CN101987967A - Hydrotreatment method of deep vacuum distillation wax oil - Google Patents
Hydrotreatment method of deep vacuum distillation wax oil Download PDFInfo
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Abstract
The invention relates to a hydrotreatment method of deep vacuum distillation wax oil. The mixture of raw oil and hydrogen passes through two hydrogenation reaction zones in sequence, wherein a hydrogenation protective agent and a hydrogenation demetalization deasphaltenizing agent are filled in the first hydrogenation reaction zone, and a hydrogenation desulfurizing agent and a hydrogenation denitrification desulfurizing agent are filled in the second hydrogenation reaction zone. Reaction products are cooled and separated to obtain refined heavy fraction oil, and the refined heavy fraction oil is a high quality raw material for catalytic cracking. In the invention, the raw oil has strong adaptability and can be used for processing deep vacuum distillation wax oil with high sulphur content, high nitrogen content, high metal and high asphaltene content and mixed oil thereof, and moreover, the device has long running period.
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 hydroprocessing process of reduce pressure deep drawing wax oil and mixing oil thereof.
Background technology
At present, crude oil price is more and more higher, and the ratio that the crude oil purchase cost accounts in the oil refining total cost significantly rises, and makes the profit margin of refinery dwindle greatly.On the other hand, the trend of crude resources poor qualityization and heaviness is obvious in the world wide, and U.S. imported crude oil API degree has reduced by 4 more than the unit so far from early eighties, and the situation of China is suitable therewith.Under this background, how to utilize limited resources, the oil Refining Technologies of byproducts such as maximum production purpose oil product (mainly being light oil and intermediate oil), reduction coke becomes the key that refinery is increased the benefit.
Wherein, the decompression deep drawing technology that can improve the straight run extracting rate has obtained many application in recent years.Common vacuum distillate (VGO) boiling range mostly is 350 ℃～540 ℃ greatly, and when vacuum distillation tower was taked the deep drawing operation, the final boiling point of the decompression deep drawing wax oil of acquisition was much larger than the final boiling point of common VGO.The lighter crude oil that abroad processes raw material, as Brunt oil or high-sulfur Arabian light, final boiling point can reach more than 610 ℃, processing heavy crude or the high crude oil of asphalt content, final boiling point also can reach more than 565 ℃.Decompression deep drawing technology can access the straight-run gas oils that can be used as catalytically cracked material more, thereby reduces yield of bottoms, improves full factory purpose product yield.But after adopting decompression deep drawing technology, resulting decompression deep drawing wax oil character is relatively poor, shows as sulphur content and nitrogen content height, and coking precursor amounts height such as bituminous matter, carbon residue, metal content also obviously rise.
On the other hand, the catalytic cracking technology in that China's refinery is widely applied for the needs of environment protection and improving constantly of petrol and diesel oil target level of product quality, also needs fcc raw material is made certain restriction.The catalytically cracked material of high sulfur content not only makes in the catalytic cracking flue gas SOx discharging not meet environmental requirement, and the sulphur content of petrol and diesel oil product and diesel cetane-number all can not meet the product specification requirement.High nitrogen-containing in the catalytically cracked material can increase the agent consumption of cracking catalyst, increases process cost.Catalytically cracked material hydrogenation preconditioning technique can reduce its sulphur nitrogen content significantly, increases hydrogen richness, thereby reduces the sulphur nitrogen content of cracked product, improves product and distributes, and has therefore obtained increasing application.
When decompression deep drawing wax oil being carried out the hydrogenation pre-treatment as catalytically cracked material with existing conventional wax oil hydrogenation treatment technology, because decompression deep drawing wax oil boiling range is heavy, foreign matter content is high, density is big, sulfide and nitride hydrogenation reaction activity in the decompression deep drawing wax oil are low, must improve the hydrogenation reaction temperature and just can reach the desired hydrogenation degree of depth, can cause shortening the catalyst runs cycle and improve temperature of reaction.Even more serious is that because the change of decompression deep drawing wax oil boiling range makes that asphalt content increases, carbon residue increases after weighing, the coking rate on the hydrogenation catalyst is accelerated, and causes adopting shorten the running period of conventional hydrogenation preconditioning technique processing deep drawing wax oil.In addition, because the final boiling point height of decompression deep drawing wax oil causes metallic compounds such as some nickel, vanadium to enter into decompression deep drawing wax oil.These metals easily cause the rising of poisoning of catalyst and bed pressure drop, cause catalyzer permanent deactivation, running period to shorten, and have reduced the economic benefit of wax oil hydrogenation treating processes.Therefore, must adopt the technological method of cutting the garment according to the figure to handle decompression deep drawing wax oil.
US4780193 has announced a kind of method of hydrorefining catalyst cracked charge, this method adopts hydrorefined method to improve the quality of catalytically cracked material, the temperature of reaction of hydro-refining unit is lower than 390 ℃, and reaction pressure should be preferably in more than the 12.0MPa more than 10.0MPa.Helping under the saturated processing condition of aromatic hydrocarbons, improving the cracking performance of catalytic cracking unit raw material, thereby improving the transformation efficiency of catalytic cracking unit, producing the high gasoline blend component of octane value by hydrofining.Reduce catalytically cracked material sulphur and nitrogen content significantly by the hydrofining meeting, thereby, can reduce the content of SOx in the catalytic cracking flue gas significantly, the cracking catalyst deactivation rate also can reduce owing to the minimizing of nitrogen content in the raw material.
CN101007964A discloses a kind of method of hydrotreating of producing fine quality catalytic cracking raw material, and this method is provided with the technology of catalyst combination processing decompressed wax oil, wax tailings, the low nitrogen content fine quality catalytic cracking charging of diasphaltene wet goods production low-sulfur.The catalyst activity height that this technology adopts, flow process is simple, and working pressure is lower.But such technology will face that coking rate is fast, running period short, the hydrotreatment degree of depth does not reach the shortcoming of requirement when the higher decompression deep drawing wax slop of process asphaltene, carbon residue and metal content.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of hydroprocessing process of reduce pressure deep drawing wax oil and mixing oil thereof.Specifically, be that lack and the not enough problem of the hydrotreatment degree of depth running period of existence in the time of will solving the method for prior art processing decompression deep drawing wax slop production high-quality FCC charging inferior.
Method provided by the invention, comprise: decompression deep drawing wax oil and optional last running oil-hydrogen mixture pass through two hydroconversion reaction zones successively, filling hydrogenation protecting agent and the agent of hydrodemetallation (HDM) diasphaltene in first hydroconversion reaction zone, filling hydrogenating desulfurization agent and hydrodenitrification sweetening agent in second hydroconversion reaction zone, resultant of reaction obtain refining heavy distillate after refrigerated separation; With the first hydroconversion reaction zone integer catalyzer is benchmark, and the admission space ratio of the hydrogenation protecting agent of first hydroconversion reaction zone and the agent of hydrodemetallation (HDM) diasphaltene is 10～50: 50～90; With the second hydroconversion reaction zone integer catalyzer is benchmark, and the admission space ratio of the hydrogenating desulfurization agent of second hydroconversion reaction zone and hydrodenitrification sweetening agent is 10～30: 70～90.
Know that in heavy distillate hydrotreatment process, coking deactivation is the major cause of hydrogenation catalyst inactivation, and the asphalt content in coke deposit rate and the stock oil is closely related, asphalt content is high more, and coke deposit rate is fast more.Therefore in common heavy distillate hydrotreatment process, the asphalt content that requires stock oil is preferably in below 100～200 μ g/g less than 400～800 μ g/g.And the decompression deep drawing wax oil asphalt content of poor quality of the present invention often surpasses 400 μ g/g.The final boiling point of described decompression deep drawing wax oil is 550～610 ℃, and asphalt content is 400 μ g/g～2500 μ g/g.Stock oil of the present invention can be various decompression deep drawing wax oil raw materials inferior, and the deasphalted oil that coker gas oil and deasphalting unit produced that perhaps reduce pressure deep drawing wax oil and other various straight-run gas oil cut, cokers are produced is by different ratios blended mixing oil.The raw material total metal contents in soil is not more than 15 μ g/g, and is the most desirable below 5 μ g/g.
The present invention is directed to the transformation rule of hydrotreatment process medium pitch matter, design a kind of rational reactor catalyst grading method and technical process and handle decompression deep drawing heavy wax oil.Method provided by the invention specifically describes as follows:
Raw material decompression deep drawing wax oil after the strainer of filter core suitable size filters, boosts and all or part of hydrogen-rich recycle body enter process furnace and be heated to temperature of reaction, enter first hydroconversion reaction zone that is filled with hydrogenation protecting agent and the agent of hydrodemetallation (HDM) diasphaltene then.The average bed temperature of controlling first hydroconversion reaction zone is between 320～375 ℃, and reactor hydrogen pressures is at 5.0～11.0MPa, and hydrogen-oil ratio is at 200～600Nm
3/ m
3Between, volume space velocity is at 2.0～15.0h
-1Between.Control hydrogenation protecting agent and hydrodemetallation (HDM) diasphaltene agent bed are in lower temperature of reaction; can reduce bitum coking rate, make bituminous matter the aperture greater than the hydrogenation protecting agent of 150 dusts and hydrodemetallation (HDM) diasphaltene agent effect under and hydrogen generation depolymerization reaction.When bituminous matter is carried out hydrodepolymerization, first hydroconversion reaction zone will remove most of alkene, carbon residue and metal.
The first hydroconversion reaction zone effluent without intermediate section from, enter second hydroconversion reaction zone that is filled with the less hydrogenating desulfurization agent/hydrodenitrification sweetening agent in pore volume aperture after replenishing the part hydrogen-rich gas simultaneously.The Hydrobon catalyst of second hydroconversion reaction zone has littler than the catalyzer of first hydroconversion reaction zone, but than the big pore volume aperture of hydrodenitrification sweetening agent, can promote the bitum further hydrogenation of depolymerization, the metal that holding portion first hydroconversion reaction zone does not remove, this catalyzer has high direct hydrodesulfurization activity simultaneously, helps improving the hydrogenating desulfurization degree of depth with follow-up hydrodenitrification sweetening agent integrally combined.The reactive hydrogen branch of second hydroconversion reaction zone is pressed between 5.0～11.0MPa, and the average bed temperature of reaction of catalyzer is that hydrogen-oil ratio is at 300～1200Nm between 355～430 ℃
3/ m
3Between, volume space velocity is at 1.0～5.0h
-1Between.Under the effect of the second hydroconversion reaction zone catalyzer and hydrogen, the first hydroconversion reaction zone effluent carries out the bitum hydrogenation of depolymerization, deep hydrodesulfurizationof and hydrodenitrification reaction.Second hydroconversion reaction zone outlet logistics enters high pressure hot separator through after the suitable heat exchange, is divided into gas phase and liquid product in the high pressure hot separator reactant flow.Hot high score gas-phase product enters cold high pressure separator after the water cooler cooling, the low boiler cut that the cold high pressure separator bottom obtains enters the cold low separator, the hydrogen-rich gas that the cold high pressure separator top obtains goes amine to wash that tower removes hydrogen sulfide after the circulating hydrogen compressor supercharging, a part is as the cold hydrogen of catalyst bed interlayer, a part with get back to first and second reaction zones after additional new hydrogen mixes and enter the mouth.The liquid product of high pressure hot separator then enters thermal low-pressure separators, the thermal low-pressure separators gas-phase product enters the cold low separator, thermal low-pressure separators liquid product and cold low separator liquid phase product are mixed into hydrogen sulfide stripping tower and separation column, cut into petroleum naphtha, diesel oil and refining heavy distillate.
When unit scale is less; also can merge into a reactor to first and second hydroconversion reaction zones; be divided into two different reaction zones; hydrogenation protecting agent/hydrodemetallation (HDM) deasphalting medium is seated in first hydroconversion reaction zone (top), and hydrogenating desulfurization agent/hydrodenitrification sweetening agent is seated in second hydroconversion reaction zone (bottom).The processing parameter of two reaction zones of control reaches aforesaid scope and also can reach the ideal effect.
Described hydrogenation protecting agent contains a kind of alumina supporter and the molybdenum and/or the tungsten that load on this alumina supporter, and nickel and/or cobalt.Gross weight with catalyzer is a benchmark, and in oxide compound, the consisting of of described preferred hydrogenation protecting agent: the alumina supporter of 0.5～5.0 heavy % nickel oxide, 2.0～10.0 heavy % molybdenum oxides and surplus.Described hydrogenation protecting agent has two kinds at least, and different hydrogenation protecting agent has same carrier and same reactive metal, but the reactive metal charge capacity of the hydrogenation protecting agent of top filling is less than the reactive metal charge capacity of the hydrogenation protecting agent of bottom filling.The granularity of the hydrogenation protecting agent of top filling is greater than the granularity of the hydrogenation protecting agent of bottom filling.The purpose that adopts multiple hydrogenation protecting agent is in order to form active and the granularity gradient, fresh decompression deep drawing wax oil is touched be unlikely to reaction behind the catalyzer too violent, helps reducing beds pressure drop climbing speed, raising running period.
The agent of described hydrodemetallation (HDM) diasphaltene contains a kind of alumina supporter and the molybdenum and/or the tungsten that load on this carrier, and nickel and/or cobalt metal component, the mean pore sizes of wherein said alumina supporter is 25～35nm, and pore volume is 1.2～2.0ml/g, and specific surface area is 200～350m
2/ g.Consisting of of preferred hydrodemetallation (HDM) diasphaltene agent: the gross weight with catalyzer is a benchmark, and in oxide compound, molybdenum and/or tungsten 4.0～12.0%, nickel and/or cobalt 0.8～5.5%.Compare the hydrodemetallation (HDM) of hydrodemetallation (HDM) deasphalting medium provided by the invention and bituminous matter depolymerization performance height with existing catalyzer.
Described hydrogenating desulfurization agent is a metal load type catalyst, and wherein carrier is aluminum oxide and optional silicon oxide, and reactive metal is cobalt and molybdenum.The carrier of preferred described hydrogenating desulfurization agent is an aluminum oxide, be benchmark with the gross weight of catalyzer, and in oxide compound, molybdenum is 8～20 weight %, and cobalt is 0.3～8 weight %.
Described hydrodenitrification sweetening agent is a metal load type catalyst, and wherein carrier is aluminum oxide and optional silicon oxide, and reactive metal is nickel, molybdenum and tungsten.Preferred described hydrodenitrification sweetening agent is to be fluorine-containing, the phosphorus hydrogenation catalyst of carrier with the silica-alumina, consisting of after this catalyzer roasting: nickel oxide 1～10 weight %, molybdenum oxide and Tungsten oxide 99.999 sum are 10～50 weight %, fluorine 1～10 weight %, phosphorus oxide 0.5～8 weight %, surplus is a silica-alumina.
The reactive metal of described Hydrobon catalyst is cobalt and molybdenum, has good direct desulfurization activity, under demulcent condition comparatively, just can remove those easily sulfide and the medium sulfide of most of reactivity worth of reaction in the stock oil.The reactive metal of described hydrodenitrification sweetening agent is nickel, molybdenum and tungsten, the hydrogenation performance is good, the denitrification activity height, and the carrying out that helps the hydrogenation reaction of the most difficult reaction sulfide, to needs through aromatic nucleus hydrogenation saturated elimination space steric effect again the sulfide of hydrogenolysis desulfurization approach have than high desulfurization activity.Under demulcent reaction conditions comparatively, can with in the raw material the sulfide of difficult reaction remove.At second hydroconversion reaction zone above-mentioned two kinds of catalyzer are carried out combining and configuring, can improve the hydrogenating desulfurization and the hydrodenitrification degree of depth of decompression deep drawing wax oil inferior.
Advantage of the present invention:
(1) stock oil adaptability is strong, can process the decompression deep drawing wax oil and the mixing oil thereof of high sulfur content, high nitrogen-containing, high metal, high asphalt content.
(2) first hydroconversion reaction zone that hydrogenation activity is lower, the pore volume aperture is bigger is set, can effective elimination metal and alkene under demulcent processing condition comparatively, promote bitum depolymerization, reduce catalyzer coking speed, delay bed pressure drop and rise.
(3) high, the active second strong hydroconversion reaction zone of desulfurization removing nitric of amount on the metal is set, under higher temperature of reaction, can strengthen bitum further hydrogenation (being converted into oil), the Co-Mo type hydrogenating desulfurization agent of second hydroconversion reaction zone configuration simultaneously and the combination of Ni-W-Mo type hydrodenitrification sweetening agent can improve the hydrogenating desulfurization and the hydrodenitrification degree of depth of deep drawing wax oil inferior.
(4) adopt the present invention to handle decompression deep drawing wax oil inferior and mixing oil thereof, running period is long, can reach the running period more than 3 years, guarantees to overhaul synchronously with catalytic cracking unit.
Embodiment
The following examples will give further instruction to present method, but therefore not limit present method.The trade names of the hydrogenation protecting agent I that uses among the embodiment are RG-10A; the trade names of hydrogenation protecting agent II are RG-10B; the trade names of hydrodemetallation (HDM) diasphaltene agent are RDM-x; the trade names of hydrogenating desulfurization agent are RMS-1; the trade names of hydrodenitrification sweetening agent are RN-32V, and above-mentioned catalyzer is produced by Sinopec catalyzer branch office Chang Ling catalyst plant.
Embodiment 1
The stock oil of present embodiment is decompression deep drawing wax oil A, and its character is as shown in table 1.Adopt method provided by the invention, on the medium-sized hydropyrolysis experiment device of the fixed bed that is provided with two reactors, handle.The commercial trade mark of the catalyst combination that first reactor adopts is RG-10A/RG-10B/RDM-x, and the admission space ratio is 20: 20: 60, and second reactor adopts RMS-1/RN-32V, and its admission space ratio is respectively 15: 85 (volume ratio).Catalyzer is reprocessed stock oil through after the sulfidizing.Processing parameter and product oil nature see Table 2.
As can be seen from Table 2, by method provided by the invention, the carbon residue of the refining heavy distillate of acquisition is less than 0.2 weight %, and total metal contents in soil is less than 0.3 μ g/g, and sulphur content only is 1200 μ g/g, and nitrogen content only is 630 μ g/g, is the fine catalytically cracked material.In addition, the device smooth operation is after 1500 hours, and the reactor bed pressure drop does not have considerable change, and the reactor bed average reaction temperature is a little more than 2 ℃ of device initial operating stages.
The character of table 1 decompression deep drawing wax oil A
| Project | Numerical value |
| Density (20 ℃), g/cm 3 | 0.9587 |
| Carbon residue, % | 1.99 |
| Bituminous matter, μ g/g | 760 |
| Total sulfur content, μ g/g | 39500 |
| Total nitrogen content, μ g/g | 1700 |
| Total metal, μ g/g | 4.9 |
| Boiling range ASTM D1160, ℃ | |
| Initial boiling point | 410 |
| 50％ | 525 |
| 90％ | 585 |
| Final boiling point | 610 |
Table 2
| The first reactor process parameter | |
| Temperature of reaction, ℃ | 346 |
| The hydrogen dividing potential drop, MPa | 8.0 |
| Volume space velocity, h -1 | 4.0 |
| Hydrogen to oil volume ratio, v/v | 400 |
| The second reactor process parameter | |
| Temperature of reaction, ℃ | 371 |
| The hydrogen dividing potential drop, MPa | 8.0 |
| Volume space velocity, h -1 | 1.9 |
| Hydrogen to oil volume ratio, v/v | 600 |
| Product purification heavy distillate character | |
| Density (20 ℃), g/cm 3 | 0.901 |
| Carbon residue, weight % | ＜0.2 |
| Total metal contents in soil, μ g/g | ＜0.3 |
| Sulphur content, μ g/g | 1200 |
| Nitrogen content, μ g/g | 630 |
| Boiling range D-1160 ℃ | |
| Initial boiling point | 363 |
| 50％ | 490 |
| Final boiling point | 602 |
Embodiment 2
Stock oil B in the present embodiment mixes the mixed gatch that obtains for reduce pressure deep drawing wax slop and coker gas oil (CGO) by mass ratio at 85: 15.Its character is as shown in table 3.Adopt method provided by the invention, on the medium-sized hydropyrolysis experiment device of the fixed bed that is provided with two reactors, handle.The commercial trade mark of the catalyst combination that first reactor adopts is RG-10A/RG-10B/RDM-x, and the admission space ratio is 10: 15: 75, and second reactor adopts RMS-1/RN-32V, and its admission space ratio was respectively 20: 80.Catalyzer is reprocessed stock oil through after the sulfidizing.Processing parameter and product oil nature see Table 4.
As can be seen from Table 4, by method provided by the invention, the carbon residue of the refining heavy distillate of acquisition is less than 0.1 weight %, and total metal contents in soil is less than 0.1 μ g/g, and sulphur content only is 950 μ g/g, and nitrogen content only is 750 μ g/g, is the fine catalytically cracked material.In addition, the device smooth operation is after 1500 hours, and the reactor bed pressure drop does not have considerable change, and the reactor bed average reaction temperature is a little more than 3 ℃ of device initial operating stages.
The character of table 3 mixed gatch B
| Project | Numerical value |
| Density (20 ℃), g/cm 3 | 0.8967 |
| Sulphur, μ g/g | 11000 |
| Nitrogen, μ g/g | 2700 |
| Carbon residue, % | 0.90 |
| Bituminous matter, μ g/g | 1900 |
| Total metal, μ g/g | 6.2 |
| Boiling range D-1160, ℃ | |
| Initial boiling point | 260 |
| 50％ | 430 |
| 90％ | 525 |
| Final boiling point | 595 |
Table 4
| The first reactor process parameter | |
| Temperature of reaction, ℃ | 352 |
| The hydrogen dividing potential drop, MPa | 9.5 |
| Volume space velocity, h -1 | 3.7 |
| Hydrogen to oil volume ratio, v/v | 450 |
| The second reactor process parameter | |
| Temperature of reaction, ℃ | 375 |
| The hydrogen dividing potential drop, MPa | 9.5 |
| Volume space velocity, h -1 | 1.4 |
| Hydrogen to oil volume ratio, v/v | 650 |
| Product purification heavy distillate character |
| Density (20 ℃), g/cm 3 | 0.870 |
| Carbon residue, weight % | ＜0.1 |
| Total metal contents in soil, μ g/g | ＜0.1 |
| Sulphur content, μ g/g | 950 |
| Nitrogen content, μ g/g | 750 |
| Boiling range D-1160 ℃ | |
| Initial boiling point | 349 |
| 50％ | 426 |
| Final boiling point | 580 |
Claims (10)
1. hydroprocessing process of deep drawing wax oil that reduces pressure, it is characterized in that, decompression deep drawing wax oil and optional last running oil-hydrogen mixture pass through two hydroconversion reaction zones successively, filling hydrogenation protecting agent and the agent of hydrodemetallation (HDM) diasphaltene in first hydroconversion reaction zone, filling hydrogenating desulfurization agent and hydrodenitrification sweetening agent in second hydroconversion reaction zone, resultant of reaction obtain refining heavy distillate after refrigerated separation; With the first hydroconversion reaction zone integer catalyzer is benchmark, and the admission space ratio of the hydrogenation protecting agent of first hydroconversion reaction zone and the agent of hydrodemetallation (HDM) diasphaltene is 10～50: 50～90; With the second hydroconversion reaction zone integer catalyzer is benchmark, and the admission space ratio of the hydrogenating desulfurization agent of second hydroconversion reaction zone and hydrodenitrification sweetening agent is 10～30: 70～90.
2. in accordance with the method for claim 1, it is characterized in that the final boiling point of described decompression deep drawing wax oil is 550～610 ℃, asphalt content is 400 μ g/g～2500 μ g/g.
3. in accordance with the method for claim 1, it is characterized in that described heavy distillate is to be selected from vacuum distillate, coker gas oil and the deasphalted oil one or more.
4. in accordance with the method for claim 1, it is characterized in that the reaction conditions of described first hydroconversion reaction zone is that average bed temperature of reaction is 320～375 ℃, the hydrogen dividing potential drop is 5.0～11.0MPa, and hydrogen-oil ratio is 200～600Nm
3/ m
3, volume space velocity is 2.0～15.0h during liquid
-1
5. in accordance with the method for claim 1, it is characterized in that the reaction conditions of described second hydroconversion reaction zone is that average bed temperature of reaction is 355～430 ℃, the hydrogen dividing potential drop is 5.0～11.0MPa, and hydrogen-oil ratio is 300～1200Nm
3/ m
3, volume space velocity is 1.0～5.0h during liquid
-1
6. in accordance with the method for claim 1, it is characterized in that, the agent of described hydrodemetallation (HDM) diasphaltene contains a kind of alumina supporter and the molybdenum and/or the tungsten that load on this carrier, and nickel and/or cobalt metal component, the mean pore sizes of wherein said alumina supporter is 25～35nm, pore volume is 1.2～2.0ml/g, and specific surface area is 200～350m
2/ g.
7. in accordance with the method for claim 1, it is characterized in that described hydrogenating desulfurization agent is a metal load type catalyst, wherein carrier is aluminum oxide and optional silicon oxide, and reactive metal is cobalt and molybdenum.
8. in accordance with the method for claim 7, it is characterized in that the carrier of described hydrogenating desulfurization agent is an aluminum oxide, be benchmark with the gross weight of catalyzer, and in oxide compound, molybdenum is 8～20 weight %, and cobalt is 0.3～8 weight %.
9. in accordance with the method for claim 1, it is characterized in that described hydrodenitrification sweetening agent is a metal load type catalyst, wherein carrier is aluminum oxide and optional silicon oxide, and reactive metal is nickel, molybdenum and tungsten.
10. in accordance with the method for claim 1, it is characterized in that, described hydrodenitrification sweetening agent is to be fluorine-containing, the phosphorus hydrogenation catalyst of carrier with the silica-alumina, consisting of after this catalyzer roasting: nickel oxide 1～10 weight %, molybdenum oxide and Tungsten oxide 99.999 sum are 10～50 weight %, fluorine 1～10 weight %, phosphorus oxide 0.5～8 weight %, surplus is a silica-alumina.
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| CN102899081A (en) * | 2011-07-28 | 2013-01-30 | 中国石油化工股份有限公司 | Wax oil hydrotreating method |
| CN103074103A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Combined hydrotreating method |
| CN103131466A (en) * | 2011-11-25 | 2013-06-05 | 中国石油天然气股份有限公司 | Aromatic hydrocarbon-rich wax oil hydrotreating method |
| CN105524653A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Hydrotreatment method for residual oil |
| CN108003928A (en) * | 2016-11-01 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of Heavy oil hydrogenation method for improving catalyst utilization |
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| CN1202212C (en) * | 2002-10-10 | 2005-05-18 | 中国石油化工股份有限公司 | Heavy hydrocarbon hydroprocessing method |
| CN1990834B (en) * | 2005-12-30 | 2010-08-25 | 中国石油化工股份有限公司 | Residual oil hydroprocessing method |
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| CN102899081A (en) * | 2011-07-28 | 2013-01-30 | 中国石油化工股份有限公司 | Wax oil hydrotreating method |
| CN102899081B (en) * | 2011-07-28 | 2015-03-18 | 中国石油化工股份有限公司 | Wax oil hydrotreating method |
| CN103074103A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Combined hydrotreating method |
| CN103131466A (en) * | 2011-11-25 | 2013-06-05 | 中国石油天然气股份有限公司 | Aromatic hydrocarbon-rich wax oil hydrotreating method |
| CN105524653A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Hydrotreatment method for residual oil |
| CN105524653B (en) * | 2014-09-29 | 2017-05-24 | 中国石油化工股份有限公司 | Hydrotreatment method for residual oil |
| CN108003928A (en) * | 2016-11-01 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of Heavy oil hydrogenation method for improving catalyst utilization |
| CN108003928B (en) * | 2016-11-01 | 2020-02-14 | 中国石油化工股份有限公司 | Heavy oil hydrogenation method for improving catalyst utilization rate |
| RU2708252C1 (en) * | 2017-12-29 | 2019-12-05 | Чайна Петролиум энд Кемикал Корпорейшн | Method and apparatus for hydrogenating waxy oil |
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