO2 |
| Comparative examples | |
| 1 | 5.0%NiO-20%MnO2-10%CaO-55%ZnO-5%Al2O3-5%ZSM5 |
| 2 | 10.0%NiO/20%MnO2-10%CaO-45%ZnO-10%FeO/5%Al2O3 |
| 3 | 13%NiO/18%CaO-10%FeO-20%ZnO-10%MnO/20%Al2O3-10%SiO2 |
| 4 | 15%NiO/20%ZnO-40%CaO/25%MCM-41 |
| 5 | 15%NiO/40%ZnO-30%CaO/15%SiO2 |
TABLE 2 reaction conditions and results
| Examples | Temperature, C | Pressure, MPa | Space velocity, h-1 | Hydrogen oil bodyProduct ratio, v/v | Desulfurization rate% | Sulfur capacity, g S/g catalyst |
| 1 | 200 | 0.1 | 0.2 | 10 | 89 | 0.16 |
| 2 | 500 | 5.0 | 5.0 | 600 | 100 | 0.3 |
| 3 | 400 | 3.0 | 4.0 | 300 | 100 | 0.3 |
| 4 | 450 | 10.0 | 3.0 | 200 | 100 | 0.3 |
| 5 | 250 | 7.0 | 2.0 | 100 | 95 | 0.27 |
| 6 | 280 | 2.0 | 2.0 | 100 | 97 | 0.28 |
| 7 | 300 | 2.0 | 2.0 | 100 | 99 | 0.29 |
| 8 | 320 | 2.0 | 2.0 | 100 | 100 | 0.3 |
| Comparative example | ||||||
| 1 | 450 | 10.0 | 3.0 | 200 | 90 | 0.22 |
| 2 | 250 | 7.0 | 2.0 | 100 | 82 | 0.12 |
| 3 | 280 | 2.0 | 2.0 | 100 | 85 | 0.14 |
| 4 | 300 | 2.0 | 2.0 | 100 | 90 | 0.18 |
| 5 | 320 | 2.0 | 2.0 | 100 | 95 | 0.27 |
Claims (7)
1. A coating catalyst is characterized by comprising three parts of a hydrodesulfurization active component, a sulfur adsorbent and a carrier, wherein the mass fraction of the hydrodesulfurization active component is 2.0-20.0wt%, the mass fraction of the sulfur adsorbent is 30.0-80.0wt%, and the balance is the carrier, the sulfur adsorbent is at least one of zinc oxide, manganese oxide, iron oxide and calcium oxide, the carrier is at least one of silicon oxide, aluminum oxide and a molecular sieve, the hydrodesulfurization active component consists of two parts AB, A: the molar ratio of B is 0.1-10, A is at least one of nickel oxide and cobalt oxide, B is at least one of molybdenum oxide and tungsten oxide, and the preparation method of the coating catalyst comprises the following steps
(1) Uniformly kneading the sulfur adsorbent or the precursor thereof, the carrier or the precursor thereof and the promoter, extruding and molding;
(2) drying the sample obtained in the step (1), increasing the temperature from room temperature to 150 ℃ at the heating rate of 10-20 ℃/min during drying, and drying for 6-24h at the temperature;
(3) roasting the sample obtained in the step (2) at the temperature of 400-600 ℃ for 3-12 h;
(4) preparing the precursor of the component B into a solution with the concentration of 0.05-1 mol/L;
(5) adding the solution obtained in the step (4) into the sample obtained in the step (3) for soaking for 2-20h, filtering and drying the sample, increasing the temperature from room temperature to 150 ℃ at the heating rate of 10-20 ℃/min, and drying for 6-24h at the temperature;
(6) roasting the sample obtained in the step (5) at the temperature of 400-600 ℃ for 3-12 h;
7) preparing the precursor of the component A into a solution with the concentration of 0.05-1 mol/L;
(8) adding the solution obtained in the step (7) into the sample obtained in the step (6) for soaking for 2-20h, filtering and drying the sample, increasing the temperature from room temperature to 150 ℃ at the heating rate of 10-20 ℃/min during drying, and drying for 6-24h at the temperature;
(9) and (4) roasting the sample obtained in the step (8) at the temperature of 400-600 ℃ for 3-12h to obtain the required catalyst.
2. A coated catalyst according to claim 1, wherein the sulfur sorbent precursor of step (1) is a hydroxide or carbonate of the sulfur sorbent.
3. The coated catalyst of claim 1 wherein the support precursor of step (1) is a supported hydroxide.
4. A coated catalyst according to claim 1, wherein the promoter in step (1) is sesbania powder or soluble starch, and is added in an amount of 0.5 to 10wt% of the sulfur adsorbent.
5. The coated catalyst of claim 1 wherein said B-component precursor of step (4) is an ammonium salt of the B-component.
6. The coated catalyst according to claim 1, wherein the component A precursor in the step (7) is a nitrate of the component A.
7. The use of a coated catalyst as claimed in any of claims 1 to 6, wherein the catalyst is used for the desulfurization of sulfur-containing fuel oil by feeding the sulfur-containing fuel oil directly after the reaction temperature is raised to 200 ℃ and 500 ℃ and the reaction pressure is 0.1 to 10.0MPa, fuel oil mass airspeed of 0.2-5.0h-1，H2The volume ratio of oil/oil is 10-600.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1123310A (en) * | 1994-11-25 | 1996-05-29 | 中国石化齐鲁石油化工公司 | Hydrodevulcanizing catalyst for hydro-carbons and preparation method thereof |
| CN104056632A (en) * | 2014-06-10 | 2014-09-24 | 中国科学院山西煤炭化学研究所 | Fuel oil deep-adsorption desulfurizationn catalyst, preparation method and application thereof |
| WO2015083704A1 (en) * | 2013-12-03 | 2015-06-11 | Ｊｘ日鉱日石エネルギー株式会社 | Desulfurization system, hydrogen production system, fuel cell system, method of desulfurizing fuel gas, and method of producing fuel gas desulfurization catalyst |
-
2018
- 2018-06-05 CN CN201810568061.6A patent/CN108855115B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1123310A (en) * | 1994-11-25 | 1996-05-29 | 中国石化齐鲁石油化工公司 | Hydrodevulcanizing catalyst for hydro-carbons and preparation method thereof |
| WO2015083704A1 (en) * | 2013-12-03 | 2015-06-11 | Ｊｘ日鉱日石エネルギー株式会社 | Desulfurization system, hydrogen production system, fuel cell system, method of desulfurizing fuel gas, and method of producing fuel gas desulfurization catalyst |
| CN104056632A (en) * | 2014-06-10 | 2014-09-24 | 中国科学院山西煤炭化学研究所 | Fuel oil deep-adsorption desulfurizationn catalyst, preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| S Zorb反应吸附脱硫剂的制备、表征及竞争吸附和反应机理的研究;于晓玲;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20160815(第08期);第11-13页第2.4.2节，第14页第2.4.3节 * |
| 催化裂化汽油吸附法脱硫技术开发;熊纯青;《工业催化》;20090430;第17卷(第4期);第1.1节 * |
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