CN113578350A - Completely-vulcanized hydrogenation modified catalyst, preparation method and application thereof - Google Patents
Completely-vulcanized hydrogenation modified catalyst, preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
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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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/06—Sulfides
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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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
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Abstract
The invention discloses a completely-vulcanized hydro-upgrading catalyst, a preparation method and application thereof. Wherein, the preparation method comprises the following steps: s1, uniformly mixing alumina, molecular sieve powder and an extrusion aid, adding an adhesive and a peptizing agent, kneading into colloid, extruding into strips by using a strip extruding machine, drying, roasting, and performing hydrothermal stabilization to obtain a catalyst carrier; s2, mixing zinc salt, nickel salt, a sulfur-containing reagent and a dispersing agent, adding deionized water, and dissolving to form a sulfur-containing active metal salt impregnation liquid; and S3, adsorbing the sulfur-containing active metal salt impregnation liquid prepared in the step S2 on the catalyst carrier prepared in the step S1 in a sealed environment, and heating to remove moisture to obtain the completely-vulcanized gasoline hydro-upgrading catalyst. Compared with the conventional in-situ and out-situ presulfurization, the presulfurization catalyst has the advantages of simple preparation process, low preparation cost, short start-up period and the like.
Description
Technical Field
The invention relates to the technical field of gasoline hydro-upgrading, in particular to a fully-vulcanized hydro-upgrading catalyst, and a preparation method and application thereof.
Background
The gasoline hydrogenation modification technology is an important oil refining production process for producing clean gasoline, and is mainly used for producing clean gasoline products from catalytic cracking gasoline raw materials with high olefin and sulfur contents. With the continuous upgrading of the quality of clean gasoline products, the stricter environmental protection regulations, and the deterioration and heaviness of gasoline raw materials, the hydro-upgrading technology is widely regarded and applied.
The processing capacity of gasoline hydrogenation devices of oil refining enterprises in China is continuously increased, the demand of hydrogenation catalysts is increased year by year, and as is well known, active metal components in hydrogenation modified catalyst products produced in industry are generally in an oxidation state, and metal sulfides have the function of hydrogenation modification, so that before the catalysts are used, the catalysts need to be vulcanized to obtain better hydrogenation modification performance. Therefore, the conversion of the active metal component from the oxide state to the sulfide state is one of the important links in the application of the catalyst.
The sulfidation process currently used in industry for hydrogenation catalysts is an in-situ presulfiding process, i.e., the conversion of the active metals of the catalyst from an oxidized state to a sulfided state in a hydrogenation unit. In the in-situ presulfurization process, vulcanizing agents such as carbon disulfide, dimethyl disulfide and the like are required to be added into vulcanized oil; the device needs to additionally establish a vulcanization system facility special for the start-up of the catalyst; the in-catalyst sulfurization start-up process is complex and needsThe injection rate of the vulcanizing agent and the temperature rise speed of the catalyst bed are accurately controlled, and the control indexes such as the concentration of hydrogen sulfide in the reaction system are detected in real time, so that the device has complicated starting steps and long starting period, not only occupies the effective production running time of the gasoline hydrogenation device, but also cannot completely vulcanize active metal components, and has low active metal utilization rate; furthermore, during the catalyst sulfiding, the apparatus is at a high concentration H2Under the S atmosphere, the problems of potential safety production hazards, environmental pollution and the like exist in the vulcanization start-up process in the device. The ex-situ presulfurization technology is a technological method for presulfurizing the oxidation state catalyst outside a hydrogenation reactor before the fresh or regenerated oxidation state catalyst is loaded into the hydrogenation reactor. The hydrogenation catalyst "outside the reactor" presulfurization technology mainly adopts the following two technical routes:
(1) the first technological route is that the sulfurizing agent (comprising olefin-containing petroleum solvent, sulfur element, vegetable oil, organic sulfide, organic polysulfide, sulfone, sulfoxide, sulfurizing promoter, etc.) is first sublimated, molten or soaked into the pore channel of oxidized hydrogenating catalyst, the catalyst is then pre-sulfurized partially in the presence of inert gas through heating treatment, and finally the catalyst is loaded into the hydrogenating reactor and pre-sulfurized in the course of heating and in the presence of hydrogen;
(2) the second technical route is that the catalyst is presulfurized in a special presulfurization device in the presence of hydrogen and hydrogen sulfide or easily decomposed organic vulcanizing agent in the temperature rising process, and then the catalyst is passivated by gas containing a small amount of oxygen to prepare the non-self-ignition presulfurization catalyst.
The traditional ex-situ prevulcanization technology still has some problems: the hydrogenation catalyst is soaked and treated with sulfur-containing organic liquid, and then the treated catalyst is sulfurized with hydrogen or the mixture of hydrogen and hydrogen sulfide in a pressure container and finally passivated in oxygen-containing atmosphere. The vulcanization treatment process is complicated, and the preparation cost is high. Secondly, elemental sulfur is used as a vulcanizing agent, sulfur is carried by adopting a dry sulfur sublimation method or a wet sulfur-containing suspension method, and the problems of serious sulfur loss, concentrated heat release and the like exist in the process of start-up, so that the operation difficulty in the process of start-up is increased, and the production cost is increased. For example:
chinese patent 200610046941.4 discloses a hydrogenation catalyst sulfurization method, which comprises introducing thiuram substance, sulfurizing agent, and organic solvent into oxidation state catalyst, and treating in dynamic heating equipment to realize catalyst sulfurization.
Chinese patent ZL200410039450.8 discloses a new method for on-site and off-site presulfurization of hydrogenation catalyst, which mainly adopts ammonium sulfide (NH) containing sulfur4)2And the S solution is used as a vulcanizing agent, and the vulcanizing agent is loaded on the hydrogenation catalyst to convert the oxide of the active metal component or the precursor thereof into the metal sulfide with hydrogenation activity, so that the vulcanization of the catalyst is realized.
Chinese patent ZL200410039449.5 discloses a preparation method of a vulcanization type hydrogenation catalyst, which mainly comprises the steps of loading VIB group metals Mo and W on a catalyst carrier in a soluble thiomolybdate and thiotungstate solution mode, drying and roasting in an inert atmosphere, then loading Co or Ni metal salt, and continuing drying and roasting in the inert atmosphere to obtain the vulcanization type hydrogenation catalyst.
Disclosure of Invention
The invention aims to provide a fully-vulcanized hydro-upgrading catalyst, a preparation method and application thereof, and aims to solve the technical problems that the hydro-upgrading catalyst in the prior art is high in production cost or needs to be activated during operation.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a fully sulfided hydro-upgrading catalyst. The preparation method comprises the following steps: s1, uniformly mixing alumina, molecular sieve powder and an extrusion aid, adding an adhesive and a peptizing agent, kneading into colloid, extruding into strips by using a strip extruding machine, drying, roasting, and performing hydrothermal stabilization to obtain a catalyst carrier; s2, mixing zinc salt, nickel salt, a sulfur-containing reagent and a dispersing agent, adding deionized water, and dissolving to form a sulfur-containing active metal salt impregnation liquid; and S3, adsorbing the sulfur-containing active metal salt impregnation liquid prepared in the step S2 on the catalyst carrier prepared in the step S1 in a sealed environment, and heating to remove moisture to obtain the completely-vulcanized gasoline hydro-upgrading catalyst.
Further, the sulfur-containing reagent is one or more selected from the group consisting of allicin, ethylicin, thiourea and methallyl trisulfide.
Further, in S3, the sealed atmosphere is a sealed can with a heating jacket, and the sealed can is evacuated to remove air from the can.
Further, in S3, when the sulfur-containing active metal salt impregnation liquid is adsorbed onto the catalyst carrier in a sealed environment, the seal tank is rotated, and after adsorption is completed, the seal tank is heated to remove the deionized water on the catalyst, thereby obtaining the fully-sulfided gasoline hydro-upgrading catalyst.
Further, the dispersant is ethylene glycol.
Further, the nickel salt is nickel nitrate and/or nickel acetate, and the zinc salt is zinc nitrate and/or zinc acetate.
Further, in S3, the heating temperature is 180-240 ℃, and the heating time is 2-8 hours.
According to another aspect of the present invention, a fully sulfided gasoline hydro-upgrading catalyst is provided. The completely vulcanized gasoline hydrogenation modification catalyst is prepared by any one of the preparation methods.
Further, the catalyst comprises ZnS 3.5-6.0% and NiS 0.8-2.2% by dry mass of the catalyst, and the balance alumina, and the specific surface area of the catalyst is 250-450 m2The pore volume is 0.25 to 0.6 mL/g.
According to another aspect of the invention, a start-up method of a fully-sulfurized gasoline hydro-upgrading catalyst is provided. The start-up method comprises the following steps: the completely vulcanized hydro-upgrading catalyst is used as a catalyst, vulcanization and activation are not needed in the start-up process of the catalyst, and the start-up temperature condition is as follows: heating the gasoline raw material to 120-160 ℃ at a heating rate of 10-50 ℃/h, heating the gasoline raw material to 360-400 ℃ at a heating rate of 10-50 ℃/h, wherein the hydrogen partial pressure is 1.5-3.0 MPa, the volume ratio of hydrogen to oil is 200: 1-500: 1, and the volume airspeed is 0.5-2.0 h-1Complete hydrogenation modification of fully sulfurized gasolineAnd (5) starting the catalyst.
By applying the technical scheme of the invention, active metal components of the catalyst and sulfur-containing compounds are prepared into sulfur-containing metal salt impregnation liquid, then the sulfur-containing metal salt is loaded on a catalyst carrier, and a pre-vulcanized (fully vulcanized) catalyst is obtained through low-temperature oxygen-free activation; compared with the conventional in-situ and out-situ presulfurization, the presulfurization catalyst has the advantages of simple preparation process, low preparation cost, short start-up period and the like; the catalyst of the invention is suitable for the hydro-upgrading process of poor quality catalytic cracking gasoline in the field of petroleum refining.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
Aiming at the technical problems of high production cost or activation required during start-up of a hydrogenation modified catalyst in the prior art described in the background art, the invention provides a fully-vulcanized gasoline hydrogenation modified catalyst and a preparation method thereof.
According to an exemplary embodiment of the present invention, a method for preparing a fully sulfided hydro-upgrading catalyst is provided. The method comprises the following steps: s1, uniformly mixing alumina, molecular sieve powder and an extrusion aid, adding an adhesive and a peptizing agent, kneading into colloid, extruding into strips by using a strip extruding machine, drying, roasting, and performing hydrothermal stabilization to obtain a catalyst carrier; s2, mixing zinc salt, nickel salt, a sulfur-containing reagent and a dispersing agent, adding deionized water, and dissolving to form a sulfur-containing active metal salt impregnation liquid; and S3, adsorbing the sulfur-containing active metal salt impregnation liquid prepared in the step S2 on the catalyst carrier prepared in the step S1 in a sealed environment, and heating to remove moisture to obtain the completely-vulcanized gasoline hydro-upgrading catalyst.
By applying the technical scheme of the invention, active metal components of the catalyst and sulfur-containing compounds are prepared into sulfur-containing metal salt impregnation liquid, then the sulfur-containing metal salt is loaded on a catalyst carrier, and a pre-vulcanized (fully vulcanized) catalyst is obtained through low-temperature oxygen-free activation; compared with the conventional in-situ and out-situ presulfurization, the presulfurization catalyst has the advantages of simple preparation process, low preparation cost, short start-up period and the like; the catalyst of the invention is suitable for the hydro-upgrading process of poor quality catalytic cracking gasoline in the field of petroleum refining.
Preferably, the sulfur-containing reagent is one or more selected from the group consisting of allicin, ethylicin, thiourea and methallyl trisulfide, and the sulfur-containing reagents are low in cost, easy to obtain and suitable for industrial production. In an exemplary embodiment of the present invention, in S3, the sealed environment is a sealed tank with a heating jacket, the sealed tank is vacuumized, and air in the tank is exhausted, and the sealed vacuum environment can prevent the oxidation reaction in the presence of oxygen. Preferably, in S3, when the sulfur-containing active metal salt impregnation solution is adsorbed onto the catalyst carrier in a sealed environment, the seal tank is rotated, and after adsorption is completed, the seal tank is heated to remove deionized water on the catalyst, thereby obtaining the fully-sulfided gasoline hydro-upgrading catalyst.
In one embodiment of the present invention, the dispersant is preferably ethylene glycol, the nickel salt is nickel nitrate and/or nickel acetate, and the zinc salt is zinc nitrate and/or zinc acetate. And S3, heating at 180-240 ℃ for 2-8 hours to ensure normal running of the vulcanization reaction.
According to an exemplary embodiment of the present invention, a fully sulfided gasoline hydro-upgrading catalyst is provided. The completely vulcanized gasoline hydro-upgrading catalyst is prepared by the preparation method, comprises 3.5-6.0% of ZnS, 0.8-2.2% of NiS and the balance of alumina by taking the dry mass of the catalyst as 100%, and has the specific surface area of 250-450 m2The pore volume is 0.25 to 0.6 mL/g.
According to an exemplary embodiment of the present invention, a method for operating a fully sulfided gasoline hydro-upgrading catalyst is provided. The method comprises the following steps: the completely vulcanized hydro-upgrading catalyst is used as a catalyst, vulcanization and activation are not needed in the start-up process of the catalyst, and the start-up temperature condition is as follows: heating to 120-160 ℃ at a heating rate of 10-50 ℃/hHeating the gasoline raw material to 360-400 ℃ at a heating rate of 10-50 ℃/h, wherein the hydrogen partial pressure is 1.5-3.0 MPa, the volume ratio of hydrogen to oil is 200: 1-500: 1, and the volume airspeed is 0.5-2.0 h-1And completing the start-up of the completely vulcanized gasoline hydrogenation modification catalyst. Because vulcanization or activation is not needed in the start-up process, the start-up time is greatly shortened, the workload is reduced, the safety risk is avoided, and the method has a good application prospect.
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
Example 1
Taking 100g (dry basis weight) of molecular sieve, 20g (dry basis weight) of alumina powder and 4g of sesbania powder, adding the mixture into 5.5g of deionized water containing 65% concentrated nitric acid, kneading for 30 minutes, extruding the kneaded materials by a strip extruder to form strips, drying at 120 ℃, roasting at 500 ℃, and performing hydrothermal stabilization at 400-600 ℃ to obtain a catalyst carrier finished product A.
Adding 52ml of deionized water into 22g of zinc nitrate, 7.5g of nickel nitrate and 8.5g of allicin, and fully stirring and dissolving to prepare a steeping fluid.
Adding 100g of the finished catalyst carrier product into a 250ml three-neck flask, vacuumizing the three-neck flask for 30min by using a vacuum pump, then adding the impregnation liquid by 3 times, keeping the vacuum state in the impregnation process, simultaneously turning over the catalyst, stopping vacuumizing after the impregnation is finished, introducing nitrogen at a gas flow rate of 5L/h, heating the three-neck flask containing the catalyst to 200 ℃ at a heating rate of 80 ℃/h, keeping the temperature for 2 hours, and then cooling to obtain the completely vulcanized catalyst.
Example 2
Taking 100g (dry basis weight) of molecular sieve, 20g (dry basis weight) of alumina powder and 4g of sesbania powder, adding the mixture into 5.5g of deionized water containing 65% concentrated nitric acid, kneading for 30 minutes, extruding the kneaded materials by a strip extruder to form strips, drying at 120 ℃, roasting at 500 ℃, and performing hydrothermal stabilization at 400-600 ℃ to obtain a catalyst carrier finished product.
Adding 52ml of deionized water into 22g of zinc nitrate, 7.5g of nickel nitrate and 10.5g of allicin, and fully stirring and dissolving to prepare a steeping fluid.
Adding 100g of the finished catalyst carrier product into a 250ml three-neck flask, vacuumizing the three-neck flask for 30min by using a vacuum pump, then adding the impregnation liquid by 3 times, keeping the vacuum state in the impregnation process, simultaneously turning over the catalyst, stopping vacuumizing after the impregnation is finished, introducing nitrogen at a gas flow rate of 5L/h, heating the three-neck flask containing the catalyst to 200 ℃ at a heating rate of 80 ℃/h, keeping the temperature for 2 hours, and then cooling to obtain the completely vulcanized catalyst B.
Example 3
Taking 100g (dry basis weight) of molecular sieve, 20g (dry basis weight) of alumina powder and 4g of sesbania powder, adding the mixture into 5.5g of deionized water containing 65% concentrated nitric acid, kneading for 30 minutes, extruding the kneaded materials by a strip extruder to form strips, drying at 120 ℃, roasting at 500 ℃, and performing hydrothermal stabilization at 400-600 ℃ to obtain a catalyst carrier finished product.
Adding 52ml of deionized water into 22g of zinc nitrate, 7.5g of nickel nitrate and 13.5g of allicin, and fully stirring and dissolving to prepare a steeping fluid.
Adding 100g of the finished catalyst carrier product into a 250ml three-neck flask, vacuumizing the three-neck flask for 30min by using a vacuum pump, then adding the impregnation liquid for 3 times, keeping the vacuum state in the impregnation process, simultaneously turning over the catalyst, stopping vacuumizing after the impregnation is finished, introducing nitrogen at a gas flow rate of 5L/h, heating the three-neck flask containing the catalyst to 200 ℃ at a heating rate of 80 ℃/h, keeping the temperature for 2 hours, and then cooling to obtain the completely vulcanized catalyst C.
Example 4
Taking 100g (dry basis weight) of molecular sieve, 20g (dry basis weight) of alumina powder and 4g of sesbania powder, adding the mixture into 5.5g of deionized water containing 65% concentrated nitric acid, kneading for 30 minutes, extruding the kneaded materials by a strip extruder to form strips, drying at 120 ℃, roasting at 500 ℃, and performing hydrothermal stabilization at 400-600 ℃ to obtain a catalyst carrier finished product.
Adding 52ml of deionized water into 22g of zinc nitrate, 7.5g of nickel nitrate, 10.5g of allicin and 2.4g of ethylene glycol, and fully stirring and dissolving to prepare a steeping fluid.
Adding 100g of the finished catalyst carrier product into a 250ml three-neck flask, vacuumizing the three-neck flask for 30min by using a vacuum pump, then adding the impregnation liquid by 3 times, keeping the vacuum state in the impregnation process, simultaneously turning over the catalyst, stopping vacuumizing after the impregnation is finished, introducing nitrogen at a gas flow rate of 5L/h, heating the three-neck flask containing the catalyst to 200 ℃ at a heating rate of 80 ℃/h, keeping the temperature for 2 hours, and then cooling to obtain the completely vulcanized catalyst D.
Comparative example 1
The comparative example provides a conventional gasoline hydrogenation modification catalyst E, and the hydrogenation active metals are zinc and nickel. The catalyst is prepared by using a molecular sieve and alumina as carriers, preparing impregnation liquid by using zinc nitrate and nickel nitrate, loading the impregnation liquid on the carriers in an equal-volume impregnation mode, drying at 120 ℃ for 2 hours, and roasting at 500 ℃ for 4 hours.
TABLE 1 physicochemical Properties of the catalyst
| Item | Zn | Ni | S |
| A | 4.7 | 1.3 | 2.6 |
| B | 4.7 | 1.3 | 2.6 |
| C | 4.7 | 1.3 | 2.6 |
| D | 4.7 | 1.3 | 2.5 |
| E | 4.7 | 1.3 | 2.9 |
Example 5
This example describes the results of evaluation analysis of the above catalyst.
And respectively carrying out an activity evaluation test on the catalyst A, B, C, D, E by adopting a 100mL evaluation experimental device, wherein the loading amount of the catalyst is 100mL, the catalyst A-D directly enters a catalytic heavy gasoline raw material at 150 ℃ in the start-up process, and the temperature is raised to 380 ℃ at 30 ℃/h, so that the start-up of the completely vulcanized catalyst is completed. And (3) vulcanizing the catalyst E in a traveling device, cooling to 280 ℃, catalyzing heavy gasoline raw materials, heating to 380 ℃ at the speed of 30 ℃/h, and finishing the vulcanization start-up of the oxidation-state catalyst. A catalytic heavy gasoline with the sulfur content of 150mg/kg, the olefin content of 29.8 percent and the aromatic hydrocarbon content of 27.6 percent is used as an evaluation raw material to carry out a hydrogenation modification activity comparison test under the reaction conditions of the reaction temperature of 380 ℃, the hydrogen partial pressure of 2.0MPa, the hydrogen-oil volume ratio of 350:1 and the volume space velocity of 1.5h-1. The results of the evaluation and analysis of the catalyst are shown in Table 2.
Table 2 evaluation analysis data
| Sample (I) | Olefin, v% | Arene, v% | Octane number |
| Catalytic gasoline feedstock | 29.8 | 27.6 | 86.8 |
| A | 13.6 | 29.2 | 89.4 |
| B | 13.8 | 29.1 | 89.2 |
| C | 13.9 | 29.1 | 89.2 |
| D | 13.6 | 29.2 | 89.4 |
| E | 13.6 | 29.2 | 89.4 |
As can be seen from Table 2, compared with the catalyst E of the comparative example, the catalyst A, B, C, D has better hydro-upgrading activity, the olefin reduction amplitude is 15.9-16.2 units, and the octane number is improved by 2.4-2.6 units by using the catalytic heavy gasoline as the raw material. And the hydro-upgrading activity of catalyst A, B, C, D was comparable to the catalyst E activity. In addition, the completely vulcanized hydro-upgrading catalyst provided by the invention can be directly used without vulcanization and activation during startup, the startup time can be shortened from 52 hours to 13 hours, the work of vulcanizing agent injection, hydrogen sulfide detection and the like is avoided, and the startup process is simple and easy to operate.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a fully-vulcanized hydro-upgrading catalyst is characterized by comprising the following steps:
s1, uniformly mixing alumina, molecular sieve powder and an extrusion aid, adding an adhesive and a peptizing agent, kneading into colloid, extruding into strips by using a strip extruding machine, drying, roasting, and performing hydrothermal stabilization to obtain a catalyst carrier;
s2, mixing zinc salt, nickel salt, a sulfur-containing reagent and a dispersing agent, adding deionized water, and dissolving to form a sulfur-containing active metal salt impregnation liquid; and
s3, adsorbing the sulfur-containing active metal salt impregnation liquid prepared in the step S2 to the catalyst carrier prepared in the step S1 in a sealed environment, and heating to remove moisture to obtain the completely-vulcanized gasoline hydro-upgrading catalyst.
2. The method according to claim 1, wherein the sulfur-containing reagent is one or more selected from the group consisting of allicin, ethylicin, thiourea and methallyl trisulfide.
3. The method of claim 1, wherein in the step S3, the sealed environment is a sealed tank with a heating jacket, and the sealed tank is evacuated to remove air from the tank.
4. The preparation method according to claim 1, wherein in S3, when the sulfur-containing active metal salt impregnation solution is adsorbed onto the catalyst carrier in a sealed environment, the seal pot is rotated, and after adsorption is completed, the seal pot is heated to remove deionized water on the catalyst, thereby obtaining the fully sulfided gasoline hydro-upgrading catalyst.
5. The method according to claim 1, wherein the dispersant is ethylene glycol.
6. The method according to claim 1, wherein the nickel salt is nickel nitrate and/or nickel acetate, and the zinc salt is zinc nitrate and/or zinc acetate.
7. The method according to claim 1, wherein the heating in S3 is performed at 180 to 240 ℃ for 2 to 8 hours.
8. A fully sulfided gasoline hydro-upgrading catalyst, characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. The fully sulfided gasoline hydro-upgrading catalyst according to claim 8, comprising ZnS 3.5-6.0%, NiS 0.8-2.2%, and alumina in balance, based on 100% of the dry mass of the catalyst, and having a specific surface area of 250-450 m2G, pore volume0.25 to 0.6 mL/g.
10. A method for starting up a fully-vulcanized gasoline hydro-upgrading catalyst is characterized by comprising the following steps: the fully-sulfided hydro-upgrading catalyst of claim 8 or 9 is used as a catalyst, the catalyst does not need to be sulfided and activated during the start-up process, and the start-up temperature condition is as follows: heating the gasoline raw material to 120-160 ℃ at a heating rate of 10-50 ℃/h, heating the gasoline raw material to 360-400 ℃ at a heating rate of 10-50 ℃/h, wherein the hydrogen partial pressure is 1.5-3.0 MPa, the volume ratio of hydrogen to oil is 200: 1-500: 1, and the volume airspeed is 0.5-2.0 h-1And completing the start-up of the completely vulcanized gasoline hydrogenation modification catalyst.
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