CN103361111B - A kind of gasoline hydrogenation processes the catalyst vulcanization method of technique - Google Patents
A kind of gasoline hydrogenation processes the catalyst vulcanization method of technique Download PDFInfo
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Abstract
The invention discloses a kind of catalyst vulcanization method of gasoline hydrogenation technique.The method includes: (1) high sulfur-containing diesel hydro-refining unit runs well；(2) filling oxidation state gasoline hydrogenation catalyst in gasoline hydrotreater reactor；(3) gasoline hydrotreater carries out gas displacement, catalyst is dried and device air tight work；(4) the part H 2 S-containing gas obtained by high sulfur-containing diesel hydro-refining unit, introduces gasoline hydrotreater, the catalyst in gasoline hydrotreater reactor is carried out vulcanisation operation；(5) vulcanize by the normal conditions of vulcanization of gasoline hydrogenation technique, until sulfuration terminates；(6) after sulfuration terminates, gasoline hydrotreater carries out the circulation operation of repeats itself hydrogen, adjusts bed and carries out gasoline hydrotreater to reaction temperature, switching raw oil.The inventive method can improve curing efficiency, reduce vulcanizing agent consumption.
Description
Technical field
The present invention relates to a kind of gasoline hydrogenation and process the catalyst vulcanization method of technique, include that especially for oil refining enterprise high sulfur-containing diesel hydro-refining unit and gasoline hydrogenation process the catalyst vulcanization method of the gasoline hydrogenation process technique of process unit simultaneously.
Technical background
Owing to crude output increasess slowly and heaviness increasingly, and clear gusoline demand is continuously increased by the world today, and product quality requires more and more stricter.Petroleum distillate hydrogen addition technology is the major technique currently producing clear gusoline, and wherein the technology of preparing of hydrogenation catalyst is the key of hydrogen addition technology.The active metal component of the hydrogenation catalyst of preparation is oxidation state, and oxidized catalyst is before industrial application, and its active metal need to be converted into sulphided state and just have higher catalysis activity.Therefore, the sulfuration of catalyst has material impact to the performance of catalyst, is the important process step before catalyst application.
The method for pre-sulphuration of catalyst can be divided into in-situ presulfurization and ex situ presulfiding by the mode carrying sulfur.Up to now, domestic and international most refinery introduces vulcanizing agent after still using in-situ presulfurization mode, the freshest or regenerated catalyst to be loaded into reactor and vulcanizes, or sulfur loaded agent in the catalyst, carries out vulcanization reaction in reactor.State according to vulcanizing agent is different, and in-situ presulfurization mode can be divided into again wet method sulfuration with dry pre-sulfiding.Wet method sulfuration also referred to as liquid phase sulfuration, is in presence of hydrogen, liquid sulfur agent is first dissolved in light distillate formation sulfurized oil, then contacts with hydrogenation catalyst in input reactor and carry out vulcanization reaction.Dry pre-sulfiding also referred to as gas-phase presulfiding, refers to catalyst in the presence of hydrogen gas, directly with certain density sulfurizing agent and vulcanize.
CN99123716.1 discloses a kind of reformer start-up method again loading double/multimetal reforming catalyst, including using nitrogen purging reaction unit, then dry catalyst at 350～420 DEG C, backward reforming reactor in be passed through raw oil, control water chloride balance until reaching the operating condition normally produced.
USP4725571 discloses the method for a kind of catalyst wet sulfuration, and the method adds two kinds of vulcanizing agents by using in sulfurized oil, completes the presulfurization of catalyst.
CN1362493A discloses the vulcanization process of a kind of catalyst for hydroprocessing of heavy oil, first the inorganic sulphide of solid-state is mixed homogeneously with Hydrodemetalation catalyst, then by using the means combined with wet method vulcanization process under high temperature dry pre-sulfiding under low temperature, decrease the consumption of sulfurized oil, reduce sulfuration cost, and vulcanizing agent sulfurization rate is good, give full play to the performance of catalyst.
CN01106022.0 discloses the vulcanization process of a kind of catalyst for hydroprocessing of heavy oil, it is characterized in mixing homogeneously the inorganic sulphide of solid-state with Hydrodemetalation catalyst, then by using the means combined with wet method vulcanization process under high temperature dry pre-sulfiding under low temperature, decrease the consumption of sulfurized oil, reduce sulfuration cost, and vulcanizing agent sulfurization rate is good, give full play to the performance of catalyst.
In modern oil refining enterprise, generally comprise and overlap hydrogenation plant more, generally comprise that wax oil hydrogenation processes, is hydrocracked, residual hydrocracking, diesel oil hydrofining, gasoline hydrogenation modifying, kerosene hydrogenation are refined, hydrorefining basic oil lubricating oil, hydrorefining paraffin wax etc., and for large-scale oil refining enterprise, the hydrogenation plant of a certain type the most also includes overlapping more, and hydrogenation plant has become the processing unit (plant) that in oil refining enterprise, quantity is most.Though the purpose of different hydrogenation plants is different, but desulphurization reaction is jointly to react present in numerous hydrogenation plant, along with the development that raw material is high-sulfurized, and the requirement of the cleaning low sulfuration of fuel, one of desulphurization reaction critical function becoming hydrogenation plant, the main purpose of some hydrogenation plant is exactly hydrodesulfurization, such as diesel oil hydrogenation process etc..Prior art hydrogenation catalyst sulfidation, only for certain a set of hydrogenation plant, does not accounts for overlapping the joint operation of hydrogenation plant more.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of gasoline hydrogenation to process the catalyst vulcanization method of technique, carries out catalyst vulcanization in conjunction with high sulfur-containing diesel hydro-refining unit and goes into operation, and improves curing efficiency, reduces vulcanizing agent consumption.
Gasoline hydrogenation of the present invention processes the catalyst vulcanization method of technique and includes following content:
(1) high sulfur-containing diesel hydro-refining unit runs well；
(2) filling oxidation state gasoline hydrogenation catalyst in gasoline hydrotreater reactor；
(3) gasoline hydrotreater carries out gas displacement, catalyst is dried and device air tight work；
(4) H 2 S-containing gas obtained by high sulfur-containing diesel hydro-refining unit, introduces gasoline hydrotreater, the catalyst in gasoline hydrotreater reactor is carried out vulcanisation operation；
(5) sulfidation of gasoline hydrotreater includes: constant temperature 2h ~ 16h, H at 190 DEG C ~ 250 DEG C2It is 500 μ L/L ~ 15000 μ L/L that the concentration of S controls；Constant temperature 5h ~ 16h hour, H at 260 DEG C ~ 350 DEG C2It is 5000 μ L/L ~ 30000 μ L/L that the concentration of S controls；
(6) after sulfuration terminates, gasoline hydrotreater carries out the circulation operation of repeats itself hydrogen, adjustment bed to reaction temperature, and switching raw oil carries out gasoline hydrogenation and processes reaction.
In the inventive method, the high sulfur-containing diesel hydro-refining unit of the steady running described in step (1), usually the medium-pressure or high pressure device of steady production operating in oil refining enterprise, pressure rating is generally 4 ~ 10MPa.The operating condition of high sulfur-containing diesel hydro-refining unit is carried out by normal operating.The feed sulphur content of high sulfur-containing diesel hydro-refining unit is generally more than 0.5wt%, preferably 0.5wt% ~ 5wt%.In step (1), the process conditions of Diesel Oil Hydrofining Unit are generally: reaction pressure 4 ~ 10MPa, reaction temperature 280 DEG C ~ 400 DEG C, volume space velocity 0.1 ~ 10h-1, hydrogen to oil volume ratio 100 ~ 2000.
In the inventive method, the gasoline hydrotreater described in step (2) can be gasoline hydrogenation device, reformed pre-hydrogenated device or Hydrogenation of Coker Gasoline device.
In the inventive method, the gasoline hydrogenation catalyst described in step (2) is typically with porous, inorganic refractory oxide such as aluminium oxide, silicon oxide, amorphous silicon aluminium, titanium oxide, molecular sieve and the composite oxides of several element or mixed oxide etc. as carrier.It is carrier that gasoline hydrogenation catalyst generally uses no acidic or weakly acidic material, such as aluminium oxide, silicon oxide, amorphous silicon aluminium etc., loads hydrogenation active metals component.The hydrogenation active component of Gasoline Hydrotreating Catalysts is one or more in W, Mo, Ni and Co, and in terms of oxide, hydrogenation active component content is generally 3wt% ~ 50wt%.Gasoline Hydrotreating Catalysts can by technological process need select suitable commercial catalyst, it is also possible to prepare by existing method, it is also possible to the regenerated catalyst being decaying catalyst after regeneration.
In the inventive method, the start-up method that the gas displacement described in step (3), catalyst are dried and the device operation such as airtight is well known to those skilled in the art.As all described the operational approach of said process in " being hydrocracked ", " hydroprocessing technique and engineering " and " hydrocracking process and engineering ".
In the inventive method, described in step (4) the H 2 S-containing gas of high sulfur-containing diesel hydro-refining unit is introduced gasoline hydrogenation device can be to include following two mode: a part for diesel hydrotreating unit high score gas is introduced gasoline hydrogenation device, the gas obtained through gasoline hydrogenation device high score through or without gasoline hydrogenation device desulfurizing tower after as the supplementary hydrogen of Diesel Oil Hydrofining Unit, return (one-level or two grades) entrance of diesel hydrotreating unit make-up hydrogen compressor, or be directly discharged into hydrogen pipe network；Or in step (4) after high sulfur-containing diesel hydro-refining unit desulfurizing tower, after circulating hydrogen compressor, preferably draw a part of H 2 S-containing gas, introduce after suitable blood pressure lowering in the reactor of gasoline hydrogenation device.Described gasoline hydrogenation device desulfurizing tower typically uses the hydrogen sulfide in amine liquid elution cycles gas, by regulating the injection rate of lean amine liquid to regulate hydrogen sulfide stripping rate.In gas after gasoline hydrogenation device desulfurizing tower processes, concentration of hydrogen sulfide is typically at 500 below μ L/L.
In the inventive method, in step (5), concentration of hydrogen sulfide during gasoline hydrogenation device catalyst vulcanization generally can directly meet the sulfuration needs of gasoline hydrogenation catalyst, or can be adjusted, so that it better meets sulfidation needs by filling into the new hydrogen of part.If directly after Diesel Oil Hydrofining Unit desulfurizing tower, extension H 2 S-containing gas to gasoline hydrotreater, then can regulate hydrogen sulfide content in gas by the operation of regulation diesel hydrotreating unit desulfurizing tower.
In the inventive method, the sulfidation of step (5) gasoline hydrogenation device can be dry pre-sulfiding；Can also vulcanize for wet method, i.e. while utilizing hydrogen sulfide containing hydrogen to vulcanize, carry out wet method sulfidation toward introduction sulfurized oil in gasoline hydrogenation reactor.
In the inventive method, the sulfidation of step (5) gasoline hydrotreater is as follows: be warming up to 130 DEG C ~ 180 DEG C periods at gasoline hydrotreater reactor, a part of H 2 S-containing gas of high sulfur-containing diesel hydro-refining unit high-pressure separator (abbreviation high score) is introduced gasoline hydrogenation process unit go into operation, and confirm H2S penetrates the beds of gasoline hydrogenation process reactor.Afterwards, the content of hydrogen sulfide in the gas of gasoline hydrogenation process reactor can be adjusted into by suitably regulating new hydrogen mixed volume, reach the concentration of hydrogen sulfide needed for gasoline hydrotreater sulfidation.With the speed of 1 DEG C/h ~ 30 DEG C/h, gasoline hydrogenation is processed each bed of process reactor and rise to 190 DEG C ~ 250 DEG C, constant temperature 2h ~ 16h hour, then with the speed of 1 DEG C/h ~ 30 DEG C/h, gasoline hydrogenation is processed each bed of process reactor and rise to 260 DEG C ~ 350 DEG C, constant temperature 2h ~ 16h hour.Concentration of hydrogen sulfide when gasoline hydrogenation process unit goes into operation refers to H in gasoline hydrogenation process reactor entrance hydrogen2The concentration of S.In described gasoline hydrogenation reactor sulfidation, the temperature of the H 2 S-containing gas introduced can be adjusted by gasoline hydrogenation unit furnace, or the temperature simultaneously adjusting H 2 S-containing gas and sulfurized oil adjusts the curing temperature of gasoline hydrogenation reactor.If using wet method sulfuration, described sulfurized oil is oil product well known in the art, such as, can be straight-run naphtha, virgin kerosene, normal two wires oil, atmosphere 3rd side cut oil or straight-run diesel oil etc..
In the inventive method, after the gasoline hydrotreater sulfuration described in step (6) terminates, start the circulating hydrogen compressor of gasoline hydrogenation device, be adjusted to normal workflow, adjust operating condition by method well known to those skilled in the art, switch raw oil.
The recycle hydrogen that high sulfur-containing diesel hydro-refining unit high score is obtained by the inventive method, processes the vulcanization process of the vulcanisation cycle hydrogen of the sulfur-bearing agent of process unit, has the advantage that as gasoline hydrogenation
1, the vulcanization process of the oxidation state Gasoline Hydrotreating Catalysts that the present invention provides, it is ensured that higher cure efficiency.Owing to high sulfur-containing diesel hydro-refining unit high score gas containing the hydrogen sulfide of higher concentration, it is when gasoline hydrogenation catalyst vulcanizes, hydrogen sulfide directly vulcanizes with gasoline hydrogenation catalyst effect, both ensure that preferable cure efficiency, and also reduced in sulfidation simultaneously and concentrate highly exothermic generation.
2, the method that the present invention provides, it is only necessary to simply transform existing equipment, it is possible to reach requirement, such that it is able to reduce sulfuration investment.
3, the method that the present invention provides, it is to avoid be artificially injected the vulcanizing agent murder by poisoning to human body in prior art, easy sulfuration goes into operation operation, has considerable economic benefit and social benefit.
4, due in the method, use the high score output gas of high sulfur-containing diesel hydro-refining unit, introduce gasoline hydrotreater, H 2 S-containing gas is made to be utilized, there is provided gasoline hydrogenation process process unit at sulfidation vulcanizing agent, efficiently utilize the hydrogen sulfide in high sulfur-containing diesel hydro-refining unit output gas.
5, using the sulfuration start-up method of the gasoline hydrotreater of present invention offer, its technique is simple, simple operation, and safety is good, environmental friendliness, and has higher catalysis activity.
6, gasoline hydrogenation device directly uses diesel hydrotreating unit high score output gas to vulcanize, this process will not occur vulcanizing agent in prior art to generate hydrogen sulfide and the reaction of methane with hydrogen, therefore after even across sulfuration, the hydrogen purity that gasoline hydrogenation device obtains gas is the highest, after processing with or without gasoline hydrogenation device desulfurizing tower, diesel hydrotreating unit make-up hydrogen compressor can be entered be used as to supplement hydrogen, or hydrogen pipe network can be returned.
Accompanying drawing explanation
Fig. 1 is a kind of schematic diagram that gasoline hydrogenation of the present invention processes the vulcanization process of process catalyst.
Fig. 2 is the another kind of schematic diagram that gasoline hydrogenation of the present invention processes the vulcanization process of process catalyst.
Wherein high sulfur-containing diesel hydrogenation plant mainly includes diesel oil hydrogenation reactor 2, high score 4 and circulating hydrogen compressor 6；And gasoline hydrogenation device mainly includes gasoline hydrogenation reactor 9, separator 11 and desulfurizing tower 12, figure eliminates some non-critical devices, but these equipment are the most all known.
Detailed description of the invention
For a more detailed description to the method for present disclosure with specific embodiment below in conjunction with the accompanying drawings.
As shown in Figure 1, during high sulfur-containing diesel hydrogenation plant runs well, raw material diesel oil enters diesel oil hydrogenation reactor 2 through pipeline 1, recycle hydrogen after the supplementary hydrogen mixing that pipeline 7 and make-up hydrogen compressor 14 introduce, reaction effluent enters high-pressure separator (high score) 4 through pipeline 3, major part high score gas obtains recycle hydrogen after pipeline 5 and circulating hydrogen compressor 6, and liquid through line 12 is discharged.Gasoline hydrogenation device through gas displacement, catalyst be dried and device airtight qualified after, prepare to go into operation sulfuration.Diesel hydrotreating unit high score 4 gained a part of high score gas is after suitable decompression, gasoline hydrogenation reactor 9 is entered through pipeline 8, in certain embodiments, sulfurized oil can also be introduced by pipeline 15, the gasoline hydrogenation catalyst of filling in gasoline hydrogenation reactor is carried out sulfur, reactor 9 obtains effluent and enters gasoline hydrogenation device high score 11 through pipeline 10, liquid (including that sulfidation generates water) is discharged through pipeline 13, high score gas is after gasoline hydrogenation device desulfurizing tower 17, return one-level or the split-compressor entrance of the make-up hydrogen compressor 14 of diesel oil hydrogenation reactor through pipeline 16 as supplementary hydrogen.After the sulfuration of gasoline hydrogenation device terminates, oil hydrotreater carries out the circulation operation of repeats itself hydrogen, adjusts bed and carries out gasoline hydrogenation reaction to gasoline hydrogenation reaction temperature, switching raw oil.
As shown in Figure 2, the another embodiment of present disclosure method is: during high sulfur-containing diesel hydrogenation plant runs well, raw material diesel oil enters diesel oil hydrogenation reactor 2 through pipeline 1, recycle hydrogen after the supplementary hydrogen mixing that pipeline 7 and make-up hydrogen compressor 14 introduce, reaction effluent enters high-pressure separator (high score) 4 through pipeline 3, major part high score gas obtains recycle hydrogen after pipeline 5 and circulating hydrogen compressor 6, and liquid through line 12 is discharged.Gasoline hydrogenation device through gas displacement, catalyst be dried and device airtight qualified after, prepare to go into operation sulfuration.The secured satisfactory grades gas of diesel hydrotreating unit high score 4 processes and after circulating hydrogen compressor 6 compresses through desulfurization, a part of circulating air is after suitable decompression, gasoline hydrogenation reactor 9 is entered through pipeline 8, in certain embodiments, sulfurized oil can also be introduced by pipeline 15, the gasoline hydrogenation catalyst of filling in gasoline hydrogenation reactor is carried out sulfur, reactor 9 obtains effluent and enters gasoline hydrogenation device high score 11 through pipeline 10, liquid (including that sulfidation generates water) is discharged through pipeline 13, high score gas is after gasoline hydrogenation device desulfurizing tower 17, return one-level or the split-compressor entrance of the make-up hydrogen compressor 14 of diesel oil hydrogenation reactor through pipeline 16 as supplementary hydrogen.After the sulfuration of gasoline hydrogenation device terminates, oil hydrotreater carries out the circulation operation of repeats itself hydrogen, adjusts bed and carries out gasoline hydrogenation reaction to gasoline hydrogenation reaction temperature, switching raw oil.
Following specific embodiment is for being specifically described the method for present disclosure, but it is not intended that the restriction to present disclosure method.
Embodiment 1
Use technological process shown in Fig. 1.During high sulfur-containing diesel hydrogenation plant runs well.Diesel raw material sulfur content is 2.03wt%, and process conditions are: reactive hydrogen dividing potential drop 6.3MPa, volume space velocity 2.0h-1, average reaction temperature 360 DEG C, hydrogen to oil volume ratio 350.Reformed pre-hydrogenated device through gas displacement, catalyst be dried and device airtight qualified after, prepare to go into operation sulfuration.After reformed pre-hydrogenated device reaction device 9 reaction bed temperature rises to 150 DEG C, introduce sulfurized oil by pipeline 15.Reactor 9 obtains effluent and enters reformed pre-hydrogenated device high score 11 through pipeline 10.After reactor 9 reaction bed temperature rises to 180 DEG C, the hydrogenation catalyst of filling in reformation pre-hydrogenator is vulcanized.Diesel hydrotreating unit high score 4 gained a part of high score gas, after decompression, enters reformed pre-hydrogenated reactor 9 through pipeline 8.Liquid (including that sulfidation generates water) is discharged through pipeline 13, and high score gas, after reformed pre-hydrogenated device desulfurizing tower 12, returns to the suction port of compressor of the make-up hydrogen compressor 14 of diesel oil hydrogenation reactor as supplementary hydrogen through pipeline 16.After flow process is got through, and confirm H2S penetrates reformed pre-hydrogenated process reactor 9 beds.With the speed of 8 DEG C/h, reformed pre-hydrogenated process reactor 9 bed is risen to 230 DEG C, H2It is 5000 μ L/L that the concentration of S controls, constant temperature 8 hours；Then with the speed of 6 DEG C/h, reformed pre-hydrogenated process reactor 9 bed is risen to 290 DEG C, H2It is 10000 μ L/L that the concentration of S controls, constant temperature 10 hours.
Catalyst property: containing MoO316.0wt%, NiO4.5wt% and CoO0.1wt%.Conditions of vulcanization is, pressure 2.0MPa, sulfurized oil volume space velocity 5.0h-1, hydrogen-oil ratio 100.Sulfurized oil is virgin kerosene.
After sulfuration terminates, adjust temperature, introduce raw oil.After introducing raw material, adjusting process condition is: volume space velocity 5.0h-1, pressure 2.0MPa, hydrogen-oil ratio 100, average reaction temperature 285 DEG C.Operating 48 hours, adopt finished product oil sample and be analyzed, catalyst activity the results are shown in Table 1.
Table 1 raw oil character and refined oil character.
| Oil product title | Feed naphtha | Refined oil |
| Density (20 DEG C), g cm-3 | 0.7416 | 0.7408 |
| Boiling range/DEG C | 38～174 | 40～176 |
| S, μ g/g | 163 | ＜ 0.5 |
| N, μ g/g | 1.31 | ＜ 0.5 |
Embodiment 2
Use technological process shown in Fig. 1.During high sulfur-containing diesel hydrogenation plant runs well.Diesel raw material sulfur content 2.03wt%, process conditions are: reactive hydrogen dividing potential drop 6.3MPa, volume space velocity 2.0h-1, average reaction temperature 360 DEG C, hydrogen to oil volume ratio 350.Hydrogenation of Coker Gasoline device through gas displacement, catalyst be dried and device airtight qualified after, prepare to go into operation sulfuration.After Hydrogenation of Coker Gasoline device reaction device 9 reaction bed temperature rises to 160 DEG C, introduce sulfurized oil by pipeline 15.Reactor 9 obtains effluent and enters Hydrogenation of Coker Gasoline device high score 11 through pipeline 10.After reactor 9 reaction bed temperature rises to 180 DEG C, the hydrogenation catalyst of filling in Hydrogenation of Coker Gasoline reactor is vulcanized.Diesel hydrotreating unit high score 4 gained a part of high score gas is after suitable decompression, gasoline hydrogenation reactor 9 is entered through pipeline 8, liquid (including that sulfidation generates water) is discharged through pipeline 13, high score gas, after Hydrogenation of Coker Gasoline device desulfurizing tower 12, returns to the suction port of compressor of the make-up hydrogen compressor 14 of diesel oil hydrogenation reactor as supplementary hydrogen through pipeline 16.After flow process is got through, and confirm H2S penetrates Hydrogenation of Coker Gasoline reactor 9 beds.With the speed of 6 DEG C/h, Hydrogenation of Coker Gasoline reactor 9 bed is risen to 230 DEG C, H2It is 6000 μ L/L that the concentration of S controls, constant temperature 8 hours；Then with the speed of 15 DEG C/h, Hydrogenation of Coker Gasoline reactor 9 bed is risen to 310 DEG C, H2It is 10000 μ L/L that the concentration of S controls, constant temperature 10 hours.
Catalyst property is: containing MoO316.0wt%, NiO4.5wt% and CoO0.1wt%.Conditions of vulcanization is, pressure 3.0MPa, sulfurized oil volume space velocity 5.0h-1, hydrogen-oil ratio 100.Sulfurized oil is virgin kerosene.
After sulfuration terminates, adjust temperature, introduce raw oil.After introducing raw material, adjusting process condition is: volume space velocity 3.8h-1, pressure 3.0MPa, hydrogen-oil ratio 350, reactor inlet temperature 190 DEG C, reactor outlet temperature 300 DEG C.Operating 48 hours, adopt finished product oil sample and be analyzed, catalyst activity the results are shown in Table 2.
Embodiment 3
Use flow process shown in Fig. 2.During high sulfur-containing diesel hydrogenation plant runs well.Diesel raw material sulfur content 2.03wt%, process conditions are: reactive hydrogen dividing potential drop 6.3MPa, volume space velocity 2.0h-1, average reaction temperature 360 DEG C, hydrogen to oil volume ratio 350.Hydrogenation of Coker Gasoline device through gas displacement, catalyst be dried and device airtight qualified after, prepare to go into operation sulfuration.After Hydrogenation of Coker Gasoline device reaction device 9 reaction bed temperature rises to 180 DEG C, now, adjust high sulfur-containing diesel hydrogenation plant recycle hydrogen de sulfuration hydrogen production device, hydrogen sulfide containing circulating hydrogen is after circulating hydrogen compressor 6, part H 2 S-containing gas circulating hydrogen, Hydrogenation of Coker Gasoline reactor 9 is entered through pipeline 8, liquid (including that sulfidation generates water) is discharged through pipeline 13, high score gas, after Hydrogenation of Coker Gasoline device desulfurizing tower 12, returns to the suction port of compressor of the make-up hydrogen compressor 14 of diesel oil hydrogenation reactor as supplementary hydrogen through pipeline 16.After flow process is got through, and confirm H2S penetrates Hydrogenation of Coker Gasoline reactor 9 beds.With the speed of 10 DEG C/h, Hydrogenation of Coker Gasoline process reactor 9 bed is risen to 230 DEG C, H2It is 5000 μ L/L that the concentration of S controls, constant temperature 8 hours；Then with the speed of 10 DEG C/h, Hydrogenation of Coker Gasoline process reactor 9 bed is risen to 315 DEG C, H2It is 10000 μ L/L that the concentration of S controls, constant temperature 10 hours.
Catalyst is with embodiment 2.Conditions of vulcanization is, pressure 3.0MPa, sulfurized oil volume space velocity 5.0h-1, hydrogen-oil ratio 100.Sulfurized oil is virgin kerosene.
After sulfuration terminates, adjust temperature, introduce raw oil.After introducing raw material, adjusting process condition is: volume space velocity 3.8h-1, pressure 3.0MPa, hydrogen-oil ratio 350, reactor inlet temperature 190 DEG C, reactor outlet temperature 300 DEG C.Operating 48 hours, adopt finished product oil sample and be analyzed, catalyst activity the results are shown in Table 2.
Table 2 raw oil character and refined oil character.
| Oil product title | Coker gasoline raw material | Embodiment 2 | Embodiment 3 |
| Density (20 DEG C), g cm-3 | 0.7413 | 0.7405 | 0.7397 |
| Boiling range/DEG C | 57～204 | 58～205 | 55～203 |
| S, μ g/g | 5676 | 65 | 56 |
| N, μ g/g | 226 | 2 | 1 |
Embodiment 4
Use flow process shown in Fig. 2.During high sulfur-containing diesel hydrogenation plant runs well.Diesel raw material sulfur content 2.03wt%, process conditions are: reactive hydrogen dividing potential drop 6.3MPa, volume space velocity 2.0h-1, average reaction temperature 360 DEG C, hydrogen to oil volume ratio 350.Gasoline hydrogenation device through gas displacement, catalyst be dried and device airtight qualified after, prepare to go into operation sulfuration.Gasoline hydrogenation device reaction device 9 reaction bed temperature rises to 180 DEG C, now, adjust the sulfuration hydrogen production device operation of high sulfur-containing diesel hydrogenation plant recycle hydrogen de, hydrogen sulfide containing circulating hydrogen follows after ring hydrogen compressor 6, part H 2 S-containing gas circulating hydrogen enters gasoline hydrogenation reactor 9 through pipeline 8, liquid (including that sulfidation generates water) is discharged through pipeline 13, high score gas, after gasoline hydrogenation device desulfurizing tower 12, returns make-up hydrogen compressor 14 entrance of diesel oil hydrogenation reactor as supplementary hydrogen through pipeline 16.After flow process is got through, and confirm H2S penetrates Processes of FCC Naphtha Hydrotreating process reactor 9 beds.With the speed of 8 DEG C/h, gasoline hydrogenation process reactor 9 bed is risen to 230 DEG C, H2It is 4000 μ L/L that the concentration of S controls, constant temperature 9 hours；Then with the speed of 10 DEG C/h, gasoline hydrogenation process reactor 9 bed is risen to 315 DEG C, H2It is 10000 μ L/L that the concentration of S controls, constant temperature 10 hours.
Catalyst property: containing MoO13.2wt%, containing CoO4.5wt%.Conditions of vulcanization is, pressure 2.0MPa, sulfurized oil volume space velocity 5.0h-1, hydrogen-oil ratio 300.Sulfurized oil is virgin kerosene.
After sulfuration terminates, adjust temperature, introduce raw oil.After introducing raw material, adjusting process condition is: pressure 2.0MPa, volume space velocity 5.0h-1, hydrogen to oil volume ratio 300, reactor inlet temperature 190 DEG C, reactor outlet temperature 260 DEG C.Operating 48 hours, adopt finished product oil sample and be analyzed, catalyst activity the results are shown in Table 3.
Embodiment 5
Use flow process shown in Fig. 2.During high sulfur-containing diesel hydrogenation plant runs well.Diesel raw material sulfur content 2.03wt%, process conditions are: reactive hydrogen dividing potential drop 6.3MPa, volume space velocity 2.0h-1, average reaction temperature 360 DEG C, hydrogen to oil volume ratio 350.Raw material diesel oil enters diesel oil hydrogenation reactor 2 through pipeline 1, recycle hydrogen after the supplementary hydrogen mixing that pipeline 7 and make-up hydrogen compressor 14 introduce, reaction effluent enters high score 4 through pipeline 3, major part high score gas obtains recycle hydrogen after pipeline 5 and circulating hydrogen compressor 6, and liquid through line 12 is discharged.Gasoline hydrogenation device through gas displacement, catalyst be dried and device airtight qualified after, prepare to go into operation sulfuration.After gasoline hydrogenation device reaction device 9 reaction bed temperature rises to 150 DEG C, introduce sulfurized oil by pipeline 15.Reactor 9 obtains effluent and enters gasoline hydrogenation device high score 11 through pipeline 10.After reactor 9 reaction bed temperature rises to 160 DEG C, the hydrogenation catalyst of filling in gasoline hydrogenation reactor is vulcanized.Diesel hydrotreating unit high score 4 gained a part of high score gas is after suitable decompression, gasoline hydrogenation reactor 9 is entered through pipeline 8, liquid (including that sulfidation generates water) is discharged through pipeline 13, high score gas, after gasoline hydrogenation device desulfurizing tower 12, returns the entrance of the make-up hydrogen compressor 14 of diesel oil hydrogenation reactor as supplementary hydrogen through pipeline 16.After flow process is got through, and confirm H2S penetrates gasoline hydrogenation process reactor 9 beds.With the speed of 6 DEG C/h, gasoline hydrogenation process reactor 9 bed is risen to 220 DEG C, H2It is 6000 μ L/L that the concentration of S controls, constant temperature 9 hours；Then with the speed of 15 DEG C/h, gasoline hydrogenation process reactor 9 bed is risen to 270 DEG C, H2It is 10000 μ L/L that the concentration of S controls, constant temperature 10 hours.
Catalyst property is with embodiment 4.Conditions of vulcanization is, pressure 2.0MPa, sulfurized oil volume space velocity 5.0h-1, hydrogen-oil ratio 300.Sulfurized oil is virgin kerosene.
After sulfuration terminates, adjust temperature, introduce raw oil.After introducing raw material, adjusting process condition is: pressure 2.0MPa, volume space velocity 5.0h-1, hydrogen to oil volume ratio 300, reactor inlet temperature 190 DEG C, reactor outlet temperature 260 DEG C.Operating 48 hours, adopt finished product oil sample and be analyzed, catalyst activity the results are shown in Table 3.
Table 3 raw oil character and refined oil character
| Oil product title | Catalytic gasoline raw material | Embodiment 4 | Embodiment 5 |
| Density (20 DEG C), g cm-3 | 0.7386 | 0.7361 | 0.7358 |
| Boiling range/DEG C | 42～196 | 40～195 | 41～197 |
| S, μ g/g | 564 | 49 | 50 |
| RON | 93 | 91 | 91 |
Claims (11)
1. gasoline hydrogenation processes a catalyst vulcanization method for technique, including following content:
(1) high sulfur-containing diesel hydro-refining unit runs well；
(2) filling oxidation state gasoline hydrogenation catalyst in gasoline hydrotreater reactor；
(3) gasoline hydrotreater carries out gas displacement, catalyst is dried and device air tight work；
(4) the part H 2 S-containing gas obtained by high sulfur-containing diesel hydro-refining unit, introduces gasoline hydrotreater, the catalyst in gasoline hydrotreater reactor is carried out vulcanisation operation；
(5) sulfidation of gasoline hydrotreater includes: constant temperature 2h ~ 16h, H at 190 DEG C ~ 250 DEG C2It is 500 μ L/L ~ 15000 μ L/L that the concentration of S controls；Constant temperature 5h ~ 16h, H at 260 DEG C ~ 350 DEG C2It is 5000 μ L/L ~ 30000 μ L/L that the concentration of S controls；
(6) after sulfuration terminates, gasoline hydrotreater carries out the circulation operation of repeats itself hydrogen, adjustment bed to reaction temperature, and switching raw oil carries out gasoline hydrogenation and processes reaction.
The most in accordance with the method for claim 1, it is characterised in that the high sulfur-containing diesel hydro-refining unit feed sulphur content described in step (1) is more than 0.5wt%.
The most in accordance with the method for claim 1, it is characterised in that the process conditions of the high sulfur-containing diesel hydro-refining unit described in step (1) are: reaction pressure 4 ~ 10MPa, reaction temperature 280 DEG C ~ 400 DEG C, volume space velocity 0.1 ~ 10h-1, hydrogen to oil volume ratio 100 ~ 2000.
The most in accordance with the method for claim 1, it is characterised in that the gasoline hydrotreater described in step (2) is gasoline hydrogenation device, reformed pre-hydrogenated device or Hydrogenation of Coker Gasoline device.
The most in accordance with the method for claim 1, it is characterized in that, the mode that gasoline hydrogenation device uses that the H 2 S-containing gas of high sulfur-containing diesel hydro-refining unit introduced described in step (4) is: a part of high score gas of diesel hydrotreating unit is introduced gasoline hydrogenation device, the gas that gasoline hydrogenation device high score obtains through or without gasoline hydrogenation device desulfurizing tower after as the supplementary hydrogen of Diesel Oil Hydrofining Unit or be directly discharged into hydrogen pipe network.
The most in accordance with the method for claim 1, it is characterized in that, the described mode that the H 2 S-containing gas of high sulfur-containing diesel hydro-refining unit introduces the employing of gasoline hydrogenation device is: draws a part of H 2 S-containing gas after high sulfur-containing diesel hydro-refining unit desulfurizing tower, introduces in the reactor of gasoline hydrogenation device after suitable blood pressure lowering.
The most in accordance with the method for claim 1, it is characterised in that the sulfidation of step (5) gasoline hydrogenation device is dry pre-sulfiding.
The most in accordance with the method for claim 1, it is characterized in that, the sulfidation of step (5) gasoline hydrogenation device is wet method sulfuration, in gasoline hydrogenation reactor, sulfurized oil is introduced while introducing H 2 S-containing gas from Diesel Oil Hydrofining Unit, while being passed through sulfurized oil, hydrogen sulfide containing hydrogen is utilized to carry out sulfidation.
The most in accordance with the method for claim 1, it is characterised in that the hydrogenation active component of the gasoline hydrogenation catalyst described in step (2) is one or more in W, Mo, Ni and Co, with oxide count hydrogenation active component content as 3wt% ~ 50wt%.
The most in accordance with the method for claim 1, it is characterised in that the concentration of hydrogen sulfide during step (5) gasoline hydrogenation device catalyst vulcanization is adjusted by filling into the new hydrogen of part.
11. in accordance with the method for claim 1, it is characterised in that described in step (5), the programming rate of sulfidation is 1 DEG C/h ~ 30 DEG C/h.
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| CN104403685B (en) * | 2014-09-27 | 2016-04-20 | 宁夏宝塔石化科技实业发展有限公司 | A kind of sulfuration process of gasoline selective hydrodesulfurizationmodification device |
| CN105344293B (en) * | 2015-11-28 | 2018-06-22 | 王荣超 | The hydrogen sulfide compression method and device of hydrotreating |
| CN107434981A (en) * | 2016-05-26 | 2017-12-05 | 中石化广州工程有限公司 | A kind of method of continuous reformer note sulphur |
| CN111822058B (en) * | 2019-04-19 | 2023-01-10 | 中国石油化工股份有限公司 | Pre-sulfurizing process of hydrogenation catalyst |
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| CN100432191C (en) * | 2005-10-19 | 2008-11-12 | 中国石油化工股份有限公司 | Method for FCC gasoline proceeding hydrodesulphurization and olefin removal |
| CN101376835A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Gasoline hydrofinishing startup method and gasoline hydrofinishing operation method |
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| CN100432191C (en) * | 2005-10-19 | 2008-11-12 | 中国石油化工股份有限公司 | Method for FCC gasoline proceeding hydrodesulphurization and olefin removal |
| CN101376835A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Gasoline hydrofinishing startup method and gasoline hydrofinishing operation method |
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