CN101992048A - Reactor and application thereof to hydrocarbon oil liquid-solid two-phase hydrogenation - Google Patents
Reactor and application thereof to hydrocarbon oil liquid-solid two-phase hydrogenation Download PDFInfo
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- CN101992048A CN101992048A CN2009100657224A CN200910065722A CN101992048A CN 101992048 A CN101992048 A CN 101992048A CN 2009100657224 A CN2009100657224 A CN 2009100657224A CN 200910065722 A CN200910065722 A CN 200910065722A CN 101992048 A CN101992048 A CN 101992048A
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Abstract
The invention discloses a hydrocarbon oil hydrogenation reactor, which comprises a reactor barrel body and a catalyst bed layer. An outlet and an inlet are respectively formed at the upper part and lower part of the reactor. The reactor is characterized in that: at least one mixer is arranged in the reactor; the reactor is provided with a raw material mixture and a hydrogen inlet and also a hydrogen-containing mixture and a gas outlet; and the inlet of the mixer is connected with the inlet of reactor. Due to the adoption of the reactor, pressure difference of the pressure in the mixer and the pressure outside the mixture is reduced, wall thickness of the reactor is thinned, and equipment investment and operating cost are decreased.
Description
Technical field
The present invention relates to hydrogen and have hydrocarbon ils processing technique field under the situation, particularly a kind of hydrocarbon ils liquid-phase hydrogenatin method.
Background technology
In the hydrocarbon ils process technology, hydrogen addition technology is to improve one of hydrocarbon ils quality technology commonly used, the crude oil that is tending towards higher sulfur content along with the global crude oil market supply, the refinery need process the higher hydrocarbon ils inferior of sulfur-bearing, sulphur, nitrogen, oxygen and metal impurities are removed in refining process, change its quality by the molecular structure that changes hydrocarbon ils, thereby make various products satisfy code requirement.The hydrogen that the hydrocarbon oil hydrogenation process participates in reaction in fact only is useful on the hydrogen that chemical hydrogen consumes, and traditional trickle bed reactor hydrogen addition technology, need excessive hydrogen and exist, make that the volume ratio of reactor is bigger, and keep the exess of H2 gas and need use circulating hydrogen compressor.
Hydrogen need be delivered to liquid phase from gas phase in traditional hydrogenation technique, is adsorbed on the surface of catalyst then jointly, reacts under the effect of catalyst active center.Because hydrogenation reaction is a strong exothermal reaction, in order to keep reaction temperature, utilize a large amount of hydrogen and feedstock oil to take away the heat that reaction produces by beds, and the hydrogen of actual needs (chemical hydrogen consumption) is fewer in hydrogenation process, do not participate in the hydrogen of reaction by separator and liquid phase separation and after removing impurity, by circulating hydrogen compressor its pressure is elevated to the required pressure of reaction and delivers to reactor continuation participation hydrogenation reaction, the hydrogen raising pressure that the effect of circulating hydrogen compressor will not participate in hydrogenation reaction exactly recycles it, therefore the circulating hydrogen compressor becomes imperative equipment in existing hydrogen addition technology, be called the heart of hydrogenation plant in the industry, this shows its importance in hydrogenation plant.
It is to keep the hydrogen dividing potential drop of hydrocarbon oil hydrogenation reaction that tradition hydrocarbon oil hydrogenation technology adopts another main cause of excessive hydrogen, keeps higher hydrogen branch and is pressed in and helps hydrofinishing and hydrocracking reaction on the thermodynamics, and suppress to generate the condensation reaction of coke.
Be the gas, liquid, solid three-phase in traditional fixed bed hydrogenation reactor and deposit that gas phase is the steam of hydrogen and hydrocarbon raw material, liquid phase is the hydrocarbon raw material of vaporization not, and solid phase is a catalyst.Gas-liquid two-phase is to pass through beds with the form of drip, therefore also claims trickle bed reactor.
In trickle bed reactor, in order to strengthen the mass transfer dynamics, the volume ratio of hydrogen and feedstock oil is generally 50～2000: 1, therefore the hydrogenation reactor design is bigger, and the actual feedstock oil that reacts of participating in is relevant with liquid hourly space velocity (LHSV), air speed has reflected the disposal ability of device, and bigger air speed operation is adopted in industrial hope, but air speed is subjected to the restriction of reaction speed.Air speed is unusual at 0.5～10h according to catalyst activity, feedstock property, reaction depth
-1Between the fluctuation.The unifining process of commercial Application can improve alkene saturation factor, hydrodesulfurization rate and hydrodenitrogeneration rate at certain reaction temperature condition decline low-speed at present.Under hydrocracking condition, it is little to total conversion ratio influence to improve air speed, but the decline of the light component content in the product is more.
Tradition hydrogenation engineering, another purpose that adopts the exess of H2 gas is to strengthen mass transfer, takes away a large amount of heats that produce because of hydrogenation reaction.Circulating hydrogen compressor is as the heart of hydrogenation process, investment and operating cost are all higher, in order to reduce the burden of circulating hydrogen compressor, people begin to consider to utilize hydrogen supply agent to provide hydrogen source for the hydrocarbon oil hydrogenation process, USP4698147 promptly discloses and has utilized hydrogen supply agent to reduce the time of staying, reaction back hydrogen supply agent utilizes hydrogen to regenerate, and recycles after the regeneration.In order to strengthen cracking reaction, USP4857168 discloses and has utilized hydrogen supply agent and hydrogen to provide the heavy-oil hydrogenation cracking method of hydrogen source for heavy-oil hydrogenation, and hydrogen supply agent mainly works to suppress to generate the condensation reaction of coke.
Above-mentioned improvement still needs recycle hydrogen and circulating hydrogen compressor, US6428686 has proposed a kind of two-phase hydrogenation method, before reactor, be dissolved in hydrogen in the feedstock oil, recycle hydrogen and circulating hydrogen compressor have been cancelled, the investment and the operating cost of hydrogenation plant have been reduced, this technology adopts the liquid phase circulation of product, improve the meltage of hydrogen, to satisfy in the hydrogenation process requirement to hydrogen, and take reaction heat out of, this technology is with recycle oil, enter hydrogenation reactor after raw material and solvent or diluent and hydric solvent or the mixing diluents, advantage is to have reduced the investment and the operating cost of circulating hydrogen compressor, its shortcoming is the reaction speed that the existence of a large amount of recycle oil can influence fresh feed and hydrogen, because fresh feed is relatively fiercer with hydrogen reaction when beginning contacts with catalyst, recycle oil is through hydrogenation reaction, its reactivity is lower than fresh feed, therefore the existence of recycle oil has hindered contacting of fresh feed oil and hydrogen and catalyst, has reduced the mass transfer and the reaction speed of the oily and hydrogen of fresh feed.
Be recycled directly to the problem that reaction speed that reactor inlet brings descends in order to overcome US6428686 recycle oil, Chinese patent application CN200810049938.7 has proposed recycle oil is entered reactor between the beds, reaction on catalyst provides fresh hydrogen source for feedstock oil and hydrogen, and recycle oil is from high-pressure separator.As everyone knows, hydrogenation reaction is exothermic reaction, and the temperature of reactor outlet logistics is higher than reactor inlet temperature.Usually the reactor outlet logistics at first with cold logistics heat exchange, enter high-pressure separator then and carry out gas-liquid separation, it is the separator of a high pressure low temperature that high-pressure separator is compared with reactor, contain hydrogen sulfide from the recycle oil that high-pressure separator is told, these hydrogen sulfide can influence the speed of hydrodesulfurization and other hydrogenation reactions from entering reactor between reactor inlet or the bed.
Be that US6428686 or CN200810049938.7 are recycled directly to the reactor outlet logistics between reactor inlet or the beds, though CN200810049938.7 is that the liquid phase of will come out from separator is as recycle oil, the hydrogen sulfide that from the liquid phase that separator comes out, contains dissolving, these hydrogen sulfide are in the hydrogenation process, deviate from that sulfide in the raw material produces, this is the hydrogenation reaction desired response, but these hydrogen sulfide in the recycle oil can influence activity of such catalysts, suppress sulfur-containing compound near the activity of such catalysts center, reduce activity of such catalysts and selectivity, this is a unwanted results.
US6428686 still is that CN200810049938.7 is arranged at feedstock oil, recycle oil and solvent or diluent outside the reactor with the blender that mixes molten hydrogen of hydrogen, such blender need bear the pressure differential of blender inner high voltage medium and the outer atmosphere of blender, need thicker wall thickness to bear this pressure differential, such equipment investment is higher.
Summary of the invention
The present invention proposes a kind of reactor, this reactor is inserted the blender of hydrocarbon ils and hydrogen in the reactor, reduces the inside and outside pressure differential of blender, reduces its wall thickness and reduces equipment investment.
The present invention proposes the application of this reactor in the liquid-solid hydrogenation of hydrocarbon ils.
The present invention proposes a kind of reactor, comprises reactor staving, beds, reactor inlet and reactor outlet, it is characterized in that: a blender is set in reactor at least, and blender is provided with inlet, the outlet of molten hydrogen mixture and gas vent.
Described reactor is characterized in that: when a blender is set in the reactor, be arranged on reactor inlet, mixer entrance links to each other with reactor inlet, and molten hydrogen mixture outlet links to each other with beds, and gas outlet tube extends to the reactor outside.
Described reactor, it is characterized in that: when two above blenders are set in the reactor, one of them is arranged on reactor inlet, other are arranged between the beds, be arranged on the reactor inlet blender, mixer entrance links to each other with reactor inlet, and molten hydrogen mixture outlet links to each other with beds; Be arranged on the blender between the beds, mixer entrance links to each other with last beds outlet, and molten hydrogen mixture outlet links to each other with back one beds inlet; Gas outlet tube extends to the reactor outside.
Described reactor is characterized in that: reactor outlet links to each other with outlet valve.
Described reactor is characterized in that: recycle oil and hydrogen inlet are set between the reactor bed.
Described reactor is characterized in that: reactor inlet is arranged on reactor top, and reactor outlet is arranged on reactor lower part.
Described reactor is characterized in that: reactor inlet is arranged on reactor lower part, and reactor outlet is arranged on reactor top.
The present invention proposes the application of a kind of reactor in the hydrocarbon ils liquid-solid two-phase hydrogenation, be characterised in that: hydrogen, solvent or diluent, fresh feed oil enters the interior blender formation mixing logistics of reactor with part recycle oil and contacts with catalyst, the blender formation mixing logistics that another part or whole recycle oil enter between the beds contacts with catalyst, the reaction effluent part is as recycle oil, beds is immersed in the liquid phase material, mix amounts of hydrogen in the logistics and be under the reaction condition saturated molten hydrogen amount of mixing logistics 1～30 times, preferred 1.2～20 times, optimum 1.5～10 times.
The application of described a kind of reactor in the hydrocarbon ils liquid-solid two-phase hydrogenation is characterised in that: the reaction effluent part is deviate from hydrogen sulfide as recycle oil through stripping.
The application of described a kind of reactor in the hydrocarbon ils liquid-solid two-phase hydrogenation is characterised in that: the stripping medium that stripping is deviate from recycle oil hydrogen sulfide is inert gas or hydrogen.
The application of described a kind of reactor in the hydrocarbon ils liquid-solid two-phase hydrogenation is characterised in that: the stripping medium that stripping is deviate from recycle oil hydrogen sulfide is a hot high pressure hydrogen.
The application of described a kind of reactor in the hydrocarbon ils liquid-solid two-phase hydrogenation is characterised in that: it is long-pending in overall reactor to contain 0.1～15 volume % gas in the reactor.
The application of described a kind of reactor in the hydrocarbon ils liquid-solid two-phase hydrogenation is characterised in that: mix logistics and enter reactor from reactor top, reaction effluent flows out from reactor lower part.
The application of described a kind of reactor in the hydrocarbon ils liquid-solid two-phase hydrogenation is characterised in that mixing logistics enters reactor from reactor lower part, and reaction effluent flows out from reactor top.
The application of described a kind of reactor in the hydrocarbon ils liquid-solid two-phase hydrogenation is characterised in that: the mixture flow point is from going out gas, and liquid enters beds.
The application of described a kind of reactor in the hydrocarbon ils liquid-solid two-phase hydrogenation is characterised in that: solvent or diluent are at least a in the hydrocarbon ils behind heavy naphtha, naphtha, lighter hydrocarbons, light distillate, diesel oil, VGO and the hydrogenation.
The application of described a kind of reactor in the hydrocarbon ils liquid-solid two-phase hydrogenation is characterised in that: fresh feed oil is the cut of hydrocarbon ils or hydrocarbon ils.
The application of described a kind of reactor in the hydrocarbon ils liquid-solid two-phase hydrogenation is characterised in that: at least a in fresh feed oilstone oil distillate, distillate, diesel oil, deasphalted oil, residual oil, lubricating oil, liquefied coal coil and shale oil or its product.
The application of described a kind of reactor in the hydrocarbon ils liquid-solid two-phase hydrogenation is characterised in that: remove a kind of pollutant in sulphur in the hydrocarbon ils, nitrogen, oxygen, the metal impurities at least, and saturated aromatic hydrocarbons, and the molecular structure of change hydrocarbon ils.
The application of described a kind of reactor in the hydrocarbon ils liquid-solid two-phase hydrogenation is characterised in that: the volume ratio of recycle oil and fresh feed oil is 0.1: 1～20: 1, preferred 0.5: 1～15: 1.
The application of described a kind of reactor in the hydrocarbon ils liquid-solid two-phase hydrogenation is characterised in that: utilize to enter the pressure that the blender gas vent is discharged the amount control reactor of gas.
The application of described a kind of reactor in the hydrocarbon ils liquid-solid two-phase hydrogenation is characterised in that: the pressure that utilizes the amount control reactor that enters hydrogen in the blender.
The application of described a kind of reactor in the hydrocarbon ils liquid-solid two-phase hydrogenation is characterised in that: the interior liquid level of amount control reactor of utilizing the reactor outlet reaction effluent.
The application of described a kind of reactor in the hydrocarbon ils liquid-solid two-phase hydrogenation is characterised in that: utilize the liquid level in the reactor outlet valve control reactor.
The application of described a kind of reactor in the hydrocarbon ils liquid-solid two-phase hydrogenation is characterised in that: the blender that hydrogen, solvent or diluent, fresh feed oil and recycle oil enter in the reactor forms mixing logistics discharge gas, and liquid contacts with catalyst.
The application of described a kind of reactor in the hydrocarbon ils liquid-solid two-phase hydrogenation is characterised in that: catalyst is Hydrobon catalyst, catalyst for hydro-upgrading, hydrotreating catalyst or hydrocracking catalyst.
The application of described a kind of reactor in the hydrocarbon ils liquid-solid two-phase hydrogenation is characterised in that: liquid phase material by the reaction condition of hydrogenation catalyst bed is: reaction temperature is 150～450 ℃, and reaction pressure is 1～17MPa, and volume space velocity is 0.5～15h during liquid
-1
Reaction effluent part of the present invention is deviate from hydrogen sulfide through stripping and as recycle oil stripping medium is: inert gas or hydrogen, preferred hydrogen, optimum is a hot high pressure hydrogen, the pressure of its hot high pressure hydrogen is higher than the Hydrogen Vapor Pressure that mixes with fresh feed oil and solvent or diluent mixture, and temperature is lower than the temperature of reaction effluent.
The problem of a maximum of hydrogenation process is the beds coking, the coking reaction can take place under the reaction condition, if there is not enough hydrogen, the cracking reaction meeting causes coke to form, and is deposited on catalyst surface, and the present invention is owing to adopt the recycle oil circulation, it is saturated that recycle oil obtains many aromatic hydrocarbons through hydrogenation, function with hydrogen supply can suppress coke and form, and prolongs life of catalyst.
The application of a kind of reactor of the present invention in the hydrocarbon ils liquid-solid two-phase hydrogenation can be used for straight-run, FCC recycle oil, coker gas oil CGO, perhaps it mixes kerosene and diesel oil hydrogenation processing, also can be used for the FCC pretreatment of raw material, be used for new device and relax the hydrocracking transformation, be used to produce ULSD, be used for the preliminary treatment of raw material or the post processing of product.
Hydrogenation method for hydrocarbon oils of the present invention has following advantage:
1) catalyst amount is few;
2) hydrogen loss is less;
3) lower operating cost;
4) liquid yield is higher;
5) bigger operating flexibility;
6) the sulphur nitrogen content of product is very low;
7) lower investment;
8) reduced reactor volume;
9) for producing ultra-low-sulphur diesel, improvement expenses is very low.
10) reduce catalyst harm, the life cycle that prolongs catalyst.
Compare the present invention with the prior art of trickle bed hydrogenation reactor: but desulfurization 90%～98%, and the hydrogen consumption only is 70%～90% of a trickle bed hydrogenation reactor, the total consumption of catalyst only is 15%～30%.
Description of drawings
Fig. 1 is a kind of reactor.
Fig. 2 is another kind of reactor.
1. reactor shell, 2. mixture material, 3. hydrogen, 4,7,9,10. tube connector, 5. first blender, 6. gas vent, 8 first beds, 11. outlet valve, 12. reaction effluents, 13. part recycle oils, 14. gas, 15. second blenders, 16. second gas vents, 18. second beds, 19. reactor inlets, 20. mixer entrances, 21. molten hydrogen mixture outlet, 22. reactor outlets, 23. recycle oils and hydrogen inlet.
Among the present invention, the concrete hydrogenation technique condition that reactor is used and the technology contents such as selection of catalyst can according to feedstock property and product quality requirement, be determined according to the conventional knowledge in this area. The dissolved hydrogen amount can be tested mensuration under the reaction condition, can calculate according to the empirical equation that this area document provides, can estimate according to the empirical value that this area document provides that also above-mentioned empirical equation and empirical value can be with reference to " hydroprocessing technique and engineering " book related contents of Chinese petrochemical industry publishing house publication in 2004. Determination of test method reaction system dissolved hydrogen amount is technical method well known to those skilled in the art, as on the test device, adopts the condition identical with course of reaction, measures system dissolves hydrogen amount when reaching suitable reaction result.
In the inventive method, the partial hydrogenation product mixes with reaction raw materials as circulation is excellent, with the steady operation of assurance hydrogenation reaction and the service life of catalyst, internal circulating load can be determined according to the concrete condition of reaction system, suitably add big cycle volume when for example exothermic heat of reaction is big, reactive chemistry hydrogen consumes and suitably adds big cycle volume etc. when high, and in general internal circulating load is greatly favourable to course of reaction, but can cause the unfavorable results such as power consumption increase, comprehensively various factors is finally determined. The hydrogenation products that recycles can directly recycle, and also can use through recirculation after the fractionating system.
In the inventive method, the raw material that hydrogenation process uses can comprise gasoline, kerosene, diesel oil, VGO (vacuum distillate), CGO (wax tailings), LCO (catalytic cracking gently circulate oil), residual oil, depitching oil, lubricating oil etc. According to the requirement of purpose product, hydrogenation technique can comprise hydrofinishing, hydrotreatment, hydro-upgrading, hydrocracking etc.
In the inventive method, other hydrogenation conditions can determine that by the general knowledge in this area in general, reaction temperature is 150～450 ℃ according to the character of raw material, product quality requirement etc., and reaction pressure is 1～17MPa, and volume space velocity is 0.5～15h during liquid-1。
In the hydrogenation process of the present invention, hydrogen gas circulating system is not set, carrying into the dissolved hydrogen of reaction system when relying on liquid-phase product to circulate in a large number provides fresh raw material to carry out the needed hydrogen of hydrogenation reaction, because recycling of hydrogenation products still can keep the activity stability of catalyst. Reactor adopts close structural response device with trickle bed reactor, controls amount of liquid and pressure in the reactor by controlling reactor capacity and discharge opeing amount. Its advantage is to eliminate H in the wetting factor impact of catalyst and the circulation hydrogen2S and NH3Impact; Because the specific heat capacity of circulation oil is big, thereby greatly reduce the temperature rise of reactor, improve the efficient of utilizing of catalyst, and can reduce the side reaction such as cracking, simultaneously can the required amounts of hydrogen of protective reaction. One of characteristics of the present invention are to require to determine to sneak into amounts of hydrogen in the charging according to reaction, control amount of liquid and pressure in the reactor by control reactor capacity and discharge opeing amount.
The specific embodiment
As shown in Figure 1, Fig. 1 is the reactor that two beds are arranged, and reactor inlet 19 is arranged on reactor head.Reactor shown in Figure 1 comprises reactor shell 1 and two beds, i.e. first beds 8 and second beds 18,2 blenders, i.e. first blender 5 and second blender 15, wherein first blender 5 is arranged on reactor inlet 19 belows, second blender 15 is arranged between first beds 8 and second beds 18, first blender 5 and second blender 15 are provided with mixer entrance 20, molten hydrogen mixture outlet 21 and gas vent 6, reactor inlet 19 is arranged on the top of reactor and links to each other with the mixer entrance 20 of first blender 5 by tube connector 4, the molten hydrogen mixture outlet 21 of first blender 5 links to each other by tube connector 7 with first beds 8, and the gas vent 6 of first blender 5 extends to reactor shell 1 outside; 8 outlets of first beds link to each other by tube connector 9 with second mixer entrance 20, the molten hydrogen mixture outlet 21 of second blender 15 links to each other by tube connector 7 with second beds 18, reactor outlet 22 links to each other with outlet valve 11 by tube connector 10, reactor outlet 22 is arranged on reactor shell 1 bottom, is provided with recycle oil and hydrogen inlet 23 between first beds 8 and second beds 18.
As shown in Figure 2, Fig. 2 is the reactor that two beds are arranged, and reactor inlet 19 is arranged on reactor bottom.Reactor shown in Figure 2 comprises reactor shell 1 and two beds, i.e. first beds 8 and second beds 18,2 blenders, i.e. first blender 5 and second blender 15, wherein first blender 5 is arranged on reactor inlet 19 tops, second blender 15 is arranged between first beds 8 and second beds 18, first blender 5 and second blender 15 are provided with mixer entrance 20, molten hydrogen mixture outlet 21 and gas vent 6, reactor inlet 19 is arranged on the top of reactor and links to each other with mixer entrance 20 by tube connector 4, the molten hydrogen mixture outlet 21 of first blender 5 links to each other by tube connector 7 with first beds 8, and the gas vent 6 of first blender 5 extends to reactor shell 1 outside; 8 outlets of first beds link to each other by tube connector 9 with second mixer entrance 20, the molten hydrogen mixture outlet 21 of second blender 15 links to each other by tube connector 7 with second beds 18, reactor outlet 22 links to each other with outlet valve 11 by tube connector 10, reactor outlet 22 is arranged on reactor shell 1 top, is provided with recycle oil and hydrogen inlet 23 between first beds 8 and second beds 18.
Claims (30)
1. a reactor comprises reactor staving, beds, reactor inlet and reactor outlet, it is characterized in that: a blender is set in reactor at least, and blender is provided with inlet, the outlet of molten hydrogen mixture and gas vent.
2. according to the described reactor of claim 1, it is characterized in that: when a blender is set in the reactor, be arranged on reactor inlet, mixer entrance links to each other with reactor inlet, molten hydrogen mixture outlet links to each other with beds, and gas outlet tube extends to the reactor outside.
3. according to the described reactor of claim 1, it is characterized in that: when two above blenders are set in the reactor, one of them is arranged on reactor inlet, other are arranged between the beds, be arranged on the reactor inlet blender, mixer entrance links to each other with reactor inlet, and molten hydrogen mixture outlet links to each other with beds; Be arranged on the blender between the beds, mixer entrance links to each other with last beds outlet, and molten hydrogen mixture outlet links to each other with back one beds inlet; Gas outlet tube extends to the reactor outside.
4. according to the described reactor of claim 1, it is characterized in that: reactor outlet links to each other with outlet valve.
5. according to the described reactor of claim 1, it is characterized in that: recycle oil and hydrogen inlet are set between the reactor bed.
6. according to the described reactor of claim 1, it is characterized in that: reactor inlet is arranged on reactor top, and reactor outlet is arranged on reactor lower part.
7. according to the described reactor of claim 1, it is characterized in that: reactor inlet is arranged on reactor lower part, and reactor outlet is arranged on reactor top.
8. the application of the described reactor of claim 1 in the hydrocarbon ils liquid-solid two-phase hydrogenation, it is characterized in that: the blender that hydrogen, fresh feed oil and part recycle oil enter in the reactor forms the mixing logistics, liquid phase enters beds and contacts with catalyst, another part or whole recycle oil flow to into beds with hydrogen mixing formation mixture and contact with catalyst, the reaction effluent part is as recycle oil, beds is immersed in the liquid phase material, mix amounts of hydrogen in the logistics and be under the reaction condition saturated molten hydrogen amount of mixing logistics 1～30 times.
9. according to the described application of claim 8, it is characterized in that: the blender that hydrogen, solvent or diluent, fresh feed oil and part recycle oil enter in the reactor forms the mixing logistics.
10. according to the described application of claim 8, it is characterized in that: the reaction effluent part is deviate from hydrogen sulfide as recycle oil through stripping.
11. according to the described application of claim 8, it is characterized in that: another part or whole recycle oil mix formation and mix logistics discharge gas with hydrogen, liquid phase enters beds and contacts with catalyst.
12. according to the described application of claim 8, be characterised in that: the stripping medium that stripping is deviate from recycle oil hydrogen sulfide is inert gas or hydrogen.
13. according to the described application of claim 8, it is characterized in that: the stripping medium that stripping is deviate from recycle oil hydrogen sulfide is a hot high pressure hydrogen.
14. according to the described application of claim 8, it is characterized in that: it is long-pending in overall reactor to contain 0.1～15 volume % gas in the reactor.
15. according to the described application of claim 8, it is characterized in that: the mixture flow point is from going out gas, and liquid enters beds.
16. according to the described application of claim 8, it is characterized in that: amounts of hydrogen is 1.2～20 times of the saturated molten hydrogen amount of mixing logistics under reaction condition in the mixing logistics.
17. use according to claim 8 or 14 described, it is characterized in that: amounts of hydrogen is 1.5～10 times of the saturated molten hydrogen amount of mixing logistics under reaction condition in the mixing logistics.
18. according to the described application of claim 8, it is characterized in that: solvent or diluent are at least a in the hydrocarbon ils behind heavy naphtha, naphtha, lighter hydrocarbons, light distillate, diesel oil, VGO and the hydrogenation.
19. according to the described application of claim 8, it is characterized in that: fresh feed oil is the cut of hydrocarbon ils or hydrocarbon ils.
20., it is characterized in that: at least a in fresh feed oilstone oil distillate, distillate, diesel oil, deasphalted oil, residual oil, lubricating oil, liquefied coal coil and shale oil or its product according to the described application of claim 8.
21., it is characterized in that according to the described application of claim 8: remove a kind of pollutant in sulphur in the hydrocarbon ils, nitrogen, oxygen, the metal impurities at least, and saturated aromatic hydrocarbons, and the molecular structure of change hydrocarbon ils.
22. according to the described application of claim 8, it is characterized in that: the volume ratio of recycle oil and fresh feed oil is 0.1: 1～20: 1.
23. according to claim 8 or 22 described application, it is characterized in that: the volume ratio of recycle oil and fresh feed oil 0.5: 1～15: 1.
24., it is characterized in that: the pressure that utilizes the amount control reactor that enters hydrogen in the blender according to the described application of claim 8.
25., it is characterized in that: utilize to enter the pressure that the blender gas vent is discharged gas flow control reactor according to the described application of claim 8.
26., it is characterized in that: utilize reactor outlet to discharge the interior liquid level of amount control reactor of reaction effluent according to the described application of claim 8.
27., it is characterized in that: utilize the liquid level in the reactor outlet valve control reactor according to the described application of claim 8.
28. according to the described application of claim 8, it is characterized in that: the blender that hydrogen, solvent or diluent, fresh feed oil and recycle oil enter in the reactor forms mixing logistics discharge gas, and molten hydrogen mixture contacts with catalyst.
29. according to the described application of claim 8, it is characterized in that: catalyst is Hydrobon catalyst, catalyst for hydro-upgrading, hydrotreating catalyst or hydrocracking catalyst.
30. according to the described application of claim 6, it is characterized in that: hydrogenation conditions is: reaction temperature is 150～450 ℃, and reaction pressure is 1～17MPa, and volume space velocity is 0.5～15h during liquid
-1
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| CN106693841A (en) * | 2017-03-03 | 2017-05-24 | 洛阳凯美胜石化设备有限公司 | Liquid phase hydrogenation reactor and liquid phase hydrogenation process |
| US9862896B2 (en) | 2012-09-21 | 2018-01-09 | China Petroleum & Chemical Corporation | Hydrocarbon oil hydrotreating method |
| CN112705120A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Heavy oil processing device and processing method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050082202A1 (en) * | 1997-06-24 | 2005-04-21 | Process Dynamics, Inc. | Two phase hydroprocessing |
| CN101194001A (en) * | 2005-03-24 | 2008-06-04 | 过程动力学公司 | Control system method and apparatus for continuous liquid phase hydroprocessing |
| CN101280217A (en) * | 2008-06-02 | 2008-10-08 | 中国石油化工集团公司 | Liquid-solid two-phase hydrogenation method for hydrocarbon oil |
-
2009
- 2009-08-11 CN CN2009100657224A patent/CN101992048A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050082202A1 (en) * | 1997-06-24 | 2005-04-21 | Process Dynamics, Inc. | Two phase hydroprocessing |
| CN101194001A (en) * | 2005-03-24 | 2008-06-04 | 过程动力学公司 | Control system method and apparatus for continuous liquid phase hydroprocessing |
| CN101280217A (en) * | 2008-06-02 | 2008-10-08 | 中国石油化工集团公司 | Liquid-solid two-phase hydrogenation method for hydrocarbon oil |
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