CN101591566B - Grading method of catalyst of deep hydrodesulfurization of diesel oil - Google Patents
Grading method of catalyst of deep hydrodesulfurization of diesel oil Download PDFInfo
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Abstract
The invention discloses a grading method of catalyst of deep hydrodesulfurization of diesel oil, comprising the following steps: base oil and hydrogen are mixed, then the mixture is led into a hydrogenation reactor to carry out hydrogenation reaction; reaction effluent is cooled and separated to obtain hydrogen-rich gas and liquid product; the hydrogenation reactor sequentially comprises four hydrogenation reaction zones, wherein, the first hydrogenation reaction zone is filled with hydrogenation protective agent, the second hydrogenation reaction zone is filled with hyrorefining catalyst (1)containing active metal cobalt-molybdenum, the third hydrogenation reaction zone is filled with the mixture of the hyrorefining catalyst (1) and hyrorefining catalyst (2), and the fourth hydrogenation reaction zone is filled with the hyrorefining catalyst (2) containing active metal nickel-tungsten. The invention carries out reasonable grading on catalyst of different systems, gives full play to the advantages of each catalyst in different desulphurizing states, improves whole catalyst activity by synergy of each catalyst, and can obtain ultra low sulfur diesel oil, sulfur content of which satisfies Euro IV standard under moderate operation condition.
Description
Technical field
The invention belongs to a kind ofly in the method that has under the situation of hydrogen refining hydrocarbon ils, more particularly, is a kind of grading method of catalyst of deep hydrodesulfurizationof of diesel oil.
Background technology
The environmental regulation of increasingly stringent is more and more stricter to the restriction of the sulphur content in the diesel oil in the world wide; The specification of sulphur content less than 500 μ g/g implemented in Europe in 1996; Further be reduced to sulphur content in 2000 less than 350 μ g/g; Sulphur content from the Europe IV standard code derv fuel oil of carrying out in 2005 is less than 50 μ g/g, and Euro V emissions then requires less than 10 μ g/g.The world fuel standard of world fuel council issue also has restriction more strictly to the diesel product sulphur content, and the sulphur content of II class diesel oil requires to be not more than 300 μ g/g, and III class and IV class are respectively the diesel oil sulphur content and are not more than 30 μ g/g and 10 μ g/g.In addition, the diesel oil standard of China is also positive walks with world's pace at a quick pace.Beijing, Shanghai, three big cities, Guangzhou take the lead in having proposed to reach in 2008 the requirement of Europe IV emission standard.This shows that reducing the diesel oil sulphur content, producing ultra-low-sulphur diesel is the significant problem that each enterprise of great oil refining is faced.
CN 1226920A discloses a kind of hydroprocessing process; This method has been taked in the presence of hydrogen; Hydrocarbon fraction is downward through the method for the folded formula bed of two kinds of hydrotreating catalysts; Contain at least a precious metal that is selected from platinum, palladium and the iridium in the hydrotreating catalyst that wherein loads in the bed of top, contain the base metal of group VIII and the metal of group vib in the hydrotreating catalyst that loads in the bed of bottom.This method can be produced low-sulfur diesel-oil, but owing to adopted noble metal catalyst, so the catalyzer cost is high, the device operational cycle is short.
US 5316658 discloses a kind of method of producing low-sulfur diesel-oil; This method has adopted the method that makes raw material pass through two reaction zones successively; The temperature of reaction of first reaction zone is 350～450 ℃, and reaction pressure is 4.5～10.0MPa, and the temperature of reaction of second reaction zone is 200～300 ℃; Reaction pressure is 4.5～10.0MPa, and the intermediate product between two reaction zones does not separate.The resulting diesel oil sulphur content of this method is less than 500 μ g/g, can not satisfy in Europe III and the Europe IV standard requirement to the diesel oil sulphur content.
US 6251262B1 discloses a kind of method of diesel hydrogenation for removal sulphur; This method adopts raw material to pass through the hydrodesulfurizationprocess process of three reaction zones successively; Filling is the catalyzer of major metal component with the cobalt-molybdenum in first reaction zone; The catalyzer of nickel-molybdenum component that in second reaction zone, has been seated on the carrier that contains the part zeolite load, filling is with cobalt and/or nickel in the 3rd reaction zone, and molybdenum is the catalyzer of major metal component.The catalyst loading ratio of three reaction zones is respectively 20～60 volume %, 20～60 volume % and 5～20 volume %.This method can be produced the diesel oil distillate that sulphur content satisfies Europe IV standard, but this is under the comparatively harsh situation of operational condition, to obtain.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of grading method of catalyst of deep hydrodesulfurizationof of diesel oil.
Method provided by the invention comprises: raw oil mixes back entering hydrogenator and carries out hydrogenation reaction with hydrogen; Reaction effluent obtains hydrogen-rich gas and product liquid after refrigerated separation; Four hydroconversion reaction zones are arranged in the hydrogenator successively; Filling hydrogenation protecting agent in first hydroconversion reaction zone; Filling contains the Hydrobon catalyst I of reactive metal cobalt-molybdenum in second hydroconversion reaction zone, and the mixture of filling Hydrobon catalyst I and Hydrobon catalyst II in the 3rd reaction zone loads the Hydrobon catalyst II that contains active metal nickel-tungsten at the 4th reaction zone; With the integer catalyzer volume is benchmark, and four hydroconversion reaction zone admission space percentage ratios are respectively 1～30 volume %, 10～50 volume %, 10～50 volume % and 20～60 volume %.
The present invention carries out rational gradation composition with the catalyzer of different systems, and giving full play to separately, catalyzer through the synergy between each catalyzer, has improved the integer catalyzer activity at the advantage function of different desulfurization stage.Adopt method provided by the invention, can handle high-sulfur, high nitrogen and the high diesel oil distillate of metal content, can under demulcent operational condition comparatively, obtain the ultra-low-sulphur diesel that sulphur content satisfies Europe IV standard.
Embodiment
Sulfocompound in diesel oil distillate mainly contains mercaptan, disulphide, thiophene, thionaphthene (BT) and dibenzothiophene (DBT).The hydrodesulfurization activity difference of all kinds of sulfide is very big, according to the difference of their reactivity worth, can it be divided into two groups.
First group is to be made up of fats sulfide and mononuclear aromatics class sulfide, comprises mercaptan, disulphide and thiophene.Second group is to be BT and DBT by polycyclic aromatic hydrocarbons sulfide (PASC), and their alkyl substituent is formed.The reactive behavior of first group of sulfide is more a lot of than second group high; Even under the demulcent hydrogenation conditions, just can remove; Belong to reactivity worth and be prone to the sulfide that removes by force, its desulfurization method is mainly the directly hydrogenolysis approach of fracture of C-S key, is the direct desulfurization approach.
Second group of sulfide is divided into medium sulfide of reactivity worth and two kinds in the difficult sulfide that reacts again; BT wherein; DBT and do not have the alkyl substituent of space steric effect to belong to the medium sulfide of reactivity worth, and some DBT class sulfide with space steric effect are the sulfide of difficult reaction.The speed of the sulfide of these difficult reactions its hydrogenating desulfurization under harsh reaction conditions is also very low; And its desulfurization method to be mainly aromatic nucleus elder generation hydrogenation saturated; After having got rid of the spatial obstacle that sulphur atom receives in the sulfide molecules, the approach of hydrogenolysis desulphurization reaction is also referred to as the hydrogenation approach again.With 4, and the 6-dimethyl Dibenzothiophene (4,6-DMDBT) be example; It is the representation compound of the most difficult reaction sulfide; When 4,6 of DBT all replaced by methyl after, formed a planar molecule, two methyl that nestle up sulphur atom produce space steric effects; Hindered contacting of sulphur atom and catalyst surface active position, reactant molecule can only be adsorbed on the catalyst surface with lying low through the πDian Zi of phenyl ring.But, after one of them benzene ring hydrogenation of sulphur ortho position is saturated, can form the hexanaphthene of chair form structure; The two dimensional structure of reactant molecule is destroyed, and has eliminated the contact steric hindrance of sulphur atom with catalyst surface, makes it well to be adsorbed in the catalyst active center; Then carry out further hydrogenolysis desulphurization reaction, the approach of the saturated desulfurization again of this first hydrogenation is called the hydrogenation approach; Also be 4,6-DMDBT carries out the main path of hydrogenating desulfurization.
Therefore, carry out deep desulfuration, the sulphur content that promptly requires product diesel oil just not only will remove the sulfide that is prone to reaction less than 350～500 μ g/g, also will remove most reactivity worth and belong to medium sulfide, even also will remove the sulfide of a small amount of difficult reaction.And want to reach the ultra-low-sulphur diesel specification that sulphur content is 10～50 μ g/g, except will all removing the medium sulfide of easy reaction and reactivity worth, also need almost all remove the most difficult sulfide that reacts.
Their boiling point and carbonatoms depended in the distribution of difficult desulfurization compound in cut.About 221 ℃ of BT boiling point, about 330 ℃ of the boiling point of the DBT of unsubstituted has the boiling point of substituent DBT to be not less than 340 ℃.That is to say that these high boiling sulfide are present in the last running of diesel oil more, and the reactive behavior of hydrogenating desulfurization is very low.
Through the in-depth analysis and the understanding of above composition to sulfide, distribution, hydrodesulfurization reaction, embodiment of the present invention is:
Raw oil mixes back entering hydrogenator and carries out hydrogenation reaction with hydrogen; Reaction effluent obtains hydrogen-rich gas and product liquid after refrigerated separation; Four hydroconversion reaction zones are arranged in the hydrogenator successively; Filling hydrogenation protecting agent in first hydroconversion reaction zone; Filling contains the Hydrobon catalyst I of reactive metal cobalt-molybdenum in second hydroconversion reaction zone, and the mixture of filling Hydrobon catalyst I and Hydrobon catalyst II in the 3rd reaction zone loads the Hydrobon catalyst II that contains active metal nickel-tungsten at the 4th reaction zone; With the integer catalyzer volume is benchmark, and four hydroconversion reaction zone admission space percentage ratios are respectively 1～30 volume %, 10～50 volume %, 10～50 volume % and 20～60 volume %.Reactor effluent carries out gas-liquid separation through HP separator, light pressure separator successively after cooling, the hydrogen-rich gas of gained recycles, and the liquid of gained gets into stripping tower, obtains the ultra-low-sulphur diesel of sulphur content less than 50 μ g/g then.
With the integer catalyzer volume is benchmark, and four preferred admission space percentage ratios of hydroconversion reaction zone are respectively 5～20 volume %, 10～30 volume %, 10～30 volume % and 20～50 volume %.Above-mentioned hydroconversion reaction zone can be successively set in the same reactor drum, also can be separately positioned in 2～4 differential responses devices.
Direct hydrogenolysis desulfurization path is mainly passed through in the hydrogenating desulfurization that contains the catalyzer of reactive metal cobalt-molybdenum, and the catalyzer that contains active metal nickel-tungsten has stronger hydrogenation activity, and the routing property of tackling the saturated back desulfurization of hydrogenation mutually is higher.The cobalt-molybdenum catalyzer is removing on most of sulfide, comprises DBT and 4-MDBT (4-MDBT), and performance is better than nickel-tungsten catalyst; And the catalyzer of nickel-tungsten remove steric hindrance sulfide (4,6-DMDBT) have superiority than cobalt-molybdenum catalyzer again on the performance.Consider above-mentioned cobalt-molybdenum catalyzer, the different desulphurization reaction performance of nickel-tungsten catalyst, and the reactive behavior that sulfide varies in the true charging, can the two be united use in the present invention, give full play to advantage separately.
To be arranged on same reactor drum is example, and in reactor head, the agent of filling hydrogenation protecting can partly remove glial component and metal impurities in the raw oil in first hydroconversion reaction zone, plays the effect of protection downstream hydrogenation catalyst.On reactor drum top, i.e. the Hydrobon catalyst I that second hydroconversion reaction zone filling contains the active metal component cobalt-molybdenum removes the sulfide of easy reaction.In the bottom of reactor drum, promptly filling contains the Hydrobon catalyst II of active metal component nickel-tungsten in the 4th hydroconversion reaction zone, is responsible for removing the sterically hindered alkyl DBT compounds that has of the most difficult reaction by it.And, the transient response district is set at the reactor drum middle part, promptly the 3rd hydroconversion reaction zone loads the mixture of Hydrobon catalyst I and Hydrobon catalyst II, to remove the active middle sulfide of other hydrogenation reactions.
The condition of described hydrogenation reaction is: hydrogen dividing potential drop 3.0～10.0MPa, 250～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 100～1500Nm
3/ m
3, volume space velocity 0.1～10.0h
-1Described temperature of reaction is 250～380 ℃ of the first hydroconversion reaction zone temperature, 250～400 ℃ of the second hydroconversion reaction zone temperature, 270～430 ℃ of the 3rd hydroconversion reaction zone temperature, 300～450 ℃ of the 4th hydroconversion reaction zone temperature.Through injecting cold hydrogen or injecting the temperature that the mode of cold oil is come hydroconversion reaction zone in the conditioned reaction device.
Described raw oil is selected from one or more in catalytic cracking diesel oil, straight-run diesel oil, coker gas oil and the visbreaking diesel oil.
Described hydrogenation protecting agent is group vib metal and/or the group VIII non-precious metal catalyst that loads on unformed aluminum oxide and/or the silica-alumina supports.Wherein the group vib metal is selected from molybdenum and/or tungsten, and the group VIII metal is selected from cobalt and/or nickel.
The metal component of preferred described hydrogenation protecting agent is molybdenum and nickel, is benchmark in oxide compound and with the catalyzer, and the content of molybdenum is 6～10 heavy %, and the content of nickel is 1～3 heavy %.
Described Hydrobon catalyst I is a kind of metal load type catalyst, and carrier is an aluminum oxide, and metal component is cobalt and molybdenum, is benchmark in oxide compound and with the catalyzer, and the content of cobalt is 1～5 heavy %, and the content of molybdenum is 9～20 heavy %.This catalyzer uses the method for dipping in alumina supporter, to introduce molybdenum salt and cobalt salt by comprising, and through super-dry and roasting preparation, said molybdenum salt is that ammonium molybdate, cobalt salt are Xiao Suangu.Said drying temperature is 100～300 ℃, and be 1～6 hour time of drying; Maturing temperature is 350～550 ℃, and be 1～6 hour time of drying.
Described Hydrobon catalyst II is a benchmark with the catalyzer, and it consists of: nickel oxide 1～10 heavy %; Molybdenum oxide and Tungsten oxide 99.999 sum are 10～50 heavy %, fluorine 1～10 heavy %, phosphorus oxide 0.5～8 heavy %; Surplus is a silica-alumina; With the carrier is benchmark, and silica content is 2～45 heavy %, and alumina content is 55～98 heavy %.Said carrier specific surface area is 50～400m
2/ g, preferred 100～300m
2/ g.Pore volume is 0.1～1.0ml/g, preferred 0.2～0.5ml/g.
Advantage of the present invention:
1, adopts method provided by the invention, can under demulcent operational condition comparatively, obtain the ultra-low-sulphur diesel of sulphur content less than 50 μ g/g.The present invention carries out rational gradation composition with the catalyzer of different systems; Give full play to separately catalyzer at the advantage function of different desulfurization stage; Through the synergy between each catalyzer and with the cooperating of differential responses district temperature of reaction gradient, it is active to have improved integer catalyzer.Under the operational condition of routine; The present invention can reduce catalyst consumption or reduce temperature of reaction reaching under the identical desulfurization degree, in addition, the present invention is provided with the transient response district; Also further improve catalyzer overall activity and catalyst stability, reduced running cost simultaneously.
2, because the preposition protective material bed of the present invention or be filled with protectant guard reactor makes the Hydrobon catalyst in downstream keep higher activity stability.
3, method provided by the invention is the one-stage serial operation, and catalyst loading is simple, appliance arrangement is few, so its equipment investment cost is lower.
Following embodiment will further explain method provided by the invention, but therefore do not limit the present invention.
The trade names of used hydrogenation protecting agent are RG-1 among the embodiment, for catalyzer Chang Ling branch office of China Petrochemical Corp. produces.
The composition of used Hydrobon catalyst I among the embodiment: in oxide compound and with the total catalyst weight is benchmark, and cobalt is 3.0 heavy %, and molybdenum is 13.5 heavy %.The specific surface area of Hydrobon catalyst I is 198m
2/ g, pore volume are 0.35ml/g.
The composition of used Hydrobon catalyst II among the embodiment: in oxide compound and with the total catalyst weight is benchmark, and nickel is 2.5 heavy %, and molybdenum is 6.8 heavy %, and tungsten is 19.6 heavy %, fluorine 1.6 heavy %, phosphorus oxide 2.5 heavy %.
Embodiment 1
Raw oil A mixes back entering hydrogenator and carries out hydrogenation reaction with hydrogen; Reaction effluent obtains hydrogen-rich gas and product liquid after refrigerated separation; In four hydroconversion reaction zones of hydrogenator: first reaction zone filling protective material RG-1, loadings 10ml; Second reaction zone filling Hydrobon catalyst I, loadings is 10ml; The 3rd reaction zone loads the mixture of Hydrobon catalyst I and Hydrobon catalyst II, and loadings is 30ml; Four reaction areas filling Hydrobon catalyst II, loadings is 50ml.
Raw oil A character is listed in table 1, and visible by table 1, the sulphur content of raw oil A is high sulphur-bearing diesels up to 13000 μ g/g.Processing condition and product property are listed in table 2 and table 3 respectively.Visible by table 2 and table 3, at hydrogen dividing potential drop 4.8MPa, air speed 2.0h
-1Operational condition under, the sulphur content of product diesel oil is less than 50 μ g/g, the visible purpose that adopts this catalyzer grading loading system to reach ultra-deep hydrodesulfuration.
Embodiment 2
Raw oil A mixes back entering hydrogenator and carries out hydrogenation reaction with hydrogen; Reaction effluent obtains hydrogen-rich gas and product liquid after refrigerated separation; In four hydroconversion reaction zones of hydrogenator: first reaction zone filling protective material RG-1, loadings 10ml; Second reaction zone filling Hydrobon catalyst I, loadings is 20ml; The 3rd reaction zone loads the mixture of Hydrobon catalyst I and Hydrobon catalyst II, and loadings is 30ml; Four reaction areas filling Hydrobon catalyst II, loadings is 40ml.
Raw oil A character is listed in table 1, and visible by table 1, the sulphur content of raw oil A is high sulphur-bearing diesels up to 13000 μ g/g.Processing condition and product property are listed in table 2 and table 3 respectively.Visible by table 2 and table 3, at hydrogen dividing potential drop 4.8MPa, air speed 2.0h
-1Operational condition under, the sulphur content of product diesel oil is less than 50 μ g/g, the visible purpose that adopts this catalyzer grading loading system to reach ultra-deep hydrodesulfuration.
Embodiment 3
Raw oil A mixes back entering hydrogenator and carries out hydrogenation reaction with hydrogen; Reaction effluent obtains hydrogen-rich gas and product liquid after refrigerated separation; In four hydroconversion reaction zones of hydrogenator: first reaction zone filling protective material RG-1, loadings 10ml; Second reaction zone filling Hydrobon catalyst I, loadings is 30ml; The 3rd reaction zone loads the mixture of Hydrobon catalyst I and Hydrobon catalyst II, and loadings is 30ml; Four reaction areas filling Hydrobon catalyst II, loadings is 30ml.
Raw oil A character is listed in table 1, and visible by table 1, the sulphur content of raw oil A is high sulphur-bearing diesels up to 13000 μ g/g.Processing condition and product property are listed in table 2 and table 3 respectively.Visible by table 2 and table 3, at hydrogen dividing potential drop 4.8MPa, air speed 2.0h
-1Operational condition under, the sulphur content of product diesel oil is less than 50 μ g/g, the visible purpose that adopts this catalyzer grading loading system to reach ultra-deep hydrodesulfuration.
Embodiment 4
Raw oil B mixes back entering hydrogenator and carries out hydrogenation reaction with hydrogen; Reaction effluent obtains hydrogen-rich gas and product liquid after refrigerated separation; In four hydroconversion reaction zones of hydrogenator: first reaction zone filling protective material RG-1, loadings 10ml; Second reaction zone filling Hydrobon catalyst I, loadings is 15ml; The 3rd reaction zone loads the mixture of Hydrobon catalyst I and Hydrobon catalyst II, and loadings is 25ml; Four reaction areas filling Hydrobon catalyst II, loadings is 50ml.
Raw oil B character is listed in table 1, and visible by table 1, the sulphur content of raw oil B is 6000 μ g/g, and nitrogen content is 271 μ g/g, belongs to the high diesel oil of nitrogen content.Processing condition and product property are listed in table 2 and table 3 respectively.Visible by table 2 and table 3, at hydrogen dividing potential drop 6.4MPa, air speed 2.0h
-1Operational condition under, the sulphur content of product diesel oil is less than 50 μ g/g, the visible purpose that adopts this catalyzer grading loading system to reach ultra-deep hydrodesulfuration.
Embodiment 5
Raw oil B mixes back entering hydrogenator and carries out hydrogenation reaction with hydrogen; Reaction effluent obtains hydrogen-rich gas and product liquid after refrigerated separation; In four hydroconversion reaction zones of hydrogenator: first reaction zone filling protective material RG-1, loadings 10ml; Second reaction zone filling Hydrobon catalyst I, loadings is 10ml; The 3rd reaction zone loads the mixture of Hydrobon catalyst I and Hydrobon catalyst II, and loadings is 20ml; Four reaction areas filling Hydrobon catalyst II, loadings is 60ml.
Raw oil B character is listed in table 1, and visible by table 1, the sulphur content of raw oil B is 6000 μ g/g, and nitrogen content is 271 μ g/g, belongs to the high diesel oil of nitrogen content.Processing condition and product property are listed in table 2 and table 3 respectively.Visible by table 2 and table 3, at hydrogen dividing potential drop 6.4MPa, air speed 2.0h
-1Operational condition under, the sulphur content of product diesel oil is less than 50 μ g/g, the visible purpose that adopts this catalyzer grading loading system to reach ultra-deep hydrodesulfuration.
Comparative Examples 1
Raw oil A mixes back entering hydrogenator and carries out hydrogenation reaction with hydrogen, reaction effluent obtains hydrogen-rich gas and product liquid after refrigerated separation, in the hydrogenator: top loading protective material RG-1, loadings 10ml; Rest part filling Hydrobon catalyst I, loadings is 90ml.
Processing condition and product property are listed in table 2 and table 3 respectively.Visible by table 2 and table 3, under the same operation condition, product diesel oil sulphur content is 89 μ g/g, all is higher than the product sulphur content of embodiment 1, embodiment 2 and embodiment 3.Explain that the sweetening effectiveness that adopts this patent method to reach is higher than employing cobalt-molybdenum type list catalyst system.
Comparative Examples 2
Raw oil A mixes back entering hydrogenator and carries out hydrogenation reaction with hydrogen, reaction effluent obtains hydrogen-rich gas and product liquid after refrigerated separation, in the hydrogenator: top loading protective material RG-1, loadings 10ml; Rest part filling Hydrobon catalyst II, loadings is 90ml.
Processing condition and product property are listed in table 2 and table 3 respectively.Visible by table 2 and table 3, under the same operation condition, product diesel oil sulphur content is 71 μ g/g, all is higher than the product sulphur content of embodiment 1, embodiment 2 and embodiment 3.Explain that the sweetening effectiveness that adopts this patent method to reach is higher than employing nickel-tungsten type list catalyst system.
Table 1
| Raw material diesel oil numbering | Raw oil A | Raw oil B |
| Density (20 ℃), g/cm 3 | 0.8495 | 0.8801 |
| Refractive power, n d 20 | 1.4803 | 1.4992 |
| S，μg/g | 13000 | 6000 |
| N，μg/g | 157 | 271 |
| The bromine valency, gBr/100g | 2.8 | 7.5 |
| Boiling range ASTM D-1160, ℃ | ||
| IBP | 195 | 199 |
| 5％ | 218 | 235 |
| 10％ | 235 | 248 |
| 50％ | 282 | 288 |
| 90％ | 339 | 352 |
| FBP | 363 | 370 |
Table 2
| Processing condition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Temperature of reaction, ℃ | 360 | 360 | 360 | 350 | 360 |
| The hydrogen dividing potential drop, MPa | 4.8 | 4.8 | 4.8 | 6.4 | 6.4 |
| Volume space velocity, h -1 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 |
| Hydrogen-oil ratio, Nm 3/m 3 | 300 | 300 | 300 | 300 | 300 |
| Processing condition | Comparative Examples 1 | Comparative Examples 2 |
| Temperature of reaction, ℃ | 360 | 360 |
| The hydrogen dividing potential drop, MPa | 4.8 | 4.8 |
| Volume space velocity, h -1 | 2.0 | 2.0 |
| Hydrogen-oil ratio, Nm 3/m 3 | 300 | 300 |
Table 3
| Product property | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Density (20 ℃), g/cm 3 | 0.8310 | 0.8305 | 0.8302 | 0.8595 | 0.8577 |
| S，μg/g | 47 | 40 | 38 | 43 | 35 |
| N，μg/g | 3 | 4 | 3 | 10 | 5 |
| Product property | Comparative Examples 1 | Comparative Examples 2 |
| Density (20 ℃), g/cm 3 | 0.8355 | 0.8290 |
| S，μg/g | 89 | 71 |
| N，μg/g | 19 | 2 |
Claims (8)
1. the grading method of catalyst of a deep hydrodesulfurizationof of diesel oil; Raw oil mixes back entering hydrogenator and carries out hydrogenation reaction with hydrogen; Reaction effluent obtains hydrogen-rich gas and product liquid after refrigerated separation; It is characterized in that four hydroconversion reaction zones are arranged in the hydrogenator successively, filling hydrogenation protecting agent in first hydroconversion reaction zone, filling contains the Hydrobon catalyst I of reactive metal cobalt-molybdenum in second hydroconversion reaction zone; The mixture of filling Hydrobon catalyst I and Hydrobon catalyst II in the 3rd reaction zone loads the Hydrobon catalyst II that contains active metal nickel-tungsten at the 4th reaction zone; With the integer catalyzer volume is benchmark, and four hydroconversion reaction zone admission space percentage ratios are respectively 1～30 volume %, 10～50 volume %, 10～50 volume % and 20～60 volume %; Wherein, temperature of reaction is: 250～380 ℃ of the first hydroconversion reaction zone temperature, 250～400 ℃ of the second hydroconversion reaction zone temperature, 270～430 ℃ of the 3rd hydroconversion reaction zone temperature, 300～450 ℃ of the 4th hydroconversion reaction zone temperature.
2. method according to claim 1 is characterized in that with the integer catalyzer volume be benchmark, and four hydroconversion reaction zone admission space percentage ratios are respectively 5～20 volume %, 10～30 volume %, 10～30 volume % and 20～50 volume %.
3. method according to claim 1 is characterized in that the condition of described hydrogenation reaction is: hydrogen dividing potential drop 3.0～10.0MPa, 250～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 100～1500Nm
3/ m
3, volume space velocity 0.1～10.0h
-1
4. method according to claim 1 is characterized in that described raw oil is selected from one or more in catalytic cracking diesel oil, straight-run diesel oil, coker gas oil and the visbreaking diesel oil.
5. method according to claim 1 is characterized in that described hydrogenation protecting agent is group vib metal and/or the group VIII non-precious metal catalyst that loads on unformed aluminum oxide and/or the silica-alumina supports.Wherein the group vib metal is selected from molybdenum and/or tungsten, and the group VIII metal is selected from cobalt and/or nickel.
6. method according to claim 1, the metal component that it is characterized in that described hydrogenation protecting agent is molybdenum and nickel, is benchmark in oxide compound and with the catalyzer, and the content of molybdenum is 6～10 heavy %, and the content of nickel is 1～3 heavy %.
7. method according to claim 1 is characterized in that described Hydrobon catalyst I is a kind of metal load type catalyst, and carrier is an aluminum oxide; Metal component is cobalt and molybdenum; In oxide compound and with the catalyzer is benchmark, and the content of cobalt is 1～5 heavy %, and the content of molybdenum is 9～20 heavy %.
8. method according to claim 1 is characterized in that described Hydrobon catalyst II, is benchmark with the catalyzer; It consists of: nickel oxide 1～10 heavy %, and molybdenum oxide and Tungsten oxide 99.999 sum are 10～50 heavy %, fluorine 1～10 heavy %; Phosphorus oxide 0.5～8 heavy %; Surplus is a silica-alumina, is benchmark with the carrier, and silica content is that 2～45 heavy % alumina contents are 55～98 heavy %.
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| CN102311759B (en) * | 2010-07-07 | 2015-02-18 | 中国石油化工股份有限公司 | Method for hydrodesulfurization of diesel |
| CN102443430B (en) * | 2010-10-13 | 2014-03-05 | 中国石油化工股份有限公司 | Method for preparing ethylene cracking material by hydrogenising liquefied petroleum gas |
| CN102443424B (en) * | 2010-10-15 | 2014-10-29 | 中国石油化工股份有限公司 | Method for producing clean diesel from coal tar |
| CN102876374B (en) * | 2011-07-11 | 2015-04-01 | 中国石油化工股份有限公司 | Inferior diesel oil hydrodesulfurization method |
| CN103059983B (en) * | 2011-10-21 | 2014-12-31 | 中国石油化工股份有限公司 | Hydrofining catalyst combined filling method |
| CN102876365B (en) * | 2012-09-18 | 2015-02-11 | 中国海洋石油总公司 | Method for grading catalysts for hydrofining of inferior distillate oil |
| CN105521791B (en) * | 2014-10-22 | 2017-10-27 | 中国石油化工股份有限公司 | The preparation method of vulcanization type catalyst for selective hydrodesulfurizationof of gasoline |
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| CN105623726B (en) * | 2014-10-28 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of method of hydrotreating for producing diesel oil |
| US11439989B2 (en) | 2018-04-10 | 2022-09-13 | China Petroleum & Chemical Corporation | Hydrofining catalyst, its preparation and application thereof |
| CN111073683B (en) * | 2018-10-22 | 2021-08-31 | 中国石油化工股份有限公司 | Method for ultra-deep desulfurization and dearomatization of diesel oil |
| CN111100695A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Wax oil hydrotreating method with sectional feeding |
| CN114433058B (en) * | 2020-10-31 | 2023-11-07 | 中国石油化工股份有限公司 | Liquid phase hydrogenation catalyst composition |
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| CN101092573A (en) * | 2006-06-22 | 2007-12-26 | 中国石油化工股份有限公司 | A hydrogenation method for producing diesel oil in low sulphur |
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| CN101092573A (en) * | 2006-06-22 | 2007-12-26 | 中国石油化工股份有限公司 | A hydrogenation method for producing diesel oil in low sulphur |
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