CN103361111A - Catalyst sulfurization method of gasoline hydrotreating technique - Google Patents
Catalyst sulfurization method of gasoline hydrotreating technique Download PDFInfo
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Abstract
The invention discloses a catalyst sulfurization method of a gasoline hydrogenation technique, which comprises the following steps: (1) normally operating a high-sulfur diesel hydrofining unit; (2) filling an oxidation-state gasoline hydrogenation catalyst in a gasoline hydrotreater reactor; (3) carrying out gas displacement, catalyst drying and airtight operation on the gasoline hydrotreater; (4) introducing part of hydrogen-sulfide-containing gas obtained from the high-sulfur diesel hydrofining unit into the gasoline hydrotreater, carrying out sulfurization on the catalyst in the gasoline hydrotreater reactor; (5) sulfurizing according to normal sulfurization conditions of the gasoline hydrogenation technique; and (6) after the sulfurization is finished, carrying out recycle hydrogen recycling operation on the gasoline hydrotreater, regulating the bed to reaction temperature, and switching to raw oil to carry out gasoline hydrotreating. The method disclosed by the invention can enhance the sulfurization efficiency and reduce the consumption of the sulfurizing agent.
Description
Technical field
The present invention relates to a kind of catalyst vulcanization method of gasoline hydrogenation treatment process, particularly comprise simultaneously the catalyst vulcanization method of the gasoline hydrogenation treatment process of high sulfur-containing diesel hydro-refining unit and gasoline hydrogenation treatment process device for oil refining enterprise.
Technical background
Because crude production rate increasess slowly and heaviness increasingly, and the world today constantly increases the clear gusoline demand, and quality product requires also more and more stricter.The petroleum fractions hydrogen addition technology is the major technique of current production 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 reactive metal need be converted into sulphided state and just have higher catalytic activity.Therefore, the sulfuration of catalyzer has material impact to the performance of catalyzer, is the important process step before catalyzer is used.
The method for pre-sulphuration of catalyzer can be divided into prevulcanized and the outer prevulcanized of device in the device by the mode of carrying sulphur.Up to now, both at home and abroad most refinery still adopts prevulcanized mode in the device, and namely fresh or regenerated catalyst loads and introduces vulcanizing agent behind the reactor and vulcanize, and perhaps load vulcanizing agent in catalyzer carries out vulcanization reaction in reactor.State according to vulcanizing agent is different, and the prevulcanized mode can be divided into again wet method sulfuration and dry method sulfuration in the device.The wet method sulfuration also claims the liquid phase sulfuration, is in the presence of hydrogen, the liquid curing agent is dissolved in forming vulcanized oil in the benzoline first, and then interior the contact with hydrogenation catalyst of input reactor carried out vulcanization reaction.Dry method sulfuration also claims the gas phase sulfuration, refers to catalyzer in the presence of hydrogen, directly contacts with certain density vulcanizing agent and vulcanizes.
CN99123716.1 discloses again start-up method of a kind of reformer that loads two/multimetallic catalyst, comprise and use the nitrogen purging reaction unit, then at 350～420 ℃ of lower dry catalysts, pass into stock oil afterwards in reforming reactor, the control water chloride balance is until reach the operational condition of normal production.
USP4725571 discloses a kind of method of catalyst wet sulfuration, and the method adds two kinds of vulcanizing agents by adopting in vulcanized oil, finish the prevulcanized of catalyzer.
CN1362493A discloses a kind of vulcanization process of catalyst for hydroprocessing of heavy oil, at first solid-state inorganic sulphide and Hydrodemetalation catalyst are mixed, then by adopting the means that dry method sulfuration under the low temperature is combined with wet method vulcanization process under the high temperature, reduced the consumption of vulcanized oil, reduced the sulfuration cost, and the vulcanizing agent sulfurization rate is good, has given full play to the performance of catalyzer.
CN01106022.0 discloses a kind of vulcanization process of catalyst for hydroprocessing of heavy oil, be characterized in solid-state inorganic sulphide and Hydrodemetalation catalyst are mixed, then by adopting the means that dry method sulfuration under the low temperature is combined with wet method vulcanization process under the high temperature, reduced the consumption of vulcanized oil, reduced the sulfuration cost, and the vulcanizing agent sulfurization rate is good, has given full play to the performance of catalyzer.
In the modern oil refining enterprise, generally comprise many cover hydrogenation units, generally comprise that wax oil hydrogenation processing, hydrocracking, residual hydrocracking, diesel oil hydrofining, gasoline hydrogenation modifying, kerosene hydrogenation are refining, hydrorefining basic oil lubricating oil, hydrorefining paraffin wax etc., and for large-scale oil refining enterprise, the hydrogenation unit of a certain type generally also comprises many covers, and hydrogenation unit has become the maximum processing unit (plant) of quantity in the oil refining enterprise.Though the purpose of different hydrogenation units is different, but desulphurization reaction is the common reaction that exists in numerous hydrogenation units, development along with the high sulfuration of raw material, and the requirement of the low sulfuration of clean fuel, desulphurization reaction becomes one of critical function of hydrogenation unit, the main purpose of some hydrogenation unit is exactly hydrogenating desulfurization, such as diesel oil hydrogenation processing etc.Prior art hydrogenation catalyst sulfidation does not have to consider the combine operations of many cover hydrogenation units only for a certain cover hydrogenation unit.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of catalyst vulcanization method of gasoline hydrogenation treatment process, carry out catalyst vulcanization in conjunction with the high sulfur-containing diesel hydro-refining unit and go into operation, improve sulfuration efficient, reduce vulcanizing agent consumption.
The catalyst vulcanization method of gasoline hydrogenation treatment process of the present invention comprises following content:
(1) the high sulfur-containing diesel hydro-refining unit runs well;
(2) filling oxidation state gasoline hydrogenation catalyst in the gasoline hydrotreater reactor;
(3) gasoline hydrotreater is carried out gas displacement, catalyzer is dry and the device airtight work;
(4) H 2 S-containing gas that the high sulfur-containing diesel hydro-refining unit is obtained is introduced gasoline hydrotreater, and the catalyzer in the gasoline hydrotreater reactor is carried out vulcanisation operation;
(5) sulfidation of gasoline hydrotreater comprises: at 190 ℃ ~ 250 ℃ lower constant temperature 2h ~ 16h, H
2The concentration of S is controlled to be 500 μ L/L ~ 15000 μ L/L; At 260 ℃ ~ 350 ℃ lower constant temperature 5h ~ 16h hours, H
2The concentration of S is controlled to be 5000 μ L/L ~ 30000 μ L/L;
(6) after sulfuration finished, gasoline hydrotreater was carried out self recycle hydrogen cyclical operation, adjusted bed to temperature of reaction, switched stock oil and carried out the gasoline hydrogenation processing reaction.
In the inventive method, the high sulfur-containing diesel hydro-refining unit of the described steady running of step (1) generally is the medium-pressure or high pressure device of stably manufactured running in the oil refining enterprise, and pressure rating is generally 4 ~ 10MPa.The operational condition of high sulfur-containing diesel hydro-refining unit is undertaken by normal running.The feed sulphur content of high sulfur-containing diesel hydro-refining unit is generally more than the 0.5wt%, is preferably 0.5wt% ~ 5wt%.The processing condition of Diesel Oil Hydrofining Unit are generally in the step (1): reaction pressure 4 ~ 10MPa, 280 ℃ ~ 400 ℃ of temperature of reaction, volume space velocity 0.1 ~ 10h
-1, hydrogen to oil volume ratio 100 ~ 2000.
In the inventive method, the described gasoline hydrotreater of step (2) can be catalytic gasoline hydrogenation unit, reformed pre-hydrogenated device or Hydrogenation of Coker Gasoline device.
In the inventive method, the gasoline hydrogenation catalyst described in the step (2) is generally take the composite oxides of porous, inorganic refractory oxide such as aluminum oxide, silicon oxide, amorphous silicon aluminium, titanium oxide, molecular sieve and several elements or mixed oxide etc. as carrier.No acidic or the weakly acidic material of gasoline hydrogenation catalyst normal operation is carrier, such as aluminum oxide, silicon oxide, amorphous silicon aluminium etc., load hydrogenation active metals component.The hydrogenation activity component of Gasoline Hydrotreating Catalysts is one or more among W, Mo, Ni and the Co, is generally 3wt% ~ 50wt% in oxide compound hydrogenation activity component concentration.Gasoline Hydrotreating Catalysts can be selected suitable commercial catalyst by the needs of technical process, can by existing method preparation, also can be that decaying catalyst is through the regenerated catalyst after regenerating also.
In the inventive method, the described gas displacement of step (3), catalyzer are dry and install the start-up method well-known to those skilled in the art that is operating as such as airtight.As in " hydrocracking ", " hydroprocessing technique and engineering " and " hydrocracking process and engineering ", all having put down in writing the working method of said process.
In the inventive method, the described H 2 S-containing gas with the high sulfur-containing diesel hydro-refining unit of step (4) is introduced the gasoline hydrogenation device and can be comprised following dual mode: the part of diesel hydrotreating unit high score gas is introduced the gasoline hydrogenation device, the gas that obtains through gasoline hydrogenation device high score through or behind the gasoline hydrogenation device thionizer as the hydrogen make-up of Diesel Oil Hydrofining Unit, return (one-level or secondary) entrance of diesel hydrotreating unit make-up hydrogen compressor, perhaps directly enter the hydrogen pipe network; Perhaps in step (4) behind high sulfur-containing diesel hydro-refining unit thionizer, preferably behind circulating hydrogen compressor, draw a part of H 2 S-containing gas, through introducing in the reactor of gasoline hydrogenation device after the suitable step-down.Described gasoline hydrogenation device thionizer generally adopts the hydrogen sulfide in the amine liquid wash-out circulation gas, and the injection rate by regulating poor amine liquid is to regulate the hydrogen sulfide stripping rate.Concentration of hydrogen sulfide is generally below 500 μ L/L in the gas after process gasoline hydrogenation device thionizer is processed.
In the inventive method, concentration of hydrogen sulfide in the step (5) in the gasoline hydrogenation device catalyst vulcanization process can both directly satisfy the sulfuration needs of gasoline hydrogenation catalyst usually, perhaps can regulate by filling into the new hydrogen of part, so that it better meets the sulfidation needs.If directly the extension H 2 S-containing gas then can come hydrogen sulfide content in the adjustments of gas by the operation of regulating the diesel hydrotreating unit thionizer to gasoline hydrotreater behind the Diesel Oil Hydrofining Unit thionizer.
In the inventive method, the sulfidation of step (5) gasoline hydrogenation device can be vulcanized for dry method; Also can vulcanize for wet method, namely when utilizing hydrogen sulfide containing hydrogen to vulcanize, introduce vulcanized oil in the gasoline hydrogenation reactor and carry out the wet method sulfidation.
In the inventive method, the sulfidation of step (5) gasoline hydrotreater is generally as follows: be warming up to during 130 ℃ ~ 180 ℃ at the 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 the gasoline hydrogenation process unit go into operation, and confirm H
2S penetrates the beds of gasoline hydrogenation process reactor.Afterwards, can adjust by the new hydrogen mixed volume of suitable adjusting the content of hydrogen sulfide in the gas that enters the gasoline hydrogenation process reactor, reach the required concentration of hydrogen sulfide of gasoline hydrotreater sulfidation.Speed with 1 ℃/h ~ 30 ℃/h rises to 190 ℃ ~ 250 ℃ with each bed of gasoline hydrogenation treatment process reactor, constant temperature 2h ~ 16h hour, then the speed with 1 ℃/h ~ 30 ℃/h rises to 260 ℃ ~ 350 ℃ with each bed of gasoline hydrogenation treatment process reactor, constant temperature 2h ~ 16h hour.Concentration of hydrogen sulfide when the gasoline hydrogenation process unit goes into operation refers to H in the gasoline hydrogenation process reactor entrance hydrogen
2The concentration of S.In the described gasoline hydrogenation reactor sulfidation, can pass through the temperature of the H 2 S-containing gas of gasoline hydrogenation unit furnace adjustment introducing, the temperature of perhaps adjusting simultaneously H 2 S-containing gas and vulcanized oil is adjusted the curing temperature of gasoline hydrogenation reactor.If adopt the wet method sulfuration, described vulcanized oil is oil product well known in the art, such as can think virgin naphtha, virgin kerosene, normal two wires oil, atmosphere 3rd side cut is oily or straight-run diesel oil etc.
In the inventive method, after the described gasoline hydrotreater sulfuration of step (6) finishes, start the circulating hydrogen compressor of gasoline hydrogenation device, adjust to normal workflow, by method adjusting operation condition well known to those skilled in the art, switch stock oil.
The recycle hydrogen that the inventive method obtains high sulfur-containing diesel hydro-refining unit high score, the vulcanization process as the vulcanisation cycle hydrogen of the Containing Sulfur agent of gasoline hydrogenation treatment process device has following advantage:
1, the vulcanization process of oxidation state Gasoline Hydrotreating Catalysts provided by the invention can guarantee higher cure efficiency.Owing to containing the hydrogen sulfide of higher concentration in the high sulfur-containing diesel hydro-refining unit high score gas, when it is used for the gasoline hydrogenation catalyst sulfuration, hydrogen sulfide directly and the gasoline hydrogenation catalyst effect vulcanize, both guarantee preferably cure efficiency, also reduced simultaneously the generation of concentrating a large amount of heat releases in the sulfidation.
2, method provided by the invention only needs existing installation is simply transformed, and just can reach requirement, thereby can reduce the sulfuration investment.
3, method provided by the invention avoids in the prior art the artificial vulcanizing agent that injects to the murder by poisoning of human body, and the easy sulfuration operation that goes into operation has considerable economic benefit and social benefit.
4, because in the method, employing is with the high score output gas of high sulfur-containing diesel hydro-refining unit, introduce gasoline hydrotreater, H 2 S-containing gas is utilized, provide gasoline hydrogenation treatment process device at the sulfidation vulcanizing agent, effectively utilized the hydrogen sulfide in the high sulfur-containing diesel hydro-refining unit output gas.
5, adopt the sulfuration start-up method of gasoline hydrotreater provided by the invention, its technique is simple, simple operation, and security is good, environmental friendliness, and have higher catalytic activity.
6, the gasoline hydrogenation device directly uses diesel hydrotreating unit high score output gas to vulcanize, the reaction that vulcanizing agent and hydrogen in the prior art generate hydrogen sulfide and methane can not occur in this process, even therefore behind over cure, the hydrogen purity that the gasoline hydrogenation device obtains gas is still very high, in process or after without the processing of gasoline hydrogenation device thionizer, the diesel hydrotreating unit make-up hydrogen compressor can be entered as hydrogen make-up, perhaps the hydrogen pipe network can be returned.
Description of drawings
Fig. 1 is a kind of schematic diagram of the vulcanization process of gasoline hydrogenation treatment process catalyzer of the present invention.
Fig. 2 is the another kind of schematic diagram of the vulcanization process of gasoline hydrogenation treatment process catalyzer of the present invention.
Wherein the high sulfur-containing diesel hydrogenation unit mainly comprises diesel oil hydrogenation reactor 2, high score 4 and circulating hydrogen compressor 6; And the gasoline hydrogenation device mainly comprises gasoline hydrogenation reactor 9, separator 11 and thionizer 12, has omitted some non-critical devices among the figure, but these equipment all are known to those skilled in the art.
Embodiment
For a more detailed description to the method that the present invention discloses below in conjunction with the drawings and specific embodiments.
As shown in Figure 1, during the high sulfur-containing diesel hydrogenation unit runs well, raw material diesel oil enters diesel oil hydrogenation reactor 2 through pipeline 1, recycle hydrogen after the hydrogen make-up of pipeline 7 and make-up hydrogen compressor 14 introducings is mixed, reaction effluent enters high-pressure separator (high score) 4 through pipeline 3, most of high score gas obtains recycle hydrogen behind pipeline 5 and circulating hydrogen compressor 6, liquid is discharged through pipeline 12.The gasoline hydrogenation device through gas displacement, catalyzer dry and install airtight qualified after, prepare to go into operation sulfuration.Diesel hydrotreating unit high score 4 gained part high score gas is through after the suitable decompression, enter gasoline hydrogenation reactor 9 through pipeline 8, in certain embodiments, can also introduce vulcanized oil by pipeline 15, the gasoline hydrogenation catalyst that loads in the gasoline hydrogenation reactor is vulcanized, reactor 9 obtains effluent and enters gasoline hydrogenation device high score 11 through pipeline 10, liquid (comprising that sulfidation generates water) is discharged through pipeline 13, behind the high score gas process gasoline hydrogenation device thionizer 17, hydrogen returns one-level or the two stage compressor entrance of the make-up hydrogen compressor 14 of diesel oil hydrogenation reactor through pipeline 16 as a supplement.After the sulfuration of gasoline hydrogenation device finished, oily hydrotreater carried out self recycle hydrogen cyclical operation, adjusted bed to the gasoline hydrogenation temperature of reaction, switched stock oil and carried out the gasoline hydrogenation reaction.
As shown in Figure 2, the another kind of embodiment that the present invention discloses method is: during the high sulfur-containing diesel hydrogenation unit runs well, raw material diesel oil enters diesel oil hydrogenation reactor 2 through pipeline 1, recycle hydrogen after the hydrogen make-up of pipeline 7 and make-up hydrogen compressor 14 introducings is mixed, reaction effluent enters high-pressure separator (high score) 4 through pipeline 3, most of high score gas obtains recycle hydrogen behind pipeline 5 and circulating hydrogen compressor 6, liquid is discharged through pipeline 12.The gasoline hydrogenation device through gas displacement, catalyzer dry and install airtight qualified after, prepare to go into operation sulfuration.Diesel hydrotreating unit high score 4 gas that secures satisfactory grades is through the desulfurization processing and after circulating hydrogen compressor 6 compressions, part circulation gas is through after the suitable decompression, enter gasoline hydrogenation reactor 9 through pipeline 8, in certain embodiments, can also introduce vulcanized oil by pipeline 15, the gasoline hydrogenation catalyst that loads in the gasoline hydrogenation reactor is vulcanized, reactor 9 obtains effluent and enters gasoline hydrogenation device high score 11 through pipeline 10, liquid (comprising that sulfidation generates water) is discharged through pipeline 13, behind the high score gas process gasoline hydrogenation device thionizer 17, hydrogen returns one-level or the two stage compressor entrance of the make-up hydrogen compressor 14 of diesel oil hydrogenation reactor through pipeline 16 as a supplement.After the sulfuration of gasoline hydrogenation device finished, oily hydrotreater carried out self recycle hydrogen cyclical operation, adjusted bed to the gasoline hydrogenation temperature of reaction, switched stock oil and carried out the gasoline hydrogenation reaction.
Following specific embodiment is used for the method that the present invention discloses is specifically described, but it does not consist of the restriction that the present invention is disclosed method.
Embodiment 1
Adopt technical process shown in Figure 1.During the high sulfur-containing diesel hydrogenation unit runs well.The diesel raw material sulphur content is 2.03wt%, and processing condition are: reactive hydrogen dividing potential drop 6.3MPa, volume space velocity 2.0h
-1, 360 ℃ of average reaction temperature, hydrogen to oil volume ratio 350.Reformed pre-hydrogenated device through gas displacement, catalyzer is dry and install airtight qualified after, prepare to go into operation sulfuration.After reformed pre-hydrogenated device reaction device 9 reaction bed temperature rise to 150 ℃, introduce vulcanized 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 rise to 180 ℃, the hydrogenation catalyst that loads in the reformation pre-hydrogenator is vulcanized.Diesel hydrotreating unit high score 4 gained part high score gas enters reformed pre-hydrogenated reactor 9 through after reducing pressure through pipeline 8.Liquid (comprising that sulfidation generates water) is discharged through pipeline 13, and high score gas is through behind the reformed pre-hydrogenated device thionizer 12, and hydrogen returns the suction port of compressor of the make-up hydrogen compressor 14 of diesel oil hydrogenation reactor through pipeline 16 as a supplement.After flow process is got through, and confirm H
2S penetrates reformed pre-hydrogenated process reactor 9 beds.Speed with 8 ℃/h rises to 230 ℃, H with reformed pre-hydrogenated process reactor 9 beds
2The concentration of S is controlled to be 5000 μ L/L, constant temperature 8 hours; Then the speed with 6 ℃/h rises to 290 ℃, H with reformed pre-hydrogenated process reactor 9 beds
2The concentration of S is controlled to be 10000 μ L/L, constant temperature 10 hours.
Catalyst property: contain MoO
316.0wt%, NiO 4.5wt% and CoO 0.1 wt%.Cure conditions is pressure 2.0MPa, vulcanized oil volume space velocity 5.0h
-1, hydrogen-oil ratio 100.Vulcanized oil is virgin kerosene.
After sulfuration finishes, adjust temperature, introduce stock oil.The adjusting process condition is after introducing raw material: volume space velocity 5.0h
-1, pressure 2.0MPa, hydrogen-oil ratio 100,285 ℃ of average reaction temperature.Turned round 48 hours, and adopted the finished product oil sample and analyze, catalyst activity the results are shown in Table 1.
Table 1 stock oil character and treated oil character.
| The oil product title | Feed naphtha | Treated oil |
| Density (20 ℃), gcm -3 | 0.7416 | 0.7408 |
| Boiling range/℃ | 38～174 | 40～176 |
| S，μg/g | 163 | ＜0.5 |
| N，μg/g | 1.31 | ＜0.5 |
Adopt technical process shown in Figure 1.During the high sulfur-containing diesel hydrogenation unit runs well.Diesel raw material sulphur content 2.03wt%, processing condition are: reactive hydrogen dividing potential drop 6.3MPa, volume space velocity 2.0h
-1, 360 ℃ of average reaction temperature, hydrogen to oil volume ratio 350.The Hydrogenation of Coker Gasoline device through gas displacement, catalyzer dry and install airtight qualified after, prepare to go into operation sulfuration.After Hydrogenation of Coker Gasoline device reaction device 9 reaction bed temperature rise to 160 ℃, introduce vulcanized 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 rise to 180 ℃, the hydrogenation catalyst that loads in the Hydrogenation of Coker Gasoline reactor is vulcanized.Diesel hydrotreating unit high score 4 gained part high score gas is through after the suitable decompression, enter gasoline hydrogenation reactor 9 through pipeline 8, liquid (comprising that sulfidation generates water) is discharged through pipeline 13, behind the high score gas process Hydrogenation of Coker Gasoline device thionizer 12, hydrogen returns the suction port of compressor of the make-up hydrogen compressor 14 of diesel oil hydrogenation reactor through pipeline 16 as a supplement.After flow process is got through, and confirm H
2S penetrates Hydrogenation of Coker Gasoline reactor 9 beds.Speed with 6 ℃/h rises to 230 ℃ with Hydrogenation of Coker Gasoline reactor 9 beds, H
2The concentration of S is controlled to be 6000 μ L/L, constant temperature 8 hours; Then the speed with 15 ℃/h rises to 310 ℃ with Hydrogenation of Coker Gasoline reactor 9 beds, H
2The concentration of S is controlled to be 10000 μ L/L, constant temperature 10 hours.
Catalyst property is: contain MoO
316.0wt%, NiO 4.5wt% and CoO 0.1 wt%.Cure conditions is pressure 3.0MPa, vulcanized oil volume space velocity 5.0h
-1, hydrogen-oil ratio 100.Vulcanized oil is virgin kerosene.
After sulfuration finishes, adjust temperature, introduce stock oil.The adjusting process condition is after introducing raw material: volume space velocity 3.8h
-1, pressure 3.0MPa, hydrogen-oil ratio 350,190 ℃ of reactor inlet temperatures, 300 ℃ of reactor outlet temperature.Turned round 48 hours, and adopted the finished product oil sample and analyze, catalyst activity the results are shown in Table 2.
Adopt flow process shown in Figure 2.During the high sulfur-containing diesel hydrogenation unit runs well.Diesel raw material sulphur content 2.03wt%, processing condition are: reactive hydrogen dividing potential drop 6.3MPa, volume space velocity 2.0h
-1, 360 ℃ of average reaction temperature, hydrogen to oil volume ratio 350.The Hydrogenation of Coker Gasoline device through gas displacement, catalyzer dry and install airtight qualified after, prepare to go into operation sulfuration.After Hydrogenation of Coker Gasoline device reaction device 9 reaction bed temperature rise to 180 ℃, at this moment, adjust high sulfur-containing diesel hydrogenation unit recycle hydrogen de sulfuration hydrogen production device, hydrogen sulfide containing circulating hydrogen is through behind the circulating hydrogen compressor 6, part H 2 S-containing gas circulating hydrogen, enter Hydrogenation of Coker Gasoline reactor 9 through pipeline 8, liquid (comprising that sulfidation generates water) is discharged through pipeline 13, behind the high score gas process Hydrogenation of Coker Gasoline device thionizer 12, hydrogen returns the suction port of compressor of the make-up hydrogen compressor 14 of diesel oil hydrogenation reactor through pipeline 16 as a supplement.After flow process is got through, and confirm H
2S penetrates Hydrogenation of Coker Gasoline reactor 9 beds.Speed with 10 ℃/h rises to 230 ℃ with Hydrogenation of Coker Gasoline process reactor 9 beds, H
2The concentration of S is controlled to be 5000 μ L/L, constant temperature 8 hours; Then the speed with 10 ℃/h rises to 315 ℃ with Hydrogenation of Coker Gasoline process reactor 9 beds, H
2The concentration of S is controlled to be 10000 μ L/L, constant temperature 10 hours.
Catalyzer is with embodiment 2.Cure conditions is pressure 3.0MPa, vulcanized oil volume space velocity 5.0h
-1, hydrogen-oil ratio 100.Vulcanized oil is virgin kerosene.
After sulfuration finishes, adjust temperature, introduce stock oil.The adjusting process condition is after introducing raw material: volume space velocity 3.8h
-1, pressure 3.0MPa, hydrogen-oil ratio 350,190 ℃ of reactor inlet temperatures, 300 ℃ of reactor outlet temperature.Turned round 48 hours, and adopted the finished product oil sample and analyze, catalyst activity the results are shown in Table 2.
Table 2 stock oil character and treated oil character.
| The oil product title | The coker gasoline | Embodiment | 2 | |
| Density (20 ℃), gcm -3 | 0.7413 | 0.7405 | 0.7397 | |
| Boiling range/℃ | 57～204 | 58～205 | 55～203 | |
| S，μg/g | 5676 | 65 | 56 | |
| N，μg/g | 226 | 2 | 1 |
Adopt flow process shown in Figure 2.During the high sulfur-containing diesel hydrogenation unit runs well.Diesel raw material sulphur content 2.03wt%, processing condition are: reactive hydrogen dividing potential drop 6.3MPa, volume space velocity 2.0h
-1, 360 ℃ of average reaction temperature, hydrogen to oil volume ratio 350.The catalytic gasoline hydrogenation unit through gas displacement, catalyzer dry and install airtight qualified after, prepare to go into operation sulfuration.Catalytic gasoline hydrogenation unit reactor 9 reaction bed temperature rise to 180 ℃, at this moment, adjust the operation of high sulfur-containing diesel hydrogenation unit recycle hydrogen de sulfuration hydrogen production device, hydrogen sulfide containing circulating hydrogen follows through behind the ring hydrogen compressor 6, part H 2 S-containing gas circulating hydrogen enters gasoline hydrogenation reactor 9 through pipeline 8, liquid (comprising that sulfidation generates water) is discharged through pipeline 13, behind the high score gas process catalytic gasoline hydrogenation unit thionizer 12, hydrogen returns make-up hydrogen compressor 14 entrances of diesel oil hydrogenation reactor through pipeline 16 as a supplement.After flow process is got through, and confirm H
2S penetrates Processes of FCC Naphtha Hydrotreating process reactor 9 beds.Speed with 8 ℃/h rises to 230 ℃, H with catalytic gasoline hydrogenation technique reactor 9 beds
2The concentration of S is controlled to be 4000 μ L/L, constant temperature 9 hours; Then the speed with 10 ℃/h rises to 315 ℃, H with catalytic gasoline hydrogenation technique reactor 9 beds
2The concentration of S is controlled to be 10000 μ L/L, constant temperature 10 hours.
Catalyst property: contain MoO 13.2wt%, contain CoO 4.5wt%.Cure conditions is pressure 2.0MPa, vulcanized oil volume space velocity 5.0h
-1, hydrogen-oil ratio 300.Vulcanized oil is virgin kerosene.
After sulfuration finishes, adjust temperature, introduce stock oil.The adjusting process condition is after introducing raw material: pressure 2.0MPa, volume space velocity 5.0h
-1, hydrogen to oil volume ratio 300,190 ℃ of reactor inlet temperatures, 260 ℃ of reactor outlet temperature.Turned round 48 hours, and adopted the finished product oil sample and analyze, catalyst activity the results are shown in Table 3.
Adopt flow process shown in Figure 2.During the high sulfur-containing diesel hydrogenation unit runs well.Diesel raw material sulphur content 2.03wt%, processing condition are: reactive hydrogen dividing potential drop 6.3MPa, volume space velocity 2.0h
-1, 360 ℃ of average reaction temperature, hydrogen to oil volume ratio 350.Raw material diesel oil enters diesel oil hydrogenation reactor 2 through pipeline 1, recycle hydrogen after the hydrogen make-up of pipeline 7 and make-up hydrogen compressor 14 introducings is mixed, reaction effluent enters high score 4 through pipeline 3, most of high score gas obtains recycle hydrogen behind pipeline 5 and circulating hydrogen compressor 6, liquid is discharged through pipeline 12.The catalytic gasoline hydrogenation unit through gas displacement, catalyzer dry and install airtight qualified after, prepare to go into operation sulfuration.After catalytic gasoline hydrogenation unit reactor 9 reaction bed temperature rise to 150 ℃, introduce vulcanized oil by pipeline 15.Reactor 9 obtains effluent and enters catalytic gasoline hydrogenation unit high score 11 through pipeline 10.After reactor 9 reaction bed temperature rise to 160 ℃, the hydrogenation catalyst that loads in the catalytic gasoline hydrogenator is vulcanized.Diesel hydrotreating unit high score 4 gained part high score gas is through after the suitable decompression, enter gasoline hydrogenation reactor 9 through pipeline 8, liquid (comprising that sulfidation generates water) is discharged through pipeline 13, behind the high score gas process catalytic gasoline hydrogenation unit thionizer 12, hydrogen returns the entrance of the make-up hydrogen compressor 14 of diesel oil hydrogenation reactor through pipeline 16 as a supplement.After flow process is got through, and confirm H
2S penetrates catalytic gasoline hydrogenation technique reactor 9 beds.Speed with 6 ℃/h rises to 220 ℃, H with catalytic gasoline hydrogenation technique reactor 9 beds
2The concentration of S is controlled to be 6000 μ L/L, constant temperature 9 hours; Then the speed with 15 ℃/h rises to 270 ℃, H with catalytic gasoline hydrogenation technique reactor 9 beds
2The concentration of S is controlled to be 10000 μ L/L, constant temperature 10 hours.
Catalyst property is with embodiment 4.Cure conditions is pressure 2.0MPa, vulcanized oil volume space velocity 5.0h
-1, hydrogen-oil ratio 300.Vulcanized oil is virgin kerosene.
After sulfuration finishes, adjust temperature, introduce stock oil.The adjusting process condition is after introducing raw material: pressure 2.0MPa, volume space velocity 5.0h
-1, hydrogen to oil volume ratio 300,190 ℃ of reactor inlet temperatures, 260 ℃ of reactor outlet temperature.Turned round 48 hours, and adopted the finished product oil sample and analyze, catalyst activity the results are shown in Table 3.
Table 3 stock oil character and treated oil character
| The oil product title | The catalytic gasoline | Embodiment | 4 | |
| Density (20 ℃), gcm -3 | 0.7386 | 0.7361 | 0.7358 | |
| Boiling range/℃ | 42～196 | 40～195 | 41～197 | |
| S，μg/g | 564 | 49 | 50 | |
| RON | 93 | 91 | 91 |
Claims (11)
1. the catalyst vulcanization method of a gasoline hydrogenation treatment process comprises following content:
(1) the high sulfur-containing diesel hydro-refining unit runs well;
(2) filling oxidation state gasoline hydrogenation catalyst in the gasoline hydrotreater reactor;
(3) gasoline hydrotreater is carried out gas displacement, catalyzer is dry and the device airtight work;
(4) the part H 2 S-containing gas that the high sulfur-containing diesel hydro-refining unit is obtained is introduced gasoline hydrotreater, and the catalyzer in the gasoline hydrotreater reactor is carried out vulcanisation operation;
(5) sulfidation of gasoline hydrotreater comprises: at 190 ℃ ~ 250 ℃ lower constant temperature 2h ~ 16h, H
2The concentration of S is controlled to be 500 μ L/L ~ 15000 μ L/L; At 260 ℃ ~ 350 ℃ lower constant temperature 5h ~ 16h hours, H
2The concentration of S is controlled to be 5000 μ L/L ~ 30000 μ L/L;
(6) after sulfuration finished, gasoline hydrotreater was carried out self recycle hydrogen cyclical operation, adjusted bed to temperature of reaction, switched stock oil and carried out the gasoline hydrogenation processing reaction.
2. in accordance with the method for claim 1, it is characterized in that, the described high sulfur-containing diesel hydro-refining unit of step (1) feed sulphur content is more than the 0.5wt%.
3. in accordance with the method for claim 1, it is characterized in that, the processing condition of the described high sulfur-containing diesel hydro-refining unit of step (1) are: reaction pressure 4 ~ 10MPa, 280 ℃ ~ 400 ℃ of temperature of reaction, volume space velocity 0.1 ~ 10h
-1, hydrogen to oil volume ratio 100 ~ 2000.
4. in accordance with the method for claim 1, it is characterized in that, the described gasoline hydrotreater of step (2) is catalytic gasoline hydrogenation unit, reformed pre-hydrogenated device or Hydrogenation of Coker Gasoline device.
5. in accordance with the method for claim 1, it is characterized in that, the described H 2 S-containing gas with the high sulfur-containing diesel hydro-refining unit of step (4) is introduced the mode that the gasoline hydrogenation device adopts: a part of high score gas of diesel hydrotreating unit is introduced the gasoline hydrogenation device, the gas that gasoline hydrogenation device high score obtains through or behind the gasoline hydrogenation device thionizer as the hydrogen make-up of Diesel Oil Hydrofining Unit or directly enter the hydrogen pipe network.
6. in accordance with the method for claim 1, it is characterized in that, the mode that described H 2 S-containing gas with the high sulfur-containing diesel hydro-refining unit is introduced the employing of gasoline hydrogenation device is: draw a part of H 2 S-containing gas behind high sulfur-containing diesel hydro-refining unit thionizer, through introducing in the reactor of gasoline hydrogenation device after the suitable step-down.
7. in accordance with the method for claim 1, it is characterized in that, the sulfidation of step (5) gasoline hydrogenation device is the dry method sulfuration.
8. the method for narrating according to claim 1, it is characterized in that, the sulfidation of step (5) gasoline hydrogenation device is the wet method sulfuration, when introducing H 2 S-containing gas from Diesel Oil Hydrofining Unit, in the gasoline hydrogenation reactor, introduce vulcanized oil, when passing into vulcanized oil, utilize hydrogen sulfide containing hydrogen to carry out sulfidation.
9. in accordance with the method for claim 1, it is characterized in that, the hydrogenation activity component of the gasoline hydrogenation catalyst described in the step (2) is one or more among W, Mo, Ni and the Co, take oxide compound hydrogenation activity component concentration as 3wt% ~ 50wt%.
10. in accordance with the method for claim 1, it is characterized in that, the concentration of hydrogen sulfide in step (5) the gasoline hydrogenation device catalyst vulcanization process is regulated by filling into the new hydrogen of part.
11. in accordance with the method for claim 1, it is characterized in that, the heat-up rate of sulfidation described in the step (5) is 1 ℃/h ~ 30 ℃/h.
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| 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 |
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