CN105524657A - Method for hydrogenation of distillate oil via fluidized bed - Google Patents
Method for hydrogenation of distillate oil via fluidized bed Download PDFInfo
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Abstract
The invention relates to a method for hydrogenation of distillate oil via a fluidized bed. The method is realized in hydrotreatment device which comprises a fluidized bed reactor, a high-pressure stripping tower, a high-pressure separator and a fractionation system. The method comprises the following steps: mixing a distillate oil raw material and hydrogen, then carrying out mixing with liquid-phase effluent from the high-pressure stripping tower, injecting the obtained mixed material into the fluidized bed reactor, carrying out catalytic hydrogenation reaction with the fluidized bed catalyst, then injecting reacted materials into the high-pressure stripping tower and carrying out gas stripping and gas-liquid separation, allowing a part of the liquid-phase effluent to return to the fluidized bed reactor, and continuing reaction. The method for hydrogenation of the distillate oil via the fluidized bed provided by the invention can achieve better reaction effect, so hydrogenated oil product with superior properties can be obtained.
Description
Technical field
The present invention relates to a kind of distillate boiling bed hydrogenation method, particularly, relate to a kind of distillate ebullated bed two-phase hydrogenation method.
Background technology
The increase day by day of world oil energy demand facilitates the rapid progress of coal liquifaction technology, and direct coal liquefaction technology is one of them outstanding representative.Representational direct coal liquefaction process comprises the NEDOL technique of Japan, German IGOR technique, the HTI technique of the U.S. and the direct coal liquefaction process of Chinese Shenhua in the world at present.
The liquefied coal coil that DCL/Direct coal liquefaction produces generally has following characteristics: boiling range 160-450 DEG C, and alkene, nitrogen and oxygen level are high, if processed not in time, very easily generates the material being unfavorable for following process and transport.The method of general employing hydrogenation carries out pre-treatment to liquefied coal coil, and the alkene in saturated liquefied coal coil, removes oxygen, removes the heteroatoms such as nitrogen and sulphur to greatest extent, and improve the stability of liquefied coal coil, this process is also referred to as stabilized hydrogenation.The hydrogenation process of usual distillate preferably uses fixed-bed reactor, but owing to there is a certain amount of fine solid particle in liquefied coal coil, comprise coal dust and DCL/Direct coal liquefaction catalyzer, these fine solid particle are difficult to by filtering all removings, if therefore use fixed bed reconstructed coal liquefaction oil or other is the same as with liquefied coal coil fine grain distillate, understand and cause the operational cycle short because pressure drop raises fast.Boiling bed hydrogenation technology can add online and take out catalyzer, and therefore catalyst performance can keep constant in the whole operational cycle.Boiling bed hydrogenation technology also has temperature of reactor and easily to control and evenly, pressure drop is low and constant, can reach the advantage such as higher transformation efficiency and longer operational cycle in addition.Therefore boiling bed hydrogenation technology is applicable to liquefied coal coil or other hydrogenation process containing fine grain distillate the same as liquefied coal coil.
Also there is obvious shortcoming in boiling bed hydrogenation technology, outstanding its catalyzed reaction efficiency that is reflected in is lower poor with quality product.For liquefied coal coil stabilized hydrogenation process, aromatic hydrocarbons approximately containing 70-90% in liquefied coal coil, the main purpose of stabilized hydrogenation device is exactly the dicyclo in liquefied coal coil and polycyclic aromatic hydrocarbons fractional saturation are generated effectively hydrogen donor component such as such as alkyl benzene, dialkyl benzene class and trialkyl benzene class etc.The aromatic saturation of polycyclic aromatic hydrocarbons is consecutive reaction, and such as polycyclic aromatic hydrocarbons wants hydrogenation to generate two alkyl benzene, first needs hydrogenation to produce an alkyl benzene, and this illustrates the reaction severity that the saturated needs of polycyclic aromatic hydrocarbons are higher.Facts have proved that the hydrogen supply capacity of the hydrogen supply dissolvent that ebullated bed reactor processes is lower, cause the finished product amount of dispatching from the factory lower than design load, reduce economic benefit.
The most important reason of ebullating bed reactor weak effect is that comparatively fixed bed is low for the catalyst concn of ebullated bed reactor, and the thinking therefore solved the problem improves the catalyst concn of ebullated bed reactor.Boiling bed hydrogenation reactor is three-phase fluidized bed, and the concentration of catalyzer is subject to the impact of gas phase and liquid phase phase content.Reduce the phase content of gas phase and liquid phase, the concentration of catalyzer can be improved.But reduce liquid and can reduce the residence time of liquid in reactor containing rate, and reduce gas holdup hydrogen supply in reactor may be caused not enough.Therefore need to consider the phase content of three-phase, make reaction effect optimization.
US6881326A describes a kind of two-phase hydrogenation preconditioning technique.Its technological process is that hydrogen is dissolved in oil through a mixed hydrogen production device by fresh feed oil, turning oil and hydrogen, and the oil of dissolving hydrogen enters reactor and catalyst exposure carries out catalyzed reaction.A reacted logistics part is circulated to mixed hydrogen production device, and a part is discharged from device as product.The method eliminates recycle hydrogen system, but this technology is provided with separator before reactor carries out waste gas separation.Although the waste gas of some effects hydrogenation reaction can be removed like this, also make the hydrogen that part has been dissolved separate from stock oil, finally affect hydrogenation reaction effect.
CN101942318A discloses a kind of hydro carbons two-phase hydrogenation treatment process, detailed process is: fresh feed and turning oil mix in catalysis gas stripping column, completes logistics air lift after hydrogenation reaction, the dissolving of hydrogen in feed oil and the hydrogenation pre-reaction process of raw material simultaneously.Molten hydrogen logistics enters in ebullated bed reactor carries out catalytic hydrogenation reaction, reacted stream portions discharger, and part enters catalysis gas stripping column in the mode of turning oil.This technology also exists following problem: one is that stock oil directly adds in high pressure gas stripper, can be taken out of high pressure gas stripper by gas stripping gas in its typical operation conditions lower part lighting end and ebullated bed reactor cannot be entered fully react, two is owing to there is catalyzed reaction in gas stripping column, and the higher fresh feed of reactive behavior is introduced in gas stripping column, this can cause reacting more violent in gas stripping column, dissolved hydrogen then in liquid phase also consumes comparatively fast, this can cause dissolved hydrogen in the liquid phase of effluent gases stripper not reach capacity, reduce the efficiency of turning oil dissolved hydrogen, and finally cause catalytic hydrogenation reaction efficiency in ebullated bed reactor to reduce.
In addition, above-mentioned technology does not all consider hydrogen loss problem in the reactor, and at the rear portion of reactor along logistics direction, the reduction of dissolve hydrogen concentration can cause catalytic hydrogenation reaction efficiency to reduce, and needs to consider hydrogen make-up in an appropriate manner.Above-mentioned technology does not consider that the solubleness of hydrogen in oil raises with the rising of temperature of reaction yet, the mixing oil of green oil and the turning oil temperature in pipeline is far below the temperature in reactor, even if therefore hydrogen reaches dissolution equilibrium in the oil of pre-treatment, after one enters reactor, because the temperature of oil raises, dissolved hydrogen is just far from reaching dissolution equilibrium.
Summary of the invention
The object of the invention is, in order to overcome above-mentioned defect existing in existing distillate boiling bed hydrogenation method, to provide a kind of new distillate boiling bed hydrogenation method.
The invention provides a kind of distillate boiling bed hydrogenation method, the method is carried out in hydrotreater, described hydrotreater comprises ebullated bed reactor, high pressure gas stripper, high-pressure separator and fractionating system, wherein, described method comprises: mix after distillate feedstock and hydrogen mixing with the liquid phase stream effluent from high pressure gas stripper again, and the mixture obtained injection ebullated bed reactor is carried out catalytic hydrogenation reaction with boiling-bed catalyst, reacted material is injected high pressure gas stripper and carries out air lift and gas-liquid separation, the Partial Liquid Phase effluent of described high pressure gas stripper is returned in described ebullated bed reactor and continue reaction, the vapor phase stream effluent of described high pressure gas stripper is injected high-pressure separator be separated, another part liquid phase stream effluent by described high-pressure separator isolated liquid phase stream effluent and described high pressure gas stripper is injected fractionating system and carries out fractionation.
In described distillate boiling bed hydrogenation method provided by the invention, on the one hand, present invention eliminates recycle hydrogen system, also eliminate the exhaust-steam separator in general two-phase hydrogenation method, save facility investment, in the inventive method, turning oil has better dissolved hydrogen and carries Hydrogen Energy power simultaneously; On the other hand, method of the present invention relies on a large amount of liquid circulation that dissolved hydrogen is brought in ebullated bed reactor, is solid-liquid two-phase system substantially, improves the residence time and the catalyst concn of liquid phase in reactor, have more excellent reaction effect in reactor.
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 schematic flow sheet of a kind of embodiment of distillate boiling bed hydrogenation method provided by the invention;
Fig. 2 is the schematic flow sheet of the another kind of embodiment of distillate boiling bed hydrogenation method provided by the invention.
Embodiment
Below in conjunction with accompanying drawing, 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 all scopes disclosed herein all comprise end points and can independently combine.The end points of scope presently disclosed and any value are all not limited to this accurate scope or value, and these scopes or value should be understood to the value comprised close to these scopes or value.
Described distillate boiling bed hydrogenation method provided by the invention is carried out in hydrotreater, and described hydrotreater comprises ebullated bed reactor, high pressure gas stripper, high-pressure separator and fractionating system.Described distillate boiling bed hydrogenation method comprises: mix after distillate feedstock and hydrogen mixing with the liquid phase stream effluent from high pressure gas stripper again, and the mixture obtained injection ebullated bed reactor is carried out catalytic hydrogenation reaction with boiling-bed catalyst, reacted material is injected high pressure gas stripper and carries out air lift and gas-liquid separation, the Partial Liquid Phase effluent of described high pressure gas stripper is returned in described ebullated bed reactor and continue reaction, the vapor phase stream effluent of described high pressure gas stripper is injected high-pressure separator be separated, another part liquid phase stream effluent by described high-pressure separator isolated liquid phase stream effluent and described high pressure gas stripper is injected fractionating system and carries out fractionation.
In described method provided by the invention, the hydrogen gas stream adopted is fresh hydrogen, that is, eliminates recycle hydrogen system in the present invention, by the direct discharger of vapor phase stream effluent of the isolated hydrogen of high-pressure separator, directly do not recycle.
In described method provided by the invention, in process distillate feedstock and hydrogen mixed, the hydrogen to oil volume ratio (under standard state, lower same) of hydrogen and distillate feedstock can be determined according to the dissolved hydrogen ability of distillate feedstock.In the present invention, preferably hydrogen and the hydrogen to oil volume ratio of distillate feedstock are controlled as the hydrogen to oil volume ratio height 20-50% than dissolution equilibrium under married operation condition.In the preferred case, the volume ratio of hydrogen and distillate feedstock is 10-100, is preferably 15-70, is more preferably 25-50.Before the mixing point of distillate feedstock and hydrogen is generally arranged on process furnace, such hydrogen can be mixed more fully and be dissolved in distillate feedstock.
In described method provided by the invention, the material of ebullated bed reactor is returned for recycle stock with the liquid phase stream effluent of high pressure gas stripper, to inject the distillate feedstock of ebullated bed reactor for fresh feed, by weight, circulated material quantity is 2-8:1 with the ratio (i.e. recycle ratio) of fresh feed amount, is preferably 3-6:1.In above-mentioned recycle ratio scope, particularly in preferred recycle ratio scope, recycle stock and fresh feed can support the normal fluidisation of catalyzer in ebullated bed reactor well, ebullated bed reactor itself is without the need to arranging recycle pump again, namely with traditional three-phase fluidized bed compared with, method of the present invention is without the need to extra facility investment.
In described method provided by the invention, the reaction conditions of described ebullated bed reactor is not particularly limited, and can implement by boiling bed hydrogenation reaction conditions conveniently.In the preferred case, the reaction conditions of described ebullated bed reactor comprises: temperature is 260-450 DEG C, is preferably 300-390 DEG C; Hydrogen dividing potential drop is 4-20MPa, is preferably 6-15MPa; During liquid, volume space velocity is 0.1-6h
-1, be preferably 0.5-2.0h
-1.In the present invention, pressure refers to absolute pressure.
In described method provided by the invention, the boiling-bed catalyst that described ebullated bed reactor adopts is not particularly limited, and can adopt conventional boiling-bed catalyst.Preferably, described boiling-bed catalyst has following character: pore volume is 0.4-1.6mL/g, and specific surface area is 50-300m
2/ g, catalyzer mean pore size is 7-12nm.In described boiling-bed catalyst, by weight, group vib metal oxide is (as WO
3or MoO
3) content can be 1-20 % by weight, be preferably 5-15 % by weight; The content of group VIII metal oxide (as NiO or CoO) can be 1-15 % by weight, is preferably 3-10 % by weight.More preferably, at least one element that described boiling-bed catalyst adds in boron, germanium, zirconium, phosphorus, chlorine and fluorine carries out modification.
In described method provided by the invention, described high pressure gas stripper can use hydrogen to carry out air lift.The operational condition of described high pressure gas stripper is not particularly limited, and can high pressure gas stripper operational condition conveniently implement.In the preferred case, the operational condition of described high pressure gas stripper comprises: temperature is 200-440 DEG C, is preferably 250-380 DEG C; Hydrogen dividing potential drop is 4-20MPa, is preferably 6-15MPa; Hydrogen to oil volume ratio is 5-100:1, is preferably 15-50:1.
In described method provided by the invention, the operational condition of described high-pressure separator is not particularly limited, and can high-pressure separator operational condition conveniently implement.
In described method provided by the invention, the material of ebullated bed reactor is returned for recycle stock with the liquid phase stream effluent of high pressure gas stripper, under preferable case, the turning oil pipeline described recycle stock being returned described ebullated bed reactor is provided with at least one and mends hydrogen entrance, for the molten hydrogen effect of hydrogenation recycle stock.This benefit hydrogen entrance is also tried one's best away from ebullated bed reactor entrance after being preferably arranged on recycle pump, and such hydrogen can be mixed fully and dissolve in recycle stock.In described high pressure gas stripper, inject hydrogen when carrying out air lift, the hydrogen to oil volume ratio supplementing hydrogen and the described recycle stock injecting described turning oil pipeline by mending hydrogen entrance can be 2-50:1, preferred 5-15:1.When turning oil pipeline is provided with hydrogen make-up entrance, described high pressure gas stripper can not inject hydrogen and carry out air lift.When described high pressure gas stripper do not inject hydrogen carry out air lift time, the hydrogen to oil volume ratio supplementing hydrogen and the described recycle stock injecting described turning oil pipeline by mending hydrogen entrance can be 10-100, and preferably 15-70, is more preferably 25-50.
In described method provided by the invention, under preferable case, described ebullated bed reactor is provided with at least one and mends hydrogen entrance, for the hydrogen consumed in postreaction.Mend hydrogen entrance and can one or more be set, preferably, mend hydrogen entrance be arranged on ebullated bed reactor tangent line height 2/1 to three/3rds between.In one embodiment, supplemented by this benefit hydrogen entrance and inject hydrogen (also namely fresh hydrogen), the hydrogen to oil volume ratio supplementing hydrogen and the distillate feedstock injected can be 2-50:1, is preferably 5-15:1.In another embodiment, the turning oil injecting and carry dissolved hydrogen is supplemented by this benefit hydrogen entrance, the described turning oil carrying dissolved hydrogen is from described turning oil pipeline, the recycle stock from described high pressure gas stripper and the mixture supplementing the hydrogen injected, wherein, the circulation oil mass of carrying dissolved hydrogen described in being injected by described benefit hydrogen entrance can account for the 10-30 % by weight of the recycle stock total amount from described high pressure gas stripper, preferred 15-25 % by weight.
In described method provided by the invention, the boiling range scope of described distillate feedstock can be 180-530 DEG C.Described distillate feedstock can be selected from least one in straight-run diesel oil, catalytic diesel oil, straight-run gas oil, wax tailings, coal tar and liquefied coal coil, is preferably the distillate containing fine solid particle or high calcium high ferro etc. and be not suitable for processing with fixed bed.
In described method provided by the invention, described ebullated bed reactor can arrange one, also can arrange multiple, when arranging multiple ebullated bed reactor, has at least an ebullated bed reactor to use method of the present invention to operate.
Below in conjunction with accompanying drawing, described process for hydrogenating residual oil provided by the invention is described further.
Fig. 1 is the schematic flow sheet of a kind of embodiment of described distillate boiling bed hydrogenation method provided by the invention.As shown in Figure 1, described distillate boiling bed hydrogenation method comprises: distillate feedstock 01 and appropriate amount of hydrogen 02-1 mix at pipeline with the liquid phase stream effluent 21-2 from high pressure gas stripper 2 after pipeline mixing again, the mode of charging below mixed logistics enters ebullated bed reactor 1 and contacts with boiling-bed catalyst, and supplemented by the benefit hydrogen entrance be arranged on ebullated bed reactor 1 and inject hydrogen 02-4, to carry out catalytic hydrogenation reaction, reacted logistics 11 enters high pressure gas stripper 2 and carry out air lift under the effect of air lift hydrogen 02-2, the vapor phase stream effluent 22 of described high pressure gas stripper 2 enters in high-pressure separator 3, vapor phase stream effluent 32 discharger of described high-pressure separator 3, fractionating system 4 is entered after the Partial Liquid Phase effluent 21-1 mixing of liquid phase stream effluent 31 and high pressure gas stripper 2, isolate gasoline 41, diesel oil 42 and tail oil 43, the remainder liquid phase stream effluent 21-2 of high pressure gas stripper 2 mixes at pipeline with the mixture of distillate feedstock 01 and appropriate amount of hydrogen 02-1 with supplementing on turning oil pipeline after the hydrogen 02-3 injected mixes again, then enter described ebullated bed reactor and continue reaction.
Fig. 2 is the schematic flow sheet of the another kind of embodiment of described distillate boiling bed hydrogenation method provided by the invention.As shown in Figure 1, described distillate boiling bed hydrogenation method comprises: distillate feedstock 01 and appropriate amount of hydrogen 02-1 mix at pipeline with the liquid phase stream effluent 21-2 from high pressure gas stripper 2 after pipeline mixing again, the mode of charging below mixed logistics enters ebullated bed reactor 1 and contacts with boiling-bed catalyst carries out catalytic hydrogenation reaction, reacted logistics 11 enters high pressure gas stripper 2 and carry out air lift under the effect of air lift hydrogen 02-2, the vapor phase stream effluent 22 of described high pressure gas stripper 2 enters in high-pressure separator 3, vapor phase stream effluent 32 discharger of described high-pressure separator 3, fractionating system 4 is entered after the Partial Liquid Phase effluent 21-1 mixing of liquid phase stream effluent 31 and high pressure gas stripper 2, isolate gasoline 41, diesel oil 42 and tail oil 43, the remainder liquid phase stream effluent of high pressure gas stripper 2 is divided into two strands of recycle stocks with supplementing on turning oil pipeline after the hydrogen 02-3 injected mixes, one recycle stock 21-2 enters described ebullated bed reactor 1 with distillate feedstock 01 and appropriate amount of hydrogen 02-1 after pipeline mixes, another gang of recycle stock 21-3 is supplemented by the benefit hydrogen entrance on ebullated bed reactor 1 and injects described ebullated bed reactor 1.
Compared with traditional fixed bed two-phase hydrogenation method, the shortcoming of ebullated bed two-phase hydrogenation is that the catalyst concn in reactor is lower, its advantage is then that its recycle ratio is comparatively large, so the dissolved hydrogen in reactor is more sufficient, but energy consumption also can be caused when recycle ratio is excessive larger.For this reason, method of the present invention is by hybrid mode and the control mixing hydrogen to oil volume ratio, make hydrogen suitably excessive in mixing process, after material enters reactor, temperature raises, simultaneous reactions also has consumption to hydrogen, so excessive hydrogen also can dissolve in oil very soon, for follow-up catalytic hydrogenation reaction provides hydrogen.
Distillate boiling bed hydrogenation method of the present invention has the following advantages:
(1) eliminate recycle hydrogen system, also eliminate the exhaust-steam separator in general two-phase hydrogenation method, save facility investment.
(2) consider the impact of service temperature on hydrogen solubleness in distillate, in pretreatment process, control hydrogen to oil volume ratio a little more than dissolution equilibrium, ensure that the dissolve hydrogen concentration in ebullated bed reactor, improve reaction efficiency.
(3) a large amount of turning oil is brought into dissolved hydrogen in ebullated bed reactor, is solid-liquid two-phase system substantially, improves the residence time and the catalyst concn of liquid phase in reactor, have more excellent reaction effect in reactor.
(4) in a preferred embodiment, consider the consumption of dissolved hydrogen in reaction process, by hydrogen or turning oil portion's hydrogen make-up in the reactor of carrying dissolved hydrogen, improve reaction efficiency.
The invention will be further described by the following examples.
The character of the catalyzer used in following examples and comparative example is as shown in table 1, and the stock oil that embodiment and comparative example adopt is liquefied coal coil, and its character is as shown in table 2.
Table 1
| Project | Catalyst A |
| MoO 3, % by weight | 22.50 |
| NiO, % by weight | 5.10 |
| Equivalent diameter, mm | 0.8 |
| Pore volume, mL/g | 0.55 |
| Specific surface, m 2/g | 240 |
| Mean pore size, nm | 8.5 |
Table 2
| Character | Numerical value |
| Density (20 DEG C), g/cm 3 | 0.9952 |
| Sulphur content, μ g/g | 121 |
| Nitrogen content, μ g/g | 3200 |
| Carbon content, % | 88.90 |
| Hydrogen richness, % | 9.19 |
| Hydrocarbon composition, % by weight | |
| Paraffinic hydrocarbons | 7.5 |
| Total naphthenic hydrocarbon | 12.0 |
| Total aromatic hydrocarbons | 80.5 |
| Mononuclear aromatics | 35.9 |
| Double ring arene | 32.0 |
| Three rings and the above aromatic hydrocarbons of three rings | 12.6 |
| Colloid | 0.0 |
| Gross weight | 100.0 |
Embodiment 1
The present embodiment is for illustration of described distillate boiling bed hydrogenation method provided by the invention.
Embodiment 1 is carried out on the ebullated bed evaluating apparatus of laboratory, its process flow sheet as shown in Figure 1, its processing condition and evaluation result as shown in table 3.
Embodiment 2
The present embodiment is for illustration of described distillate boiling bed hydrogenation method provided by the invention.
Embodiment 2 is carried out on the ebullated bed evaluating apparatus of laboratory, and its process flow sheet as shown in Figure 1, just supplements in ebullated bed reactor and injects hydrogen, its processing condition and evaluation result as shown in table 3.
Embodiment 3
The present embodiment is for illustration of described distillate boiling bed hydrogenation method provided by the invention.
Embodiment 3 is carried out on the ebullated bed evaluating apparatus of laboratory, and its process flow sheet as shown in Figure 1, does not just pass into air lift hydrogen in high pressure gas stripper, its processing condition and evaluation result as shown in table 3.
Embodiment 4
The present embodiment is for illustration of described distillate boiling bed hydrogenation method provided by the invention.
Embodiment 4 is carried out on the ebullated bed evaluating apparatus of laboratory, its process flow sheet as shown in Figure 2, the turning oil carrying dissolved hydrogen being supplemented injection by the benefit hydrogen entrance of ebullated bed reactor 1 accounts for 25 % by weight of recycle stock total amount, its processing condition and evaluation result as shown in table 3.
Comparative example 1
Comparative example 1 adopts the method for embodiment 1 in CN101942318A to carry out, and the catalyzer wherein loaded in high pressure gas stripper is 20 volume %, other processing condition and evaluation result as shown in table 3.
Table 3
| Numbering | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 |
| Ebullated bed reactor | |||||
| Temperature of reaction, DEG C | 370 | 370 | 370 | 370 | 370 |
| Hydrogen dividing potential drop, MPa | 12.0 | 12.0 | 12.0 | 12.0 | 12.0 |
| Liquid hourly space velocity, h -1 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Recycle ratio | 3：1 | 3：1 | 3：1 | 4：1 | 3：1 |
| Fresh feed hydrogen to oil volume ratio | 40：1 | 40：1 | 40：1 | 40：1 | -- |
| Hydrogen make-up hydrogen to oil volume ratio | 30：1 | -- | 30：1 | -- | -- |
| High pressure gas stripper |
| Service temperature, DEG C | 350 | 350 | 350 | 350 | 350 |
| Working pressure, MPa | 12.0 | 12.0 | 12.0 | 12.0 | 12.0 |
| Air lift hydrogen volume oil ratio | 30：1 | 30：1 | -- | 30：1 | 30：1 |
| Turning oil hydrogen to oil volume ratio | 10：1 | 10：1 | 35：1 | 10：1 | -- |
| Hydrogenated oil character | |||||
| Density (20 DEG C), g/cm 3 | 0.9476 | 0.9525 | 0.9488 | 0.9457 | 0.9614 |
| Sulphur content, μ g/g | 13 | 15 | 14 | 12 | 19 |
| Nitrogen content, μ g/g | 710 | 770 | 742 | 670 | 875 |
| Carbon content, % | 89.13 | 89.22 | 89.16 | 89.08 | 89.38 |
| Hydrogen richness, % | 10.86 | 10.77 | 10.83 | 10.92 | 10.61 |
As can be seen from the evaluation result of above-described embodiment and comparative example, more excellent reaction effect can be obtained according to described distillate boiling bed hydrogenation method provided by the invention, thus the more excellent hydrogenation oil product of character can be obtained.
Claims (21)
1. a distillate boiling bed hydrogenation method, the method is carried out in hydrotreater, described hydrotreater comprises ebullated bed reactor, high pressure gas stripper, high-pressure separator and fractionating system, wherein, described method comprises: mix after distillate feedstock and hydrogen mixing with the liquid phase stream effluent from high pressure gas stripper again, and the mixture obtained injection ebullated bed reactor is carried out catalytic hydrogenation reaction with boiling-bed catalyst, reacted material is injected high pressure gas stripper and carries out air lift and gas-liquid separation, the Partial Liquid Phase effluent of described high pressure gas stripper is returned in described ebullated bed reactor and continue reaction, the vapor phase stream effluent of described high pressure gas stripper is injected high-pressure separator be separated, another part liquid phase stream effluent by described high-pressure separator isolated liquid phase stream effluent and described high pressure gas stripper is injected fractionating system and carries out fractionation.
2. method according to claim 1, wherein, in process distillate feedstock and hydrogen mixed, the volume ratio of hydrogen and distillate feedstock is 10-100.
3. method according to claim 2, wherein, in process distillate feedstock and hydrogen mixed, the volume ratio of hydrogen and distillate feedstock is 25-50.
4. method according to claim 1, wherein, return the material of ebullated bed reactor for recycle stock with the liquid phase stream effluent of high pressure gas stripper, to inject the distillate feedstock of ebullated bed reactor for fresh feed, by weight, circulated material quantity is 2-8:1 with the ratio of fresh feed amount.
5. method according to claim 4, wherein, by weight, circulated material quantity is 3-6:1 with the ratio of fresh feed amount.
6. according to the method in claim 1-4 described in any one, wherein, the reaction conditions of described ebullated bed reactor comprises: temperature is 260-450 DEG C, and hydrogen dividing potential drop is 4-20MPa, and during liquid, volume space velocity is 0.1-6h
-1.
7. method according to claim 6, wherein, the reaction conditions of described ebullated bed reactor comprises: temperature is 300-390 DEG C, and hydrogen dividing potential drop is 6-15MPa, and during liquid, volume space velocity is 0.5-2h
-1.
8. according to the method in claim 1-4 described in any one, wherein, the operational condition of described high pressure gas stripper comprises: temperature is 200-440 DEG C, and hydrogen dividing potential drop is 4-20MPa, and hydrogen to oil volume ratio is 5-100:1.
9. method according to claim 8, wherein, the operational condition of described high pressure gas stripper comprises: temperature is 250-380 DEG C, and hydrogen dividing potential drop is 6-15MPa, and hydrogen to oil volume ratio is 15-50:1.
10. method according to claim 1, wherein, the material of ebullated bed reactor is returned for recycle stock with the liquid phase stream effluent of high pressure gas stripper, the turning oil pipeline described recycle stock being returned described ebullated bed reactor is provided with at least one and mends hydrogen entrance, supplemented by this benefit hydrogen entrance and inject hydrogen.
11. methods according to claim 10, wherein, when injecting hydrogen in described high pressure gas stripper and carrying out air lift, supplement inject the hydrogen of described turning oil pipeline and the hydrogen to oil volume ratio of described recycle stock is 2-50:1 by mending hydrogen entrance.
12. methods according to claim 11, wherein, supplement inject the hydrogen of described turning oil pipeline and the hydrogen to oil volume ratio of described recycle stock is 5-15:1 by mending hydrogen entrance.
13. methods according to claim 10, wherein, when not injecting hydrogen in described high pressure gas stripper and carrying out air lift, supplement inject the hydrogen of described turning oil pipeline and the hydrogen to oil volume ratio of described recycle stock is 10-100:1 by mending hydrogen entrance.
14. methods according to claim 13, wherein, supplement inject the hydrogen of described turning oil pipeline and the hydrogen to oil volume ratio of described recycle stock is 25-50:1 by mending hydrogen entrance.
15. according to the method in claim 1-4 described in any one, wherein, described ebullated bed reactor is provided with at least one and mends hydrogen entrance, supplemented inject hydrogen by this benefit hydrogen entrance, the hydrogen to oil volume ratio supplementing hydrogen and the distillate feedstock injected is 2-50:1.
16. methods according to claim 15, wherein, the hydrogen to oil volume ratio supplementing hydrogen and the distillate feedstock injected is 5-15:1.
17. according to the method in claim 1-4 described in any one, wherein, described ebullated bed reactor is provided with at least one and mends hydrogen entrance, the turning oil injecting and carry dissolved hydrogen is supplemented by this benefit hydrogen entrance, the described turning oil carrying dissolved hydrogen is from described turning oil pipeline, the recycle stock from described high pressure gas stripper and the mixture supplementing the hydrogen injected, wherein, the circulation oil mass by carrying dissolved hydrogen described in described benefit hydrogen entrance injection accounts for the 10-30 % by weight of the recycle stock total amount from described high pressure gas stripper.
18. methods according to claim 17, wherein, the circulation oil mass of carrying dissolved hydrogen described in being injected by described benefit hydrogen entrance accounts for the 15-25 % by weight of the recycle stock total amount from described high pressure gas stripper.
19. methods according to claim 1, wherein, described distillate feedstock is selected from least one in straight-run diesel oil, catalytic diesel oil, straight-run gas oil, wax tailings, coal tar and liquefied coal coil.
20. methods according to claim 1, wherein, the pore volume of described boiling-bed catalyst is 0.4-1.6mL/g, and specific surface area is 50-300m
2/ g, catalyzer mean pore size is 7-12nm; By weight, described boiling-bed catalyst contains the group vib metal oxide of 1-20 % by weight and the group VIII metal oxide of 1-15 % by weight.
21. methods according to claim 1 or 20, wherein, at least one element that described boiling-bed catalyst adds in boron, germanium, zirconium, phosphorus, chlorine and fluorine carries out modification.
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|---|---|---|---|
| CN201410515087.6A CN105524657B (en) | 2014-09-29 | 2014-09-29 | A kind of fraction oil boiling bed hydrogenation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107345164A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | A kind of method that straight-run diesel oil is hydrocracked production jet fuel |
| CN111073701A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Processing system and method for high-viscosity poly α olefin synthetic oil |
| CN113061462A (en) * | 2021-03-25 | 2021-07-02 | 南京延长反应技术研究院有限公司 | Refined diesel oil production system and method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787305A (en) * | 2009-01-23 | 2010-07-28 | 中国石油化工股份有限公司 | Method of liquid phase circulation hydrotreatment and reaction system |
| CN101942318A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Hydrocarbon two-phase hydrotreating method |
| CN102029128A (en) * | 2009-09-28 | 2011-04-27 | 中国石油化工股份有限公司 | Hydrotreating method of product circulation |
| CN202530049U (en) * | 2012-03-01 | 2012-11-14 | 中国石油天然气股份有限公司 | Liquid phase hydrogenation reaction system device |
| CN203238222U (en) * | 2013-04-03 | 2013-10-16 | 中国石油天然气股份有限公司 | Liquid phase hydrogenation reaction device with multistage hydrogen dissolving system |
| CN203389623U (en) * | 2013-06-28 | 2014-01-15 | 中国石油天然气集团公司 | Liquid-phase hydrogenation reaction system |
| CN103773441A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Boiling bed liquid phase hydrogenation treatment method |
-
2014
- 2014-09-29 CN CN201410515087.6A patent/CN105524657B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787305A (en) * | 2009-01-23 | 2010-07-28 | 中国石油化工股份有限公司 | Method of liquid phase circulation hydrotreatment and reaction system |
| CN101942318A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Hydrocarbon two-phase hydrotreating method |
| CN102029128A (en) * | 2009-09-28 | 2011-04-27 | 中国石油化工股份有限公司 | Hydrotreating method of product circulation |
| CN202530049U (en) * | 2012-03-01 | 2012-11-14 | 中国石油天然气股份有限公司 | Liquid phase hydrogenation reaction system device |
| CN103773441A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Boiling bed liquid phase hydrogenation treatment method |
| CN203238222U (en) * | 2013-04-03 | 2013-10-16 | 中国石油天然气股份有限公司 | Liquid phase hydrogenation reaction device with multistage hydrogen dissolving system |
| CN203389623U (en) * | 2013-06-28 | 2014-01-15 | 中国石油天然气集团公司 | Liquid-phase hydrogenation reaction system |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107345164A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | A kind of method that straight-run diesel oil is hydrocracked production jet fuel |
| CN107345164B (en) * | 2016-05-05 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of method that straight-run diesel oil is hydrocracked production jet fuel |
| CN111073701A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Processing system and method for high-viscosity poly α olefin synthetic oil |
| CN111073701B (en) * | 2018-10-19 | 2021-12-17 | 中国石油化工股份有限公司 | Processing system and method for high-viscosity poly-alpha-olefin synthetic oil |
| CN113061462A (en) * | 2021-03-25 | 2021-07-02 | 南京延长反应技术研究院有限公司 | Refined diesel oil production system and method |
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