CN105524655A - Heavy oil hydrodenitrogenation method - Google Patents
Heavy oil hydrodenitrogenation method Download PDFInfo
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Abstract
The invention discloses a heavy oil hydrodenitrogenation method. The heavy oil hydrodenitrogenation method comprises that under hydrotreatment conditions, in the presence of hydrogen, heavy oil-containing crude oil orderly contacts with a hydrodemetallization catalyst, a hydrodesulfurization catalyst, a hydrostturation catalyst and a hydro-denitrification catalyst so that hydrogenation product oil is obtained, wherein after contacting with the hydrodesulfurization catalyst and before contacting with the hydrostturation catalyst, the product obtained through contact with the hydrodesulfurization catalyst is subjected to gas stripping so that a liquid and gas containing hydrogen are obtained and the process of contact with the hydro-denitrification catalyst is carried out in the presence of a sulfur-containing material flow. The heavy oil hydrodenitrogenation method can substantially improve a heavy oil denitrification rate and a heavy oil hydrogenation rate, improve a liquid product yield in heavy oil hydrogenation and saves a production cost.
Description
Technical field
The present invention relates to a kind of method of heavy-oil hydrogenation denitrogenation.
Background technology
Residual hydrogenation technology is a kind of Heavy Oil Processing Technology of high liquid product yield, obtains Rapid Popularization at present in China.The catalytic cracking that residual hydrogenation equipment is mainly downstream provides the raw material of lower impurity (sulphur, nitrogen, metal etc.) content and low carbon residue, effectively improves yield of light oil and the product property of refinery.The nitrogen content of the generation oil in Residue Hydrotreating Technology is an important indicator, the too high acid sites poisoning and deactivation easily making catalytic cracking catalyst of nitrogen content, causes green coke amount to increase, degradation series of problems under liquid product yield.
Nitrogenous compound in oil is mainly nitrogenous heterogeneous ring compound, and along with the increase of petroleum fractions boiling range, the content of nitride increases.And residual oil is enriched nitrogenous compounds a large amount of in oil, these nitrogenous compounds mainly with pyrroles and pyridine for elementary cell, and the macromolecular cpd of upper multiple phenyl ring, naphthenic hydrocarbon and stable hydrocarbon side chain.Carrying out hydrodenitrification in hydroprocessing processes at residual oil is the reaction process of a multi-step, first hydrotreated lube base oil, the hydrogenation ring-opening reaction of outside aromatic ring is there is in nitrogenous compound under the effect of catalyzer, then just nitrogenous heterocyclic hydrotreated lube base oil can be carried out, finally there is the hydrogenolysis of C-N key, generate corresponding hydro carbons and ammonia.
The means that current fixed bed Residue Hydrotreating Technology improves denitrification percent are mainly the highly active residual hydrogenation denitrification catalyst of replacing.Such as, the prior aries such as CN1448470A, CN1339562A, CN1070418A, CN1086534A, CN101890383A, CN103627424A, US3446730A, US3444074A, US4522709A and US4406779A propose the Catalysts and its preparation method etc. being applied to heavy oil or residual hydrogenation process, can reach by using above-mentioned catalyzer described in the prior art in fixed bed residual hydrogenation reactor the method improving residual hydrogenation denitrification percent.
But, because the nitrogen content in hydrotreated feed oil is high, even also only good catalytic activity can be maintained within for some time that reactor has just been brought into use when using the catalyzer of above-mentioned prior art to carry out denitrogenation, along with duration of service extends, the catalytic activity of above-mentioned catalyzer declines more serious, thus make just to need more catalyst changeout within the shorter cycle, seriously add production cost.
Summary of the invention
The object of this invention is to provide a kind of method with high heavy-oil hydrogenation denitrification percent, the method can improve heavy-oil hydrogenation rate while significantly improving heavy oil denitrification percent, improves the yield of the product liquid in heavy-oil hydrogenation process, and then saves production cost.
To achieve these goals, the invention provides a kind of method of heavy-oil hydrogenation denitrogenation, the method comprises: under hydroprocessing conditions, in presence of hydrogen, stock oil containing heavy oil is contacted with hydrodenitrogenation catalyst with Hydrodemetalation catalyst, Hydrobon catalyst, hydrocatalyst for saturating successively, obtains hydrogenated oil; Wherein, after contacting with Hydrobon catalyst and before contacting with hydrocatalyst for saturating, the product obtained after contacting with Hydrobon catalyst is carried out air lift, obtain liquid phase thing and the gas gas-phase objects containing hydrogen, the process contacted with hydrodenitrogenation catalyst is carried out under sulfur-bearing logistics exists.
The present invention is on the basis of existing heavy-oil hydrogenation treatment process, by material being carried out after contacting with Hydrobon catalyst and before contacting with hydrocatalyst for saturating air lift to remove sulfocompound (such as hydrogen sulfide), and the method injecting sulfur-bearing logistics in hydrodenitrification effectively can reduce the nitrogen content of hydrogenated oil, improve the yield of the product liquid in heavy-oil hydrogenation process, and then save production cost.The high hydrogenated oil of this denitrification percent is made to be of value to follow-up catalytic cracking process further.As can be seen from the result of embodiments of the invention, under the prerequisite that all the other conditions are identical, the result of comparative example 1 and embodiment 4, when the content that the sulfur-bearing logistics used in hydrodenitrification reaction zone in embodiment 1 makes hydrogen sulfide is 2 % by weight, denitrification percent is than the height in embodiment 4.And method of the present invention to the nitrogen content in the kind of the kind of catalyzer, filling method, stock oil and stock oil, all there is no particular limitation, adopt the denitrification percent of method of the present invention all more than more than 50 % by weight, denitrification percent is obviously compared with the height in comparative example.And method of the present invention particularly has very high nitric efficiency for the stock oil with high nitrogen-containing; And the method for prior art often cannot make the nitrogen content had in the raw material of high nitrogen-containing significantly reduce.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the process flow sheet carrying out residual hydrogenation denitrogenation according to the method for embodiments of the invention 1.
Fig. 2 is the process flow sheet carrying out residual hydrogenation denitrogenation according to the method for comparative example 1 of the present invention.
Fig. 3 is the process flow sheet carrying out residual hydrogenation denitrogenation according to the method for comparative example 2 of the present invention.
Fig. 4 is the process flow sheet carrying out residual hydrogenation denitrogenation according to the method for comparative example 3 of the present invention.
Description of reference numerals
II hydrodemetallation (HDM) reaction zone, I hydrodemetallation (HDM) reaction zone
III high pressure air lift district IV hydrotreated lube base oil reaction zone
VI gas-oil separation district, V hydrodenitrification reaction zone
VII desulphurization of recycle hydrogen district VII-1 not sulfur-bearing circulating hydrogen compressor
VII-2 notes sulphur oil pump III-1 hydrogen make-up compressor
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of method of heavy-oil hydrogenation denitrogenation, the method comprises: under hydroprocessing conditions, in presence of hydrogen, stock oil containing heavy oil is contacted with hydrodenitrogenation catalyst with Hydrodemetalation catalyst, Hydrobon catalyst, hydrocatalyst for saturating successively, obtains hydrogenated oil; Wherein, after contacting with Hydrobon catalyst and before contacting with hydrocatalyst for saturating, the product obtained after contacting with Hydrobon catalyst is carried out air lift, obtain liquid phase thing and the gas gas-phase objects containing hydrogen, the process contacted with hydrodenitrogenation catalyst is carried out under sulfur-bearing logistics exists.
In method of the present invention, it should be noted that, when stock oil containing heavy oil contacts with hydrodenitrogenation catalyst with Hydrodemetalation catalyst, Hydrobon catalyst, hydrocatalyst for saturating successively, the main reaction occurred is hydrodemetallation (HDM) reaction, hydrodesulfurization reaction, hydrotreated lube base oil reaction and hydrodenitrification reaction respectively.But, under hydroprocessing conditions, in the process that the stock oil containing heavy oil contacts with Hydrodemetalation catalyst, also have a small amount of hydrotreated lube base oil reaction and hydrodesulfurization reaction generation; In the process contacted with Hydrobon catalyst, also have a small amount of hydrodemetallation (HDM) reaction and hydrotreated lube base oil reaction generation.To this, those skilled in the art know, and the present invention does not describe in detail.
According to method of the present invention, to the stock oil containing heavy oil successively with Hydrodemetalation catalyst, Hydrobon catalyst, there is no particular limitation for the form that hydrocatalyst for saturating contacts with hydrodenitrogenation catalyst, under preferable case, in the present invention, the process contacted with hydrodenitrogenation catalyst comprises: described sulfur-bearing logistics is introduced the hydrodenitrification reaction zone containing described hydrodenitrogenation catalyst, sulfur-bearing logistics produces hydrogen sulfide under hydroprocessing conditions, make under hydrogen sulfide exists, the product obtained after contacting with hydrocatalyst for saturating contacts with described hydrodenitrogenation catalyst and hydrodenitrification occurs reacts.
According to method of the present invention, the described process contacted with hydrodenitrogenation catalyst can be carried out in the hydrodenitrification reaction zone containing described hydrodenitrogenation catalyst.
According to method of the present invention, the consumption of preferred described sulfur-bearing logistics makes the hydrogen sulfide containing 0.1-20 weight part in the gas gas-phase objects of the hydrodenitrification reaction zone of every 100 weight parts, the hydrogen sulfide more preferably containing 1-5 weight part.Also be, in method of the present invention, in material and hydrodenitrogenation catalyst contact process, relative to the gas gas-phase objects in the region contacted with hydrodenitrogenation catalyst of 100 weight parts (in the present invention, this gas gas-phase objects comprises hydrocarbons and non-hydrocarbonaceous materials, and non-hydrocarbonaceous materials mainly comprises hydrogen, hydrogen sulfide and ammonia etc.), the consumption of described sulfur-bearing logistics is the content of hydrogen sulfide in the gas gas-phase objects in the region making to contact with hydrodenitrogenation catalyst is 0.1-20 weight part; In order to advantageously in hydrodenitrification and prevent hydrodenitrogenation catalyst life cycle too short, the content of preferred sulfocompound is 1-5 weight part.The content of the hydrogen sulfide in the gas gas-phase objects that those skilled in the art can adopt the technique means of various routine to detect in the region contacted with hydrodenitrogenation catalyst, method of the present invention is not limited to this.
According to method of the present invention, to the kind of described sulfur-bearing logistics, there is no particular limitation, as long as can hydrogen sulfide be produced under hydroprocessing conditions, and can containing materials such as dithiocarbonic anhydride in described sulfur-bearing logistics.Under preferable case, make denitrification percent higher to obtain, described sulfur-bearing logistics of the present invention comprises dithiocarbonic anhydride, dimethyl disulfide and derivative thereof, dimethyl disulfide and derivative thereof, organic polythiaether and derivative, mercaptan and derivative thereof, thiophene and derivatives, straight-run diesel oil, decompressed wax oil, catalytic diesel oil, catalytic cycle oil, catalytic slurry steam oil, coker gas oil, wax tailings, deasphalted oil and solvent treatment and extract at least one in oil out.Being more preferably described sulfur-bearing logistics is at least one in dithiocarbonic anhydride, dimethyl disulfide, straight-run diesel oil, decompressed wax oil, catalytic diesel oil and catalytic cycle oil.
In method of the present invention, to the introducing method of described sulfur-bearing logistics, there is no particular limitation, and those skilled in the art can adopt the conventional various methods used that hydrodenitrification reaction zone is introduced in described sulfur-bearing logistics.Such as in method of the present invention, can adopt note sulphur oil pump etc. that hydrodenitrification reaction zone is introduced in described sulfur-bearing logistics.
In method of the present invention, to described method of carrying out air lift, there is no particular limitation, under preferable case, in method of the present invention, in order to improve hydrogen-oil ratio and be conducive to carrying out air lift, described air lift is carried out under the existence of hydrogen make-up, and the existence of hydrogen make-up also helps carries out hydrotreated lube base oil reaction further.Particularly, according to method of the present invention, described in carry out air lift method comprise: under the existence of hydrogen make-up, the product obtained after contacting is introduced air lift district carry out air lift with Hydrobon catalyst.In the present invention, to the consumption of described hydrogen make-up, there is no particular limitation, as long as the consumption of described hydrogen make-up can make the pressure in the reactor of described hydrotreatment remain basicly stable, such as, the hydrogen dividing potential drop in the reactor of described hydrotreatment is made to maintain between 5.0-22.0MPa.And, in order to easy and simple to handle, described air lift of the present invention adopts the method for directly the product introducing air lift district obtained after contact with Hydrobon catalyst being carried out high pressure air lift to carry out, and need not to described to contact with Hydrobon catalyst after the product that obtains reduce pressure or process of lowering the temperature.The temperature and pressure in described air lift district maintains within the scope of hydroprocessing condition, and such as temperature is 330-450 DEG C, and hydrogen dividing potential drop is 5.0-22.0MPa.
In method of the present invention, the product obtained by air lift is divided into liquid phase thing and the gas gas-phase objects containing hydrogen, wherein, the liquid phase thing obtained after air lift proceeds hydrotreatment, and the gas gas-phase objects obtained is the mixture containing hydrogen, ammonia and hydrogen sulfide etc.In the method for the invention, can also comprise and being separated described gas phase mixture, obtain the hydrogen of not sulfur-bearing, the hydrogen of described not sulfur-bearing can be introduced in the hydrogenation process of heavy oil for the hydrogenation reaction that circulates by compressor.
In the method for the invention, described air lift process is carried out under the existence of hydrogen make-up, and described hydrogen make-up can introduce air lift process by compressor.
According to method of the present invention, to the condition of described hydrotreatment, there is no particular limitation, the hydroprocessing condition that those skilled in the art can adopt this area routine to use carries out hydrotreatment to heavy oil, but, under preferable case, in order to obtain higher hydrodenitrification rate, the hydroprocessing condition in method of the present invention can comprise: hydrogen dividing potential drop is 5.0-22.0MPa, temperature of reaction is 330-450 DEG C, volume space velocity is 0.1-3.0h
-1, hydrogen and stock oil volume ratio be 350-2000:1.
According to method of the present invention, preferably described contact with Hydrodemetalation catalyst, Hydrobon catalyst, hydrocatalyst for saturating and hydrodenitrogenation catalyst respectively in the hydrodemetallation (HDM) reaction zone containing Hydrodemetalation catalyst, the hydrodesulfurizationreaction reaction zone containing Hydrobon catalyst, the hydrotreated lube base oil reaction zone containing hydrocatalyst for saturating and the hydrodenitrification reaction zone of containing hydrodenitrogenation catalyst carry out.
In the present invention, described hydrodemetallation (HDM) reaction zone can be a bed of a reactor, also can be multiple beds of a reactor, can also be multiple beds of multiple reactor.
In the present invention, described hydrodesulfurizationreaction reaction zone can be a bed of a reactor, also can be multiple beds of a reactor, can also be multiple beds of multiple reactor.
In the present invention, described hydrotreated lube base oil reaction zone can be a bed of a reactor, also can be multiple beds of a reactor, can also be multiple beds of multiple reactor.
In the present invention, described hydrodenitrification reaction zone can be a bed of a reactor, also can be multiple beds of a reactor, can also be multiple beds of multiple reactor.
More preferably in situation, according to method of the present invention, described hydrodemetallation (HDM) reaction zone, hydrodesulfurizationreaction reaction zone, hydrotreated lube base oil reaction zone and hydrodenitrification reaction zone comprise at least one hydrogenator respectively; More preferably 1-5 hydrogenator is comprised respectively.
Under preferable case, according to method of the present invention, described hydrodemetallation (HDM) reaction zone, hydrodesulfurizationreaction reaction zone, hydrotreated lube base oil reaction zone and hydrodenitrification reaction zone comprise at least one beds respectively; More preferably comprise 1-5 beds respectively, wherein 1-5 beds can arrange and also can be arranged in different reactors separately in a reactor.
In method of the present invention, to the type of described hydrogenator, there is no particular limitation, and under under preferable case, described hydrogenator comprises at least one in fixed bed, moving-bed and ebullated bed, is more preferably fixed bed.
In method of the present invention, described hydrodemetallation (HDM) reaction zone can only use a kind of catalyzer, also can use multiple catalysts, multiple catalysts grating usually can be adopted to use for fixed bed hydrogenation reactor.
In method of the present invention, described hydrodesulfurizationreaction reaction zone can only use a kind of catalyzer, also can use multiple catalysts, multiple catalysts grating usually can be adopted to use for fixed bed hydrogenation reactor.
In method of the present invention, described hydrotreated lube base oil reaction zone can only use a kind of catalyzer, also can use multiple catalysts; Described hydrodenitrification reaction zone can only use a kind of catalyzer, also can use multiple catalysts.
In method of the present invention, to the kind of one or more catalyzer of above-mentioned use, there is no particular limitation.
In method of the present invention, the Hydrodemetalation catalyst, Hydrobon catalyst and the hydrodenitrogenation catalyst that load in described hydrodemetallation (HDM) reaction zone, hydrodesulfurizationreaction reaction zone and hydrodenitrification reaction zone are conventional hydrogenation catalyst kind, known by professional and technical personnel in the field, do not describe in detail at this.
In method of the present invention, residual hydrogenation saturation catalyst can be loaded in described hydrotreated lube base oil reaction zone, its active metal component can be at least one in nickel-molybdenum, nickel-cobalt-molybdenum, nickel-tungsten and nickel-cobalt-tungsten, is wherein more preferably at least one in nickel-molybdenum, nickel-tungsten and nickel-cobalt-molybdenum; Active metal charge capacity can be: molybdenum and/or tungsten 5-40 % by weight, cobalt and/or nickel 1-8 % by weight.The residual hydrogenation saturation catalyst loaded in described hydrotreated lube base oil reaction zone, its carrier can be at least one in aluminum oxide, silicon-dioxide and amorphous silicon aluminium, is wherein more preferably aluminum oxide.The residual hydrogenation saturation catalyst loaded in described hydrotreated lube base oil reaction zone, its specific surface area can be 100-300 rice
2/ gram, its pore volume can be 0.2-0.8 ml/g.
In method of the present invention, to the filling method of one or more catalyzer above-mentioned, there is no particular limitation, and those skilled in the art can adopt the conventional various filling methods used.
In method of the present invention, preferred described heavy oil comprises at least one in long residuum and vacuum residuum.
In method of the present invention, in described stock oil, distillate can also be contained.
Under preferable case, in method of the present invention, described distillate comprises decompressed wax oil, catalytically cracked oil steams oil, catalytic cracking turning oil, wax tailings, deasphalted oil, solvent treatment extract out oil and liquefied coal coil at least one.
Method of the present invention is applicable to the stock oil with various nitrogen content, and wherein, under preferable case, in the stock oil in method of the present invention, nitrogen content is not less than 3000 μ g/g; More preferably, in situation, in described stock oil, nitrogen content is 3000-8000 μ g/g.
In method of the present invention, can also comprise and the product obtained after contacting with hydrodenitrogenation catalyst is carried out gas-oil separation to obtain hydrogenated oil of the present invention.The method of described gas-oil separation is conventionally known to one of skill in the art, such as, can adopt the product obtained after contacting with hydrodenitrogenation catalyst is introduced gas-oil separation district to carry out gas-oil separation, obtains hydrogenated oil.
According to one of the present invention preferred embodiment, heavy-oil hydrogenation denitrogenation of the present invention can adopt following methods to carry out:
(1) in presence of hydrogen, the stock oil containing heavy oil is introduced hydrodemetallation (HDM) reaction zone, contacts with Hydrodemetalation catalyst, hydrodemetallation (HDM) reaction occurs, obtain hydrodemetallation (HDM) reaction zone and generate oil and gas;
(2) the hydrodemetallation (HDM) reaction zone obtained in step (1) is generated oil and introduce hydrodesulfurizationreaction reaction zone with gas, contact with Hydrobon catalyst, hydrodesulfurization reaction occurs, obtain hydrodesulfurizationreaction reaction zone and generate oil and gas;
(3) under the existence of hydrogen make-up, the hydrodesulfurizationreaction reaction zone obtained in step (2) is generated oil and introduces air lift district with gas, oil is generated to described hydrodesulfurizationreaction reaction zone and carries out air lift, and carry out gas-liquid separation, obtain liquid phase thing and the gas gas-phase objects containing hydrogen;
(4) the liquid phase thing obtained in hydrogen and step (3) is introduced hydrotreated lube base oil reaction zone, contact with hydrocatalyst for saturating, hydrotreated lube base oil reaction occurs, obtain hydrotreated lube base oil reaction zone generation oil gentle;
(5) under the existence of sulfur-bearing logistics, the hydrotreated lube base oil reaction zone obtained in step (4) is generated oily gentle introducing hydrodenitrification reaction zone, contact with hydrodenitrogenation catalyst, generation hydrodenitrification is reacted, obtain hydrodenitrification reaction zone and generate oil and gas, then carry out gas-oil separation, obtain hydrogenated oil.
It should be noted that, of the present invention above-mentioned preferred embodiment in, involved various parameter and condition all can as shown in foregoing teachings of the present invention, and the present invention does not repeat them here.
According to hydrogenated oil of the present invention, nitrogen content wherein reduces by more than 50 % by weight compared with the nitrogen content in stock oil.
Below will be described the present invention by embodiment, but not thereby limiting the invention.Embodiment and the hydrodemetallation (HDM) reaction zone described in comparative example, hydrodesulfurizationreaction reaction zone, hydrotreated lube base oil reaction zone, hydrodenitrification reaction zone are all respectively a reactor, the reactor used is fixed-bed reactor, and each reactor only has a beds.The RHT series residual oil hydrocatalyst that the catalyzer used in embodiment and comparative example is the exploitation of Sinopec Research Institute of Petro-Chemical Engineering, produced by Sinopec catalyzer Chang Ling branch office.The sulfur-bearing logistics used in embodiment and comparative example is the catalytic diesel oil containing 2 % by weight dithiocarbonic anhydride.
Hydrogen-oil ratio in following examples and comparative example refers to the volume ratio of hydrogen and stock oil.
Embodiment 1
The stock oil that the present embodiment uses is long residuum, and its character is as shown in table 1.The filling scheme of the catalyzer used in the present embodiment is as shown in table 2.The process flow sheet that the present embodiment adopts is shown in Fig. 1.Idiographic flow is:
(1) stock oil from pipeline 1 mixes with the not hydrogen sulfide containing circulating hydrogen from pipeline 3, enter hydrodemetallation (HDM) reaction zone I, contact with Hydrodemetalation catalyst, the reaction of generation hydrodemetallation (HDM) and a small amount of hydrotreated lube base oil react and hydrodesulfurization reaction, obtain hydrodemetallation (HDM) reaction zone and generate oil and gas;
(2) the hydrodemetallation (HDM) reaction zone obtained in step (1) is generated oil and enter hydrodesulfurizationreaction reaction zone II with gas through pipeline 4, contact with Hydrobon catalyst, there is hydrodesulfurization reaction and the reaction of a small amount of hydrodemetallation (HDM) and hydrotreated lube base oil to react, obtain hydrodesulfurizationreaction reaction zone and generate oil and gas;
(3) hydrodesulfurizationreaction reaction zone obtained in step (2) is generated oil and enter high pressure air lift district III with gas through pipeline 5, from pipeline 2 hydrogen make-up through hydrogen make-up compressor III-1 boost after, generate oil through pipeline 6 pairs of hydrodesulfurizationreaction reaction zone and carry out air lift, there is liquid phase sepn process in high pressure air lift district simultaneously, obtain liquid phase thing and the gas gas-phase objects containing hydrogen;
(4) gas phase after the separation of high pressure air lift district III liquid phase enters desulphurization of recycle hydrogen district VII through pipeline 7, oil phase enters hydrotreated lube base oil reaction zone IV after pipeline 8 mixes with the not hydrogen sulfide containing circulating hydrogen from pipeline 9, contact with hydrocatalyst for saturating, generation hydrotreated lube base oil reacts, and obtains hydrotreated lube base oil reaction zone generation oil gentle;
(5) the hydrotreated lube base oil reaction zone obtained in step (4) is generated oil gentle through pipeline 10 be mixed into hydrodenitrification reaction zone V through pipeline 16, the sulfur-bearing logistics of noting sulphur oil pump VII-2 and pipeline 11 successively, contact with hydrodenitrogenation catalyst, generation hydrodenitrification is reacted, and obtains hydrodenitrification reaction zone and generates oil and gas;
(6) the hydrodenitrification reaction zone obtained in step (5) generation oil is entered gas-oil separation district VI with gas through pipeline 12 and carry out gas-oil separation, obtain hydrogenated oil, described hydrogenated oil flows out through pipeline 13, the gas gas-phase objects obtained after gas-oil separation enters desulphurization of recycle hydrogen district VII through pipeline 14 and is separated, waste gas etc. are discharged through pipeline 17, the hydrogen of the not sulfur-bearing obtained enters hydrodemetallation (HDM) reaction zone I through pipeline 15, not sulfur-bearing circulating hydrogen compressor VII-1 and pipeline 3 successively, or enters hydrotreated lube base oil reaction zone IV through pipeline 9.
Test conditions is: hydrodemetallation (HDM) reaction zone entrance hydrogen dividing potential drop is 15.0MPa; Hydrodemetallation (HDM) reaction zone temperature in is 350 DEG C, hydrodesulfurizationreaction reaction zone temperature in is 365 DEG C, hydrotreated lube base oil reaction zone temperature in is 365 DEG C, hydrodenitrification reaction zone temperature in is 375 DEG C, and the volume space velocity in hydroprocessing processes is 0.25h
-1; Hydrodemetallation (HDM) reaction zone entrance hydrogen-oil ratio is 800:1, and hydrotreated lube base oil reaction zone entrance hydrogen-oil ratio is 800:1.In control hydrodenitrification reaction zone, in gas gas-phase objects, hydrogen sulfide content is 2 % by weight.
The character of the hydrogenated oil adopting the aforesaid method of the present embodiment to obtain is in table 3.As can be seen from the present embodiment, the nitrogen content in the hydrogenated oil adopting the method for the present embodiment to obtain reduces 70.6 % by weight compared with the nitrogen content in stock oil.
Table 1
| Analysis project | Long residuum |
| Density (20 DEG C)/(kg/m 3) | 976.0 |
| Viscosity (100 DEG C)/(mm 2/s) | 174.3 |
| Carbon residue/% | 11.72 |
| Carbon content/% | 86.54 |
| Hydrogen richness/% | 11.31 |
| Sulphur content/% | 1.19 |
| Nitrogen content/% | 0.51 |
| Saturated point/% | 28.1 |
| Fragrance divides/% | 36.7 |
| Colloid/% | 32.2 |
| Bituminous matter/% | 3.0 |
| Nickel content/(μ g/g) | 36.6 |
| Content of vanadium/(μ g/g) | 19.2 |
Table 2
Table 3
Comparative example 1
The stock oil that this comparative example uses is in the same manner as in Example 1.The filling scheme of the catalyzer used in this comparative example is in the same manner as in Example 1.The process flow sheet that this comparative example adopts is shown in Fig. 2.Idiographic flow is:
(1) from the stock oil of pipeline 1 with the not hydrogen sulfide containing circulating hydrogen from pipeline 3 with mix through the hydrogen of pipeline 2 and hydrogen make-up compressor III-1, enter hydrodemetallation (HDM) reaction zone I, contact with Hydrodemetalation catalyst, the reaction of generation hydrodemetallation (HDM) and a small amount of hydrotreated lube base oil react and hydrodesulfurization reaction, obtain hydrodemetallation (HDM) reaction zone and generate oil and gas;
(2) the hydrodemetallation (HDM) reaction zone obtained in step (1) is generated oil and enter hydrodesulfurizationreaction reaction zone II with gas through pipeline 4, contact with Hydrobon catalyst, there is hydrodesulfurization reaction and the reaction of a small amount of hydrodemetallation (HDM) and hydrotreated lube base oil to react, obtain hydrodesulfurizationreaction reaction zone and generate oil and gas;
(3) hydrodesulfurizationreaction reaction zone obtained in step (2) generation oil is entered hydrotreated lube base oil reaction zone IV with gas through pipeline 8, contact with hydrocatalyst for saturating, hydrotreated lube base oil reaction occurs, obtain hydrotreated lube base oil reaction zone generation oil gentle;
(4) enter hydrodenitrification reaction zone V by gentle for the hydrotreated lube base oil reaction zone obtained in step (3) generation oil through pipeline 10, contact with hydrodenitrogenation catalyst, hydrodenitrification reaction occurs, obtain hydrodenitrification reaction zone and generate oily and gas;
(5) the hydrodenitrification reaction zone obtained in step (4) generation oil is entered gas-oil separation district VI with gas through pipeline 12 and carry out gas-oil separation, obtain hydrogenated oil, described hydrogenated oil flows out through pipeline 13, the gas gas-phase objects obtained after gas-oil separation enters desulphurization of recycle hydrogen district VII through pipeline 14 and is separated, waste gas is discharged through pipeline 17, and the hydrogen of the not sulfur-bearing obtained enters hydrodemetallation (HDM) reaction zone I through pipeline 15, not sulfur-bearing circulating hydrogen compressor VII-1 and pipeline 3 successively.
Test conditions is: hydrodemetallation (HDM) reaction zone entrance hydrogen dividing potential drop is 15.0MPa; Hydrodemetallation (HDM) reaction zone temperature in is 350 DEG C, hydrodesulfurizationreaction reaction zone temperature in is 365 DEG C, hydrotreated lube base oil reaction zone temperature in is 365 DEG C, hydrodenitrification reaction zone temperature in is 375 DEG C, and the volume space velocity in hydroprocessing processes is 0.25h
-1; Hydrodemetallation (HDM) reaction zone entrance hydrogen-oil ratio is 800:1, hydrotreated lube base oil reaction zone entrance hydrogen-oil ratio is 800:1.
The character of the hydrogenated oil adopting the aforesaid method of this comparative example to obtain is in table 3.As can be seen from this comparative example, the nitrogen content in the hydrogenated oil adopting the method for this comparative example to obtain reduces 29.4 % by weight compared with the nitrogen content in stock oil.
Comparative example 2
The stock oil that this comparative example uses is in the same manner as in Example 1.The filling scheme of the catalyzer used in this comparative example is in the same manner as in Example 1.The process flow sheet that this comparative example adopts is shown in Fig. 3.Idiographic flow is:
(1) stock oil from pipeline 1 mixes with the not hydrogen sulfide containing circulating hydrogen from pipeline 3, enter hydrodemetallation (HDM) reaction zone I, contact with Hydrodemetalation catalyst, the reaction of generation hydrodemetallation (HDM) and a small amount of hydrotreated lube base oil react and hydrodesulfurization reaction, obtain hydrodemetallation (HDM) reaction zone and generate oil and gas;
(2) the hydrodemetallation (HDM) reaction zone obtained in step (1) is generated oil and enter hydrodesulfurizationreaction reaction zone II with gas through pipeline 4, contact with Hydrobon catalyst, there is hydrodesulfurization reaction and the reaction of a small amount of hydrodemetallation (HDM) and hydrotreated lube base oil to react, obtain hydrodesulfurizationreaction reaction zone and generate oil and gas;
(3) hydrodesulfurizationreaction reaction zone obtained in step (2) is generated oil and enter high pressure air lift district III with gas through pipeline 5, from pipeline 2 hydrogen make-up through hydrogen make-up compressor III-1 boost after, generate oil through pipeline 6 pairs of hydrodesulfurizationreaction reaction zone and carry out air lift, there is liquid phase sepn process in high pressure air lift district simultaneously, obtain liquid phase thing and the gas gas-phase objects containing hydrogen;
(4) gas phase after the separation of high pressure air lift district III liquid phase enters desulphurization of recycle hydrogen district VII through pipeline 7, oil phase enters hydrotreated lube base oil reaction zone IV after pipeline 8 mixes with the not hydrogen sulfide containing circulating hydrogen from pipeline 9, contact with hydrocatalyst for saturating, generation hydrotreated lube base oil reacts, and obtains hydrotreated lube base oil reaction zone generation oil gentle;
(5) enter hydrodenitrification reaction zone V by gentle for the hydrotreated lube base oil reaction zone obtained in step (4) generation oil through pipeline 10, contact with hydrodenitrogenation catalyst, hydrodenitrification reaction occurs, obtain hydrodenitrification reaction zone and generate oily and gas;
(6) the hydrodenitrification reaction zone obtained in step (5) generation oil is entered gas-oil separation district VI with gas through pipeline 12 and carry out gas-oil separation, obtain hydrogenated oil, described hydrogenated oil flows out through pipeline 13, the gas gas-phase objects obtained after gas-oil separation enters desulphurization of recycle hydrogen district VII through pipeline 14 and is separated, waste gas is discharged through pipeline 17, the hydrogen of the not sulfur-bearing obtained enters hydrodemetallation (HDM) reaction zone I through pipeline 15, not sulfur-bearing circulating hydrogen compressor VII-1 and pipeline 3 successively, or enters hydrotreated lube base oil reaction zone IV through pipeline 9.
Test conditions is: hydrodemetallation (HDM) reaction zone entrance hydrogen dividing potential drop is 15.0MPa; Hydrodemetallation (HDM) reaction zone temperature in is 350 DEG C, hydrodesulfurizationreaction reaction zone temperature in is 365 DEG C, hydrotreated lube base oil reaction zone temperature in is 365 DEG C, hydrodenitrification reaction zone temperature in is 375 DEG C, and the volume space velocity in hydroprocessing processes is 0.25h
-1; Hydrodemetallation (HDM) reaction zone entrance hydrogen-oil ratio is 800:1, hydrotreated lube base oil reaction zone entrance hydrogen-oil ratio is 800:1.
The character of the hydrogenated oil adopting the aforesaid method of this comparative example to obtain is in table 3.As can be seen from this comparative example, the nitrogen content in the hydrogenated oil adopting the method for this comparative example to obtain reduces 31.4 % by weight compared with the nitrogen content in stock oil.
Comparative example 3
The stock oil that this comparative example uses is in the same manner as in Example 1.The filling scheme of the catalyzer used in this comparative example is in the same manner as in Example 1.The process flow sheet that this comparative example adopts is shown in Fig. 4.Idiographic flow is:
(1) stock oil from pipeline 1 mixes with the not hydrogen sulfide containing circulating hydrogen from pipeline 3 and the hydrogen from pipeline 2 and through hydrogen make-up compressor III-1, enter hydrodemetallation (HDM) reaction zone I, contact with Hydrodemetalation catalyst, the reaction of generation hydrodemetallation (HDM) and a small amount of hydrotreated lube base oil react and hydrodesulfurization reaction, obtain hydrodemetallation (HDM) reaction zone and generate oil and gas;
(2) the hydrodemetallation (HDM) reaction zone obtained in step (1) is generated oil and enter hydrodesulfurizationreaction reaction zone II with gas through pipeline 4, contact with Hydrobon catalyst, there is hydrodesulfurization reaction and the reaction of a small amount of hydrodemetallation (HDM) and hydrotreated lube base oil to react, obtain hydrodesulfurizationreaction reaction zone and generate oil and gas;
(3) hydrodesulfurizationreaction reaction zone obtained in step (2) generation oil is entered hydrotreated lube base oil reaction zone IV with gas through pipeline 8, contact with hydrocatalyst for saturating, hydrotreated lube base oil reaction occurs, obtain hydrotreated lube base oil reaction zone generation oil gentle;
(4) the hydrotreated lube base oil reaction zone obtained in step (3) is generated oil gentle through pipeline 10 be mixed into hydrodenitrification reaction zone V through pipeline 16, the sulfur-bearing logistics of noting sulphur oil pump VII-2 and pipeline 11 successively, contact with hydrodenitrogenation catalyst, generation hydrodenitrification is reacted, and obtains hydrodenitrification reaction zone and generates oil and gas;
(5) the hydrodenitrification reaction zone obtained in step (4) generation oil is entered gas-oil separation district VI with gas through pipeline 12 and carry out gas-oil separation, obtain hydrogenated oil, described hydrogenated oil flows out through pipeline 13, the gas gas-phase objects obtained after gas-oil separation enters desulphurization of recycle hydrogen district VII through pipeline 14 and is separated, waste gas etc. are discharged through pipeline 17, and the hydrogen of the not sulfur-bearing obtained enters hydrodemetallation (HDM) reaction zone I through pipeline 15, not sulfur-bearing circulating hydrogen compressor VII-1 and pipeline 3 successively.
Test conditions is: hydrodemetallation (HDM) reaction zone entrance hydrogen dividing potential drop is 15.0MPa; Hydrodemetallation (HDM) reaction zone temperature in is 350 DEG C, hydrodesulfurizationreaction reaction zone temperature in is 365 DEG C, hydrotreated lube base oil reaction zone temperature in is 365 DEG C, hydrodenitrification reaction zone temperature in is 375 DEG C, and the volume space velocity in hydroprocessing processes is 0.25h
-1; Hydrodemetallation (HDM) reaction zone entrance hydrogen-oil ratio is 800:1, hydrotreated lube base oil reaction zone entrance hydrogen-oil ratio is 800:1.In control hydrodenitrification reaction zone, in gas gas-phase objects, hydrogen sulfide content is 2 % by weight.
The character of the hydrogenated oil adopting the aforesaid method of this comparative example to obtain is in table 3.As can be seen from this comparative example, the nitrogen content in the hydrogenated oil adopting the method for this comparative example to obtain reduces 29.4 % by weight compared with the nitrogen content in stock oil.
Embodiment 2
The present embodiment adopts the method identical with embodiment 1 to carry out, and difference is:
Test conditions is: hydrodemetallation (HDM) reaction zone entrance hydrogen dividing potential drop is 18.0MPa; Hydrodemetallation (HDM) reaction zone temperature in is 360 DEG C, hydrodesulfurizationreaction reaction zone temperature in is 375 DEG C, hydrotreated lube base oil reaction zone temperature in is 370 DEG C, hydrodenitrification reaction zone temperature in is 380 DEG C, and the volume space velocity in hydroprocessing processes is 0.5h
-1; Hydrodemetallation (HDM) reaction zone entrance hydrogen-oil ratio is 1000:1, and hydrotreated lube base oil reaction zone entrance hydrogen-oil ratio is 1000:1.In control hydrodenitrification reaction zone, in gas gas-phase objects, hydrogen sulfide content is 1 % by weight.
The character of the hydrogenated oil adopting the aforesaid method of the present embodiment to obtain is in table 3.As can be seen from the present embodiment, the nitrogen content in the hydrogenated oil adopting the method for the present embodiment to obtain reduces 68.6 % by weight compared with the nitrogen content in stock oil.
Embodiment 3
The present embodiment adopts the method identical with embodiment 1 to carry out, and difference is:
Test conditions is: hydrodemetallation (HDM) reaction zone entrance hydrogen dividing potential drop is 12.0MPa; Hydrodemetallation (HDM) reaction zone temperature in is 330 DEG C, hydrodesulfurizationreaction reaction zone temperature in is 355 DEG C, hydrotreated lube base oil reaction zone temperature in is 370 DEG C, hydrodenitrification reaction zone temperature in is 385 DEG C, and the volume space velocity in hydroprocessing processes is 1.5h
-1; Hydrodemetallation (HDM) reaction zone entrance hydrogen-oil ratio is 1500:1, and hydrotreated lube base oil reaction zone entrance hydrogen-oil ratio is 1200:1.In control hydrodenitrification reaction zone, in gas gas-phase objects, hydrogen sulfide content is 4 % by weight.
The character of the hydrogenated oil adopting the aforesaid method of the present embodiment to obtain is in table 3.As can be seen from the present embodiment, the nitrogen content in the hydrogenated oil adopting the method for the present embodiment to obtain reduces 64.7 % by weight compared with the nitrogen content in stock oil.
Embodiment 4
The present embodiment adopts the method identical with embodiment 1 to carry out, and difference is:
Test conditions is: hydrodemetallation (HDM) reaction zone entrance hydrogen dividing potential drop is 15.0MPa; Hydrodemetallation (HDM) reaction zone temperature in is 350 DEG C, hydrodesulfurizationreaction reaction zone temperature in is 365 DEG C, hydrotreated lube base oil reaction zone temperature in is 365 DEG C, hydrodenitrification reaction zone temperature in is 375 DEG C, and the volume space velocity in hydroprocessing processes is 0.25h
-1; Hydrodemetallation (HDM) reaction zone entrance hydrogen-oil ratio is 800:1, and hydrotreated lube base oil reaction zone entrance hydrogen-oil ratio is 800:1.In control hydrodenitrification reaction zone, in gas gas-phase objects, hydrogen sulfide content is 6 % by weight.
The character of the hydrogenated oil adopting the aforesaid method of the present embodiment to obtain is in table 3.As can be seen from the present embodiment, the nitrogen content in the hydrogenated oil adopting the method for the present embodiment to obtain reduces 58.8 % by weight compared with the nitrogen content in stock oil.
Embodiment 5
The present embodiment adopts the method identical with embodiment 3 to carry out, and difference is: the stock oil that the present embodiment uses is long residuum, and its character is as shown in table 4.
Table 4
| Analysis project | Long residuum |
| Density (20 DEG C)/(kg/m 3) | 986.2 |
| Viscosity (100 DEG C)/(mm 2/s) | 179.2 |
| Carbon residue/% | 11.05 |
| Carbon content/% | 86.45 |
| Hydrogen richness/% | 11.47 |
| Sulphur content/% | 1.37 |
| Nitrogen content/% | 0.35 |
| Saturated point/% | 28.1 |
| Fragrance divides/% | 36.7 |
| Colloid/% | 32.2 |
| Bituminous matter/% | 3.0 |
| Nickel content/(μ g/g) | 36.6 |
| Content of vanadium/(μ g/g) | 19.2 |
The character of the hydrogenated oil adopting the aforesaid method of the present embodiment to obtain is in table 3.As can be seen from the present embodiment, the nitrogen content in the hydrogenated oil adopting the method for the present embodiment to obtain reduces 57.1 % by weight compared with the nitrogen content in stock oil.
Embodiment 6
The present embodiment adopts the method identical with embodiment 1 to carry out, and difference is: the filling scheme of the catalyzer in the present embodiment is as shown in table 5.
Table 5
The character of the hydrogenated oil adopting the aforesaid method of the present embodiment to obtain is in table 3.As can be seen from the present embodiment, the nitrogen content in the hydrogenated oil adopting the method for the present embodiment to obtain reduces 68.6 % by weight compared with the nitrogen content in stock oil.
Can be found out by above result, when carrying out hydrotreatment by adopting method of the present invention, effectively can reduce the nitrogen content in hydrogenated oil, and then saving production cost.And can be found out by the result of comparative example 1 and embodiment 4, under the prerequisite that all the other conditions are identical, when in embodiment 1, the content of the hydrogen sulfide of hydrodenitrification reaction zone is 2 % by weight, denitrification percent is than the height in embodiment 4.And method of the present invention to the nitrogen content in the kind of the kind of catalyzer, filling method, stock oil and stock oil, all there is no particular limitation, adopt the denitrification percent of method of the present invention obviously compared with the height in comparative example.
It can also be seen that from the result of embodiments of the invention, method of the present invention particularly has very high nitric efficiency for the stock oil with high nitrogen-containing, and the method for prior art often cannot make the nitrogen content had in the raw material of high nitrogen-containing significantly reduce.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (11)
1. the method for a heavy-oil hydrogenation denitrogenation, the method comprises: under hydroprocessing conditions, in presence of hydrogen, the stock oil containing heavy oil is contacted with hydrodenitrogenation catalyst with Hydrodemetalation catalyst, Hydrobon catalyst, hydrocatalyst for saturating successively, obtains hydrogenated oil; Wherein, after contacting with Hydrobon catalyst and before contacting with hydrocatalyst for saturating, the product obtained after contacting with Hydrobon catalyst is carried out air lift, obtain liquid phase thing and the gas gas-phase objects containing hydrogen, wherein, the process contacted with hydrodenitrogenation catalyst is carried out under sulfur-bearing logistics exists.
2. method according to claim 1, wherein, the described process contacted with hydrodenitrogenation catalyst is carried out in the hydrodenitrification reaction zone containing described hydrodenitrogenation catalyst; The consumption of preferred described sulfur-bearing logistics makes the hydrogen sulfide containing 0.1-20 weight part in the gas gas-phase objects of the hydrodenitrification reaction zone of every 100 weight parts, the hydrogen sulfide preferably containing 1-5 weight part.
3. method according to claim 1 and 2, wherein, described sulfur-bearing logistics comprises dithiocarbonic anhydride, dimethyl disulfide and derivative thereof, dimethyl disulfide and derivative thereof, organic polythiaether and derivative, mercaptan and derivative thereof, thiophene and derivatives, straight-run diesel oil, decompressed wax oil, catalytic diesel oil, catalytic cycle oil, catalytic slurry steam oil, coker gas oil, wax tailings, deasphalted oil and solvent treatment and extract at least one in oil out; Be preferably at least one in dithiocarbonic anhydride, dimethyl disulfide, straight-run diesel oil, decompressed wax oil, catalytic diesel oil and catalytic cycle oil.
4. method according to claim 1 and 2, wherein, described air lift is carried out under hydrogen make-up exists.
5. method according to claim 1 and 2, wherein, described hydroprocessing condition comprises: hydrogen dividing potential drop is 5.0-22.0MPa, temperature of reaction is 330-450 DEG C, volume space velocity is 0.1-3.0h
-1, hydrogen and stock oil volume ratio be 350-2000:1.
6. method according to claim 1, wherein, described contact with Hydrodemetalation catalyst, Hydrobon catalyst, hydrocatalyst for saturating and hydrodenitrogenation catalyst respectively in the hydrodemetallation (HDM) reaction zone containing Hydrodemetalation catalyst, the hydrodesulfurizationreaction reaction zone containing Hydrobon catalyst, the hydrotreated lube base oil reaction zone containing hydrocatalyst for saturating and carry out containing the hydrodenitrification reaction zone of hydrodenitrogenation catalyst.
7. method according to claim 6, wherein, described hydrodemetallation (HDM) reaction zone, hydrodesulfurizationreaction reaction zone, hydrotreated lube base oil reaction zone and hydrodenitrification reaction zone comprise at least one hydrogenator respectively; Preferably comprise 1-5 hydrogenator respectively.
8. method according to claim 6, wherein, described hydrodemetallation (HDM) reaction zone, hydrodesulfurizationreaction reaction zone, hydrotreated lube base oil reaction zone and hydrodenitrification reaction zone comprise at least one beds respectively; Preferably comprise 1-5 beds respectively.
9. method according to claim 1 and 2, wherein, described heavy oil comprises at least one in long residuum and vacuum residuum.
10. method according to claim 1 and 2, wherein, also containing distillate in described stock oil, described distillate comprises decompressed wax oil, catalytically cracked oil steams oil, at least one in oil and liquefied coal coil is extracted in catalytic cracking turning oil, wax tailings, deasphalted oil, solvent treatment out; In preferred described stock oil, nitrogen content is not less than 3000 μ g/g; More preferably in described stock oil, nitrogen content is 3000-8000 μ g/g.
11. methods according to claim 1, wherein, the method comprises:
(1) in presence of hydrogen, the stock oil containing heavy oil is introduced hydrodemetallation (HDM) reaction zone, contacts with Hydrodemetalation catalyst, hydrodemetallation (HDM) reaction occurs, obtain hydrodemetallation (HDM) reaction zone and generate oil and gas;
(2) the hydrodemetallation (HDM) reaction zone obtained in step (1) is generated oil and introduce hydrodesulfurizationreaction reaction zone with gas, contact with Hydrobon catalyst, hydrodesulfurization reaction occurs, obtain hydrodesulfurizationreaction reaction zone and generate oil and gas;
(3) under the existence of hydrogen make-up, the hydrodesulfurizationreaction reaction zone obtained in step (2) is generated oil and introduces air lift district with gas, oil is generated to described hydrodesulfurizationreaction reaction zone and carries out air lift, and carry out gas-liquid separation, obtain liquid phase thing and the gas gas-phase objects containing hydrogen;
(4) the liquid phase thing obtained in hydrogen and step (3) is introduced hydrotreated lube base oil reaction zone, contact with hydrocatalyst for saturating, hydrotreated lube base oil reaction occurs, obtain hydrotreated lube base oil reaction zone generation oil gentle;
(5) under the existence of sulfur-bearing logistics, the hydrotreated lube base oil reaction zone obtained in step (4) is generated oily gentle introducing hydrodenitrification reaction zone, contact with hydrodenitrogenation catalyst, generation hydrodenitrification is reacted, obtain hydrodenitrification reaction zone and generate oil and gas, then carry out gas-oil separation, obtain hydrogenated oil.
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