CN102533330B - Method for producing low-sulfur gasoline - Google Patents
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Abstract
The invention discloses a method for producing low-sulfur gasoline. The method comprises the following steps of: (1) in the presence of hydrogen and a catalyst A, performing primary desulfurization reaction on raw gasoline, and separating to obtain hydrogenated and desulfurized gasoline distillate oil; and (2) in the presence of inert gas and a catalyst B, performing secondary desulfurization reaction on the hydrogenated and desulfurized gasoline distillate oil, and separating to obtain the low-sulfur gasoline. Compared with the prior art, the method has the advantages that: the gasoline produced by the method has low sulfur content and low olefin saturation rate, and the method has high desulfurization selectivity.
Description
Technical field
The present invention relates to a kind of method of producing low-sulphur oil.
Background technology
Atmospheric pollution is a serious environmental problem, and the discharge of a large amount of engines is to cause one of air-polluting major reason.In recent years, be protection of the environment, countries in the world have proposed stricter restriction to the composition of motor spirit, to reduce the discharge of objectionable impurities.
At present, the sulphur of China's gasoline product has 90%～99% from catalytically cracked gasoline, and therefore, reducing sulfur content of catalytic cracking gasoline is the key point that reduces finished product content of sulfur in gasoline.
Employing catalytically cracked material adds hydrogen pretreatment (front-end hydrogenation) or catalytic gasoline hydrogenation desulfurization (back end hydrogenation) is two kinds of technical schemes of the sulphur content of alternative reduction catalytically cracked gasoline.Wherein, catalytically cracked material pre-treatment can significantly reduce the sulphur content of catalytically cracked gasoline, but need to all under exacting terms, operate very much at temperature and pressure, simultaneously because unit capacity is large, cause hydrogen consumption also larger, these all will improve investment or the running cost of device.However, due to the heaviness of world's crude oil, increasing catalytic cracking unit starts to process the inferior raw material that contains normal, vacuum residuum etc., and therefore catalytically cracked material hydrogenation unit amount is also increasing year by year.
Compare front-end hydrogenation, catalytic gasoline hydrogenation desulfurization is all adding hydrogen pretreatment lower than catalytically cracked material aspect plant investment, production cost and hydrogen consumption.But traditional catalyzer and technique are in hydrogenating desulfurization, the alkene significantly saturated meeting of hydrogenation causes product loss of octane number very large.One of effective way addressing the above problem is exactly to adopt selective hydrodesulfurization technology to process catalytically cracked gasoline.Selective hydrodesulfurization technology is removing sulfide in petrol simultaneously, and gasoline olefin is saturated few, can farthest reduce product loss of octane number.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of new production low-sulphur oil.
The present inventor finds under study for action, and in gasoline hydrodesulfurizationmethod process, alkene wherein and hydrogenation reaction generate H
2s can generate new mercaptan (being called regeneration mercaptan) and remain in product.For being rich in the gasoline fraction oil of alkene, after hydrogenation, gasoline fraction sulphur content is lower, and the mercaptan proportion of wherein regenerating is larger, therefore in order to produce low-sulfur and super low-sulfur oil, must remove the regeneration mercaptan in gasoline fraction after hydrogenation.
The present invention relates to a kind of method of producing low-sulphur oil, comprise the following steps:
(1) under hydrogen and catalyst A existence, make gasoline stocks oil carry out once desulfurization reaction, be isolated to the gasoline fraction oil after hydrogenating desulfurization;
(2) under rare gas element and catalyst B existence, make the gasoline fraction after hydrogenating desulfurization carry out secondary desulfuration reaction, be isolated to low-sulphur oil,
Wherein, the condition of described once desulfurization reaction comprises: volume space velocity 3h when reaction pressure 0.8MPa-3.2MPa, 200 ℃-320 ℃ of temperature of reaction, feeding liquid
-1-8h
-1, hydrogen and stock oil volume ratio (hydrogen-oil ratio) be 200-600; The condition of described secondary desulfuration reaction comprises: temperature of reaction is 100-350 ℃, and pressure is 0.2-6MPa, and when feeding liquid, mass space velocity is 1-12h
-1, rare gas element and stock oil volume ratio are 2-200; Described catalyst A contains carrier and is carried on the metal component with hydrogenation-dehydrogenation activity on this carrier, and in oxide compound and take catalyzer as benchmark, the content with hydrogenation-dehydrogenation activity metal component in described catalyzer is 5～35 % by weight; Described catalyst B contains carrier and is carried on and has hydrogenation-dehydrogenation activity metal component on this carrier, and in oxide compound and take catalyzer as benchmark, the content with hydrogenation-dehydrogenation activity metal component in described catalyzer is 5～35 % by weight.
Described once desulfurization reaction is hydrodesulfurization reaction, and preferred reaction conditions comprises: volume space velocity 3h when reaction pressure 1MPa-2.4MPa, 220 ℃-270 ℃ of temperature of reaction, gasoline fraction fluid
-1-6h
-1, hydrogen to oil volume ratio 300-500.
It is main purpose that described secondary desulfuration reacts to remove regeneration mercaptan, is a kind of desulphurization reaction of the non-hydrogen of being realized containing decomposition under the catalyst action with hydrogenation-dehydrogenation activity metal component by mercaptan.Preferred reaction conditions comprises: temperature of reaction is 140-240 ℃, and pressure is 0.4-2.5MPa, and when feeding liquid, mass space velocity is 2-10h
-1, rare gas element and stock oil volume ratio are 5-120.
According to method provided by the invention, described catalyst A and catalyst B can be the same or different, and they can be the combinations that any its composition that prior art provides can meet catalyzer or the catalyzer of aforementioned requirement.In a preferred embodiment, described catalyst A is preferably carried out prevulcanized before use, is converted into sulfide so that wherein have hydrogenation-dehydrogenation activity metal component; Catalyst B does not need to carry out prevulcanized in use, and preferably having hydrogenation-dehydrogenation activity metal component is oxide compound.
In a kind of embodiment, the carrier of described catalyst A is preferably aluminum oxide or silica-alumina, described in there is hydrogenation-dehydrogenation activity metal component and be preferably the metal component that is selected from least one group vib and at least one VIII family.In oxide compound and take catalyzer as benchmark, the content that is selected from vib metal component in preferred described catalyzer is 5～30 heavy %, the content of VIII metal component is 0.5～5 heavy %, optionally described catalyzer can also contain adjuvant component, for example, contain a small amount of auxiliary agent that is selected from IA main group, IIA main group or VA subgroup.About the example of this type of catalyzer as, at 200710099304.8,200710099302.9,200710099834.2 disclosed catalyzer respectively, they can serve as catalyzer for the present invention.The carrier of described catalyst B is preferably aluminum oxide, described in have hydrogenation-dehydrogenation activity metal component be preferably be selected from least one VIB and and at least one VIII metal component.In oxide compound and take catalyzer as benchmark, the content that is selected from vib metal component in preferred described catalyzer is 4～15 heavy %, and the content of VIII metal component is 1～5 heavy %.
According to method provided by the present invention, wherein said separation, its method and be the usual method and apparatus adopting in this area for realizing the required device of the method.For example, adopt the usual apparatus and method in this area to carry out air lift, distillation etc. to generating oil, generate to remove the hydrogen sulfide and other the non-gasoline components that in oil, contain.
Under the prerequisite that is enough to make described charging to contact with described catalyzer under described reaction conditions, the present invention is not particularly limited described reactor.For example, described in carry out once desulfurization reaction reactor can be any reactor that is suitable for gasoline fraction oil hydrodesulfurization reaction in prior art, for example fixed bed hydrogenation reactor.The described reactor that carries out secondary desulfuration reaction can be to comprise the various forms of reactors such as fixed-bed reactor, fluidized-bed reactor, distillation column reactor or ebullated bed reactor.In a preferred embodiment, described in carry out secondary desulfuration reaction reactor be preferably counter-current reactor, the gasoline fraction after described hydrogenating desulfurization flows from top to bottom in reactor, described rare gas element flows from bottom to top and contact with catalyst B.In counter-current reactor, the gasoline fraction after hydrogenating desulfurization and rare gas element reverse contact under catalyzer exists, the H that reaction is produced
2s shifts out beds in time, and is taken out of reactor by rare gas element medium.Described counter-current reactor can be various forms, for example, can be fixed bed, fluidized-bed, distillation tower or ebullated bed reactor etc., also can carry out being filled with in the stripping tower of catalyst B or stabilizer tower.In conventional gasoline hydrogenation technique, general have stripping tower or stabilizer tower in order to remove the lighter hydrocarbons such as methane, ethane and the hydrogen sulfide in gasoline after hydrogenation, utilize stripping tower or stabilizer tower in existing hydrogenation unit, in removing reacted regeneration mercaptan and lighter hydrocarbons and hydrogen sulfide, can simplification of flowsheet, save facility investment.In the time that the reactor of described secondary desulfuration reaction is selected counter-current reactor, described rare gas element and more preferably 5-40 of stock oil volume ratio.
Described rare gas element, for arbitrarily under secondary desulfuration reaction conditions with hydrogenating desulfurization after gasoline fraction be the gas of inert reaction, for example, they can be one or more the mixtures that is selected from nitrogen, carbonic acid gas, carbon monoxide, hydro carbons, water vapour, preferably hydro carbons.
According to method provided by the invention, described gasoline stocks oil can be one or more in catalytically cracked gasoline distillate, catalytic cracking gasoline distillate, straight-run spirit distillate, coker gasoline distillate, pyrolysis gasoline cut fraction oil and pressure gasoline distillate.The boiling range of described gasoline stocks oil is the usual boiling range of gasoline fraction oil, for example: can be 30-220 ℃.
According to method provided by the invention, also comprise and introduce a kind of heavy distillate in described step (1), the initial boiling point of described heavy distillate is greater than the final boiling point of described gasoline stocks oil, volume space velocity during in liquid, and the liquid hourly space velocity of introducing heavy distillate is 0.2h
-1-2h
-1.
Contriver finds under study for action, when introducing heavy distillate and can significantly further improve the selectivity of hydrodesulfurization reaction in once desulfurization reaction.
Guaranteeing that under the condition that is enough to described heavy distillate be introduced and contacted with catalyzer, the present invention does not limit the introducing method of described heavy distillate.For example, can be that first described heavy distillate is mixed with gasoline fraction oil, introduce afterwards reactor and contact with catalyzer under gasoline selective hydrodesulfurizationmodification reaction conditions; Also can be that described heavy distillate and gasoline fraction oil raw material are introduced respectively to reactor.Wherein, described heavy distillate is selected from diesel oil distillate oil and/or lubricating oil distillate, and the temperature difference of the final boiling point of the initial boiling point of described heavy distillate and described gasoline fraction oil is not less than 1 ℃, is preferably not less than 10 ℃, further preferably be not less than 20 ℃, be more preferably not less than 40 ℃.The liquid hourly space velocity of introducing heavy distillate is preferably 0.4h
-1-1.8h
-1, more preferably 0.6h
-1-1.8h
-1.Described heavy distillate is derived from for example, in oil, synthetic oil (: be selected from olefin oligomerization synthetic oil, Fischer-Tropsch synthesis oil and biosynthesizing oil) one or more.Under reaction conditions of the present invention, wherein said heavy distillate exists with the form of liquid at least partly.
In the time that described step (1) also comprises the step of introducing a kind of heavy distillate, wherein said separation comprises distills gained reaction product the step that (comprising flash distillation distillation) separates.The gasoline fraction oil obtaining through fractionation by distillation carries out secondary desulfuration reaction, and heavy distillate can partly or entirely recycle.
In a preferred embodiment, the inventive method comprises the steps:
(1) heavy distillate, gasoline stocks oil and hydrogen are introduced to the reactor that is filled with catalyst A and carried out hydrodesulfurization reaction one time, the condition of once desulfurization reaction comprises: volume space velocity 3h when the liquid of reaction pressure 0.8MPa～3.2MPa, 200 ℃～320 ℃ of temperature of reaction, gasoline fraction oil
-1～8h
-1, heavy distillate liquid time volume space velocity 0.2h
-1-2h
-1, hydrogen to oil volume ratio 200～600;
(2) product of step (1) is introduced to stripping tower, remove the H in product through stripping
2the light constituents such as S.
(3) bottom stream of step (2) is introduced to separation column and carry out fractionation by distillation, isolate gasoline fraction and heavy distillate;
(4) counter-current reactor that gasoline fraction step (3) being obtained and rare gas element introducing are filled with catalyst B carries out secondary desulfuration reaction, the condition of secondary desulfuration reaction comprises: temperature of reaction is 100-350 ℃, pressure is 0.2-6MPa, and when feeding liquid, mass space velocity is 1-12h
-1, rare gas element and stock oil volume ratio are 2-200,
Wherein, described heavy distillate is selected from diesel oil distillate oil and/or lubricating oil distillate, and the temperature difference of the final boiling point of the initial boiling point of described heavy distillate and described gasoline fraction oil is not less than 1 ℃, is preferably not less than 10 ℃, further preferably be not less than 20 ℃, be more preferably not less than 40 ℃.Described heavy distillate is derived from for example, in oil, synthetic oil (: be selected from olefin oligomerization synthetic oil, Fischer-Tropsch synthesis oil and biosynthesizing oil) one or more.Under reaction conditions of the present invention, wherein said heavy distillate exists with the form of liquid at least partly.
The condition of preferred once desulfurization reaction comprises: volume space velocity 3h when reaction pressure 1MPa-2.4MPa, 220 ℃-270 ℃ of temperature of reaction, gasoline fraction fluid
-1-6h
-1, heavy distillate liquid time volume space velocity be 0.4h
-1-1.8h
-1, further preferably volume space velocity is 0.6h when the liquid of heavy distillate
-1-1.8h
- 1, hydrogen to oil volume ratio 300-500.
The reaction conditions of preferred secondary desulfuration comprises: temperature of reaction is 140-240 ℃, and pressure is 0.4-2.5MPa, and when feeding liquid, mass space velocity is 2-10h
-1, rare gas element and stock oil volume ratio are 5-120, more preferably 5-40.
The heavy distillate obtaining through step (3) fractionation by distillation returns to step (1) and recycles.In step (4), gasoline fraction flows through beds from top to bottom, with the rare gas element counter current contact of being introduced by reactor bottom, regeneration mercaptan in described gasoline fraction is decomposed into alkene and hydrogen sulfide on catalyzer, hydrogen sulfide, lighter hydrocarbons in fluid shift out reaction zone with stripping medium, the stripping medium of sulfide hydrogen and lighter hydrocarbons is discharged on counter-current reactor top, and reactor bottom has obtained removing the gasoline products of mercaptan.
Described catalyst A contains carrier and is carried on and has hydrogenation-dehydrogenation activity metal component on carrier, and in oxide compound and take catalyzer as benchmark, the content with hydrogenation-dehydrogenation activity metal component in described catalyzer is 5～35 % by weight; Described catalyst B contains carrier and is carried on and has hydrogenation-dehydrogenation activity metal component on carrier, and in oxide compound and take catalyzer as benchmark, the content with hydrogenation-dehydrogenation activity metal component in described catalyzer is 5～35 % by weight.The carrier of described catalyst A is preferably aluminum oxide or silica-alumina, described in there is hydrogenation-dehydrogenation activity metal component and be preferably the metal component that is selected from least one group vib and at least one VIII family.In oxide compound and take catalyzer as benchmark, the content that is selected from vib metal component in preferred described catalyzer is 5～30 heavy %, the content of VIII metal component is 0.5～5 heavy %, optionally described catalyzer can also contain adjuvant component, for example, contain a small amount of auxiliary agent that is selected from IA main group, IIA main group, IIIA or VB subgroup.About the example of this type of catalyzer as, at 200710099304.8,200710099302.9,200710099834.2 disclosed catalyzer respectively, they can serve as catalyzer for the present invention.The carrier of described catalyst B is preferably aluminum oxide, described in have hydrogenation-dehydrogenation activity metal component be preferably be selected from least one VIB and and at least one VIII metal component.In oxide compound and take catalyzer as benchmark, the content that is selected from vib metal component in preferred described catalyzer is 4～15 heavy %, and the content of VIII metal component is 1～5 heavy %.
In a preferred embodiment, described catalyst A is preferably carried out prevulcanized before use, is converted into sulfide so that wherein have hydrogenation-dehydrogenation activity metal component; Catalyst B does not need to carry out prevulcanized in use, and preferably having hydrogenation-dehydrogenation activity metal component is oxide compound.
Described counter-current reactor can be various forms, comprises fixed bed, fluidized-bed, distillation tower or ebullated bed reactor etc., also can carry out being filled with in the stripping tower of catalyst B or stabilizer tower.In conventional gasoline hydrogenation technique, general have stripping tower or stabilizer tower in order to remove the lighter hydrocarbons such as methane, ethane and the hydrogen sulfide in gasoline after hydrogenation, utilize stripping tower or stabilizer tower in existing hydrogenation unit, in removing reacted regeneration mercaptan and lighter hydrocarbons and hydrogen sulfide, can simplification of flowsheet, save facility investment.In counter-current reactor, the gasoline fraction after hydrogenating desulfurization and rare gas element reverse contact under catalyzer exists, the H that reaction is produced
2s shifts out beds in time, and is taken out of reactor by rare gas element medium.
According to method provided by the invention, described gasoline stocks oil can be one or more in catalytically cracked gasoline distillate, catalytic cracking gasoline distillate, straight-run spirit distillate, coker gasoline distillate, pyrolysis gasoline cut fraction oil and pressure gasoline distillate.The boiling range of described gasoline stocks oil is the usual boiling range of gasoline fraction oil, for example: can be 30-220 ℃.
Described rare gas element, for arbitrarily under secondary desulfuration reaction conditions with hydrogenating desulfurization after gasoline fraction be the gas of inert reaction, for example, they can be one or more the mixtures that is selected from nitrogen, carbonic acid gas, carbon monoxide, hydro carbons, water vapour, preferably hydro carbons.
Compared with prior art, the sulphur content of the inventive method production gasoline is low, olefin saturated rate is low, has good desulfuration selectivity.Particularly, in the time that described secondary desulfuration reaction is carried out in counter-current reactor, hydrogen sulfide in fluid, lighter hydrocarbons are with shifting out reaction zone on rare gas element, and the stripping medium of sulfide hydrogen and lighter hydrocarbons is discharged on counter-current reactor top, and reactor bottom has obtained removing the gasoline products of mercaptan.Therefore, can realization response product separation in completing reaction.
Accompanying drawing explanation
Fig. 1 is a kind of schematic flow sheet that the invention provides method.
Embodiment
The invention provides a kind of of method preferred embodiment realizes by the flow process shown in Fig. 1.
According to the flow process shown in Fig. 1, gasoline stocks oil, heavy distillate through pump 1 with mix from the hydrogen of pipeline 2, enter process furnace 4 through pipeline 3, material after heating enters through pipeline 5 the once desulfurization reactor 6 that is filled with catalyst A and carries out desulphurization reaction, once desulfurization generates oil and enters flashing tower 8 through pipeline 7, be gasoline fraction through flash separation, heavy distillate, wherein heavy distillate turns back to process furnace through pipeline 10, recycle, gasoline fraction enters high-pressure separator 11 after interchanger 9 heat exchange, enter compressor 14 from high-pressure separator 11 tops hydrogen-rich gas out through pipeline 12, hydrogen-rich gas after compression mixes through pipeline 15 or with the supplementary fresh hydrogen from pipeline 16, mixing hydrogen recycles through pipeline 2.Enter from separator 11 bottoms liquid stream out the secondary desulfuration reactor 14 that is filled with catalyst B through pipeline 13, the stripping tower that secondary desulfuration reactor 14 is a kind of routine, with conventional gas stripping column difference be that filler is wherein catalyst B.Hydrogen sulfide, lighter hydrocarbons in charging separate with gasoline fraction in secondary desulfuration reactor 14.Gasoline flows downward and the steam (hydrocarbon of gasification that is derived from reboiler 20 and introduce through pipeline 21 in tower, use as rare gas element herein) counter current contact in catalyst B, at the bottom of tower, liquid flows out from pipeline 19, a part is drawn as product and is reclaimed through pipeline 22, another part enters after reboiler 20 vaporizations, returns to tower internal recycle through pipeline 21.Part hydrocarbon ils steam, hydrogen sulfide and lighter hydrocarbons distillate from tower top, enter condenser through pipeline 15 and carry out condensation, after condensation, enter separator 16, from separator 16 tops, the lighter hydrocarbons such as hydrogen sulfide out and methane, ethane, propane are emptying through pipeline 17 as non-condensable gas, are back in stripping tower through pipeline 18 from separator 16 bottoms liquid product out.
Above-mentioned flow process is preferably to introduce the process of heavy distillate, do not introducing under heavy ends oil condition, reaction still can be carried out in the flow process shown in Fig. 1, difference is the flashing tower 8 that can save in flow process, and once desulfurization generation oil enters high-pressure separator 11 and separates after pipeline 7, interchanger 9 heat exchange.
The following examples will be further described method provided by the invention, but not thereby limiting the invention.
Comparative example and embodiment used catalyst A are numbered RSE-1, and in oxide compound and take catalyzer as benchmark, RSE-1 consists of: cobalt contents 2.3 % by weight, and molybdenum content 14.8 % by weight, boron oxide content 3.1 % by weight, surplus is alumina supporter; Catalyst B be numbered RSS-1, in oxide compound and take catalyzer as benchmark, RSS-1 consists of: nickel content 4.5 % by weight, W content 13.6 % by weight, surplus is alumina supporter.
Embodiment 1
Produce low-sulphur oil according to the flow process shown in Fig. 1.
The charging of gasoline stocks oil is mixing raw material C, and its character is listed in table 1, and catalyst A is RSE-1, and catalyst B is RSS-1.
Once desulfurization reaction conditions is: temperature of reaction is 270 ℃, and reaction pressure is 1.6MPa, and gasoline feeding volume space velocity is 4h
-1, gasoline feeding hydrogen to oil volume ratio is 400.After hydrogenating desulfurization, the character of gasoline fraction is listed in table 2.
Secondary desulfuration reaction conditions is: pressure is 1.3MPa, and the following beds medial temperature of charging is 220 ℃, charging mass space velocity 3h
-1, steam (rare gas element) is 7 with stock oil volume ratio.The character of gasoline products is listed in table 3.
Produce low-sulphur oil according to the flow process shown in Fig. 1.
The charging of gasoline stocks oil is mixing raw material H, and its character is listed in table 1, and catalyst A is RSE-1, and catalyst B is RSS-1.
Once desulfurization reaction conditions is: temperature of reaction is 270 ℃, and reaction pressure is 1.6MPa, and gasoline feeding volume space velocity is 4h
-1, gasoline feeding hydrogen to oil volume ratio is 400.After hydrogenating desulfurization, the character of gasoline fraction is listed in table 2.
Secondary desulfuration reaction conditions is: pressure is 1.3MPa, and the following beds medial temperature of charging is 220 ℃, charging mass space velocity 3h
-1, steam (rare gas element) is 7 with stock oil volume ratio.The character of gasoline products is listed in table 3.
Save flashing tower 8 in the flow process shown in Fig. 1, and produce low-sulphur oil according to this flow process.
The charging of gasoline stocks oil is catalytic cracking full distillate gasoline A, and its character is listed in table 1, and catalyst A is RSE-1, and catalyst B is RSS-1.
Once desulfurization reaction conditions is: temperature of reaction is 270 ℃, and reaction pressure is 1.6MPa, and gasoline feeding volume space velocity is 4h
-1, gasoline feeding hydrogen to oil volume ratio is 400.After hydrogenating desulfurization, the character of gasoline fraction is listed in table 2.
Secondary desulfuration reaction conditions is: pressure is 1.3MPa, and the following beds medial temperature of charging is 220 ℃, charging mass space velocity 3h
-1, steam (rare gas element) is 7 with stock oil volume ratio.The character of gasoline products is listed in table 3.
Embodiment 4
Produce low-sulphur oil according to the flow process shown in Fig. 1.
The charging of gasoline stocks oil is mixing raw material C, and its character is listed in table 1, and catalyst A is RSE-1, and catalyst B is RSS-1.
Once desulfurization reaction conditions is: temperature of reaction is 250 ℃, and reaction pressure is 1.6MPa, and gasoline feeding volume space velocity is 3h
-1, gasoline feeding hydrogen to oil volume ratio is 400.After hydrogenating desulfurization, the character of gasoline fraction is listed in table 2.
Secondary desulfuration reaction conditions is: pressure is 1.3MPa, and the following beds medial temperature of charging is 230 ℃, charging mass space velocity 3h
-1, steam (rare gas element) is 30 with stock oil volume ratio.The character of gasoline products is listed in table 3.
Comparative example 1
Produce gasoline products according to the flow process of embodiment 3.Difference is that the catalyst B in reactor 14 is replaced by filler.Stripping tower working pressure is 1.3MPa, charging mass space velocity 3h
-1, steam (rare gas element) is 7 with stock oil volume ratio.
After hydrogenating desulfurization, the character of gasoline fraction is listed in table 2, and the character of gasoline products is listed in table 3.
Table 1
Table 2
| Gasoline fraction after hydrogenating desulfurization | Comparative example 1 | Embodiment 1 | |
|
Embodiment 4 |
| Density (20 ℃), g/cm3 | 0.7244 | 0.7196 | 0.718 | 0.7199 | 0.7201 |
| Sulphur content, μ g/g | 59 | 37 | 43 | 45 | 41 |
| Mercaptans content, μ g/ |
21 | 18 | 20 | 22 | 20 |
| Alkene, volume % | 22.4 | 24.9 | 24.1 | 24.4 | 24.3 |
Table 3
| Full gold-plating divides gasoline products | Comparative example 1 | Embodiment 1 | |
|
Embodiment 4 |
| Sequence number | DB1 | A1 | A2 | A3 | A4 |
| Density (20 ℃), g/cm3 | 0.7239 | 0.7334 | 0.7381 | 0.7330 | 0.7309 |
| Sulphur, μ g/g | 44 | 14 | 17 | 24 | 18 |
| Mercaptans content, μ g/ |
15 | ＜3 | ＜3 | 11 | 4 |
| Alkene, volume % | 20.6 | 23.8 | 23.2 | 23.2 | 23.6 |
| Desulfurization degree, % | 93.76 | 97.76 | 97.28 | 96.16 | 97.12 |
| Olefin saturated rate, % | 30.2 | 19.32 | 21.35 | 21.35 | 20.0 |
Claims (24)
1. a method of producing low-sulphur oil, comprises the following steps:
(1) under hydrogen and catalyst A existence, make gasoline stocks oil carry out once desulfurization reaction, be isolated to the gasoline fraction oil after hydrogenating desulfurization;
(2) under rare gas element and catalyst B existence, make the gasoline fraction after hydrogenating desulfurization carry out secondary desulfuration reaction, be isolated to low-sulphur oil,
Wherein, the condition of described once desulfurization reaction comprises: reaction pressure 0.8-3.2MPa, temperature of reaction 200-320 ℃, volume space velocity 3-8h when feeding liquid
-1, hydrogen to oil volume ratio is 200-600; The condition of described secondary desulfuration reaction comprises: temperature of reaction is 100-350 ℃, and pressure is 0.2-6MPa, and when feeding liquid, mass space velocity is 1-12h
-1, rare gas element and stock oil volume ratio are 2-200; Described catalyst A contains carrier and is carried on the metal component with hydrogenation-dehydrogenation activity on this carrier, and in oxide compound and take catalyzer as benchmark, the content with hydrogenation-dehydrogenation activity metal component in described catalyzer is 5～35 % by weight; Described catalyst B contains carrier and is carried on and has hydrogenation-dehydrogenation activity metal component on this carrier, and in oxide compound and take catalyzer as benchmark, the content with hydrogenation-dehydrogenation activity metal component in described catalyzer is 5～35 % by weight.
2. method according to claim 1, is characterized in that, the reaction conditions of described once desulfurization reaction comprises: reaction pressure 1-2.4MPa, temperature of reaction 220-270 ℃, volume space velocity 3-6h when gasoline fraction fluid
-1, hydrogen to oil volume ratio 300-500; The reaction conditions of described secondary desulfuration reaction comprises: pressure is 0.4-2.5MPa, and temperature of reaction is 140-240 ℃, and when feeding liquid, mass space velocity is 2-10h
-1, rare gas element and stock oil volume ratio are 5-120.
3. method according to claim 1, it is characterized in that, the carrier of described catalyst A is aluminum oxide or silica-alumina, the described metal component that there is hydrogenation-dehydrogenation activity metal component and be selected from least one group vib and at least one group VIII, in oxide compound and take catalyzer as benchmark, the content that is selected from group vib metal component in described catalyzer is 5～30 heavy %, and the content of group VIII metal component is 0.5～5 heavy %; The carrier of described catalyst B is aluminum oxide, the described metal component with hydrogenation-dehydrogenation activity is selected from the metal component of at least one group vib and at least one group VIII, in oxide compound and take catalyzer as benchmark, the content that is selected from group vib metal component in described catalyzer is 4～15 heavy %, and the content of group VIII metal component is 1～5 heavy %.
4. according to the method described in claim 1 or 3, it is characterized in that, described catalyst A is carried out prevulcanized before use.
5. method according to claim 1, is characterized in that, the reactor of described secondary desulfuration reaction is countercurrent reactor.
6. method according to claim 1, is characterized in that, described rare gas element be arbitrarily under secondary desulfuration reaction conditions with hydrogenating desulfurization after gasoline fraction be the gas of inert reaction.
7. method according to claim 6, is characterized in that, described rare gas element is selected from one or more mixture of nitrogen, carbonic acid gas, carbon monoxide, hydro carbons, water vapour.
8. method according to claim 1, it is characterized in that, also comprise and introduce a kind of heavy distillate in described step (1), described heavy distillate is the distillate that a kind of initial boiling point is greater than the final boiling point of described gasoline stocks oil, volume space velocity during in liquid, the liquid hourly space velocity of introducing heavy distillate is 0.2-2h
-1.
9. method according to claim 8, it is characterized in that, described heavy distillate is selected from diesel oil distillate oil and/or lubricating oil distillate, and the temperature difference of the final boiling point of the initial boiling point of described heavy distillate and described gasoline fraction oil is not less than 1 ℃, and the liquid hourly space velocity of introducing heavy distillate is 0.4-1.8h
-1.
10. method according to claim 9, is characterized in that, the temperature difference of the final boiling point of the initial boiling point of described heavy distillate and described gasoline fraction oil is not less than 10 ℃, and the liquid hourly space velocity of introducing heavy distillate is 0.6-1.8h
-1.
Method described in 11. according to Claim 8,9 or 10, is characterized in that, the temperature difference of the final boiling point of the initial boiling point of described heavy distillate and described gasoline fraction oil is not less than 20 ℃.
12. methods according to claim 11, is characterized in that, the temperature difference of the final boiling point of the initial boiling point of described heavy distillate and described gasoline fraction oil is not less than 40 ℃.
13. methods according to claim 8, is characterized in that, described heavy distillate is derived from one or more in oil, synthetic oil.
14. methods according to claim 13, is characterized in that, described synthetic oil is selected from olefin oligomerization synthetic oil, Fischer-Tropsch synthesis oil and biosynthesizing oil.
15. methods according to claim 1, is characterized in that, one or more in described gasoline stocks grease separation catalytic cracking gasoline, catalytic cracking gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline and pressure gasoline.
16. methods according to claim 15, is characterized in that, the boiling range of described gasoline fraction oil is 30-220 ℃.
Produce the method for low-sulphur oil, comprise the following steps: for 17. 1 kinds
(1) heavy distillate, gasoline stocks oil and hydrogen are introduced to the reactor that is filled with catalyst A and carried out hydrodesulfurization reaction one time, the condition of once desulfurization reaction comprises: volume space velocity 3～8h when the liquid of reaction pressure 0.8～3.2MPa, 200～320 ℃ of temperature of reaction, gasoline fraction oil
-1, heavy distillate liquid time volume space velocity 0.2-2h
-1, hydrogen to oil volume ratio 200～600;
(2) product of step (1) is introduced to stripping tower, remove the light constituent in product through stripping;
(3) bottom stream of step (2) is introduced to separation column and carry out fractionation by distillation, isolate gasoline fraction and heavy distillate;
(4) gasoline fraction rare gas element and step (3) being obtained is introduced the counter-current reactor that is filled with catalyst B and is carried out secondary desulfuration reaction, the condition of secondary desulfuration reaction comprises: temperature of reaction is 100-350 ℃, pressure is 0.2-6MPa, and when feeding liquid, mass space velocity is 1-12h
-1, rare gas element and stock oil volume ratio are 2-200;
Wherein, described catalyst A contains carrier and is carried on the metal component with hydrogenation-dehydrogenation activity on this carrier, in oxide compound and take catalysis together as benchmark, the content with hydrogenation-dehydrogenation activity metal component in described catalyzer is 5～35 % by weight; Described catalyst B contains carrier and is carried on and has hydrogenation-dehydrogenation activity metal component on this carrier, and in oxide compound and take catalyzer as benchmark, the content with hydrogenation-dehydrogenation activity metal component in described catalyzer is 5～35 % by weight; Described heavy distillate is the distillate that a kind of initial boiling point is greater than the final boiling point of described gasoline stocks oil.
18. methods according to claim 17, is characterized in that, the reaction conditions of described once desulfurization reaction comprises: reaction pressure 1-2.4MPa, temperature of reaction 220-270 ℃, volume space velocity 3-6h when gasoline fraction fluid
-1, hydrogen to oil volume ratio 300-500, described heavy distillate is selected from diesel oil distillate oil and/or lubricating oil distillate, the temperature difference of the final boiling point of the initial boiling point of described heavy distillate and described gasoline fraction oil is not less than 1 ℃, and the liquid hourly space velocity of introducing heavy distillate is 0.4-1.8h
-1; The reaction conditions of described secondary desulfuration reaction comprises: pressure is 0.4-2.5MPa, and temperature of reaction is 140-240 ℃, and when feeding liquid, mass space velocity is 2-10h
-1, rare gas element and stock oil volume ratio are 5-40.
19. methods according to claim 18, is characterized in that, the temperature difference of the final boiling point of the initial boiling point of described heavy distillate and described gasoline fraction oil is not less than 10 ℃, and the liquid hourly space velocity of introducing heavy distillate is 0.6-1.8h
-1.
20. methods according to claim 19, is characterized in that, the temperature difference of the final boiling point of the initial boiling point of described heavy distillate and described gasoline fraction oil is not less than 20 ℃.
21. methods according to claim 20, is characterized in that, the temperature difference of the final boiling point of the initial boiling point of described heavy distillate and described gasoline fraction oil is not less than 40 ℃.
22. methods according to claim 17, is characterized in that, described heavy distillate is derived from one or more in oil, synthetic oil.
23. methods according to claim 22, is characterized in that, described synthetic oil is selected from olefin oligomerization synthetic oil, Fischer-Tropsch synthesis oil and biosynthesizing oil.
24. methods according to claim 17, it is characterized in that, the carrier of described catalyst A is aluminum oxide or silica-alumina, the described metal component that there is hydrogenation-dehydrogenation activity metal component and be selected from least one group vib and at least one group VIII, in oxide compound and take catalyzer as benchmark, the content that is selected from group vib metal component in described catalyzer is 5～30 heavy %, and the content of group VIII metal component is 0.5～5 heavy %; The carrier of described catalyst B is aluminum oxide, the described metal component with hydrogenation-dehydrogenation activity is selected from the metal component of at least one group vib and at least one group VIII, in oxide compound and take catalyzer as benchmark, the content that is selected from group vib metal component in described catalyzer is 4～15 heavy %, and the content of group VIII metal component is 1～5 heavy %.
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| CN105567313B (en) * | 2014-10-14 | 2018-11-30 | 中国石油化工股份有限公司 | A kind of production method of high-octane rating low-sulphur oil |
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| US6024865A (en) * | 1998-09-09 | 2000-02-15 | Bp Amoco Corporation | Sulfur removal process |
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| CN1485414A (en) * | 2002-09-26 | 2004-03-31 | 中国科学院大连化学物理研究所 | Method for non-hydroaromatizating and desulfurizing catalytically cracked gasoline |
| CN101265417A (en) * | 2008-04-30 | 2008-09-17 | 山东金诚重油化工有限公司 | Method for providing heat for petroleum fractioning hydrogenation |
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| US6024865A (en) * | 1998-09-09 | 2000-02-15 | Bp Amoco Corporation | Sulfur removal process |
| CN1448481A (en) * | 2002-03-29 | 2003-10-15 | 法国石油公司 | Method for production of low sulfur and thiol content hydrocarbon |
| CN1465666A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | Method of heavily desulfurating and reducing olefinic hydrocarbon for gasoline |
| CN1485414A (en) * | 2002-09-26 | 2004-03-31 | 中国科学院大连化学物理研究所 | Method for non-hydroaromatizating and desulfurizing catalytically cracked gasoline |
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