CN1552812A - Deep desulphurizing and dearomating process for diesel oil - Google Patents
Deep desulphurizing and dearomating process for diesel oil Download PDFInfo
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Abstract
The invention relates to deep desulfurization and dearomatization of diesel fuel. A conventional co-current hydrofining reactor is connected with deep hydrodesulfurization and dearomatization reactors. Raw oil gets through the conventional hydrofining reactor firstly, reacted liquid phase material is mixed with fresh hydrogen to feed into the tops of deep hydrodesulfurization and dearomatization reactors, taking gas-liquid co-current hydrogenation, and then, reacted material is separated in gas-liquid separating zone. Gas phase is discharged and fed into the conventional hydrofining reactor, and liquid phase flows down to contact with fresh hydrogen inlet from the bottom of the reactor, finally, refined product is discharged from the bottom of the reactor. The invention process eliminates hepatic gas etc. impurity influence to arena saturation reaction in deep hydrodesulfurization and dearomatization reacting system of process now available, utilizes fully fresh hydrogen resource in the system, improves system reacting activity, usability of different raw oil, controllability and stability of counter- current hydrogenation reaction, and has better flexibility.
Description
Technical field
The present invention relates to a kind of hydrocarbon hydroprocessing technique, a kind of specifically hydrogenation technique of gas, liquid, solid three-phase diesel oil distillate is improved one's methods.
Background technology
Along with the continuous reinforcement of people's environmental consciousness and diesel motor day by day to its fuel used proposition requirements at the higher level, produce and use clean fuel worldwide to present accelerated development trend.Diesel oil cleaning process most critical and the most difficult be deep removal sulphur and aromatic hydrocarbons wherein.Be meeting the market requirement, each company of great oil refining of the world is all in the Technology of active development with research energy deep removal diesel oil sulphur and aromatic hydrocarbons.
At present, more employing hydrogen of diesel oil hydrogenation technology and hydrocarbon raw material also flow to current downflow, contact and carry out the fixed bed hydrogenation technology of catalyzed reaction with beds, but the hydrogen sulfide that generates in the reaction process, ammonia and hydro carbons small molecules can further react this technology, as desulfurization, denitrogenation, aromatic hydrocarbons is saturated and hydrocracking etc. has bigger restraining effect, and speed of reaction is descended.Therefore segmentation hydrogenation and/or gas-liquid counter current hydrogenation technique more and more become the emphasis of refining of petroleum area research, and the hydrogen dividing potential drop that this technology can augmenting response is in time removed the H that reaction produces
2S, NH
3
USP 5,985, and 135 propose the two-stage hydrogenation method of a kind of up-flow reactor and downflow reactor, wherein connect a stripper plant in the first stage reactor back.But this technology does not still fundamentally solve the problem that removes of obnoxious flavour, and investment is bigger.In order fundamentally to solve the problem that removes of obnoxious flavour, more oil refinery company is at research gas-liquid counter current hydrogenation technique.USP 5,183, proposed the countercurrent hydrogenation purification techniques in 556: stock oil and hydrogen at first and flow to into first reaction zone and react, a part will contain the H that responds and produce in the middle of reactor
2S, NH
3Hydrogen and the charging of vaporization draw, vaporization feeding does not enter second reaction zone, reacts with the hydrogen counter current contact that reactor bottom is introduced.The gas phase material of drawing enters separator after cooling separates oil gas, and hydrogen-containing gas purifies the back and uses as recycle hydrogen, and liquid phase then first reaction zone or second reaction zone of Returning reactor continues reaction.Desulfurization degree and Tuo Fang that this technology has improved diesel oil greatly lead.But also there is shortcoming in this technology, does not promptly think over desulfurization and takes off the dynamic behavior of arylation reaction.Test-results shows: general desulfurization degree is when 98% left and right sides, and the fragrant rate of taking off of stock oil is about 55%～60% only, that is to say that sulphur removes than aromatic hydrocarbons is easy.Therefore, at USP 5,183, in 556 Technologies that propose, the H of first reaction zone
2The S isoconcentration can be higher, influence the arene engaging scraping in the stock oil greatly, if will finish the deep removal of aromatic hydrocarbons, will certainly improve the processing treatment load of second reaction zone greatly, not to increase the catalyst loading volume, increase the packing density of catalyzer exactly, operation is disadvantageous to this operating method to gas-liquid counter current again conversely.
Summary of the invention
In order to improve the deficiency of existing hydrocarbon raw material gas-liquid counter current hydrogenation technique, the present invention has proposed a kind of novel gas-liquid countercurrent hydrogenation technology from the desulfurization angle different with taking off arylation reaction speed, and technology of the present invention has the saturated function of higher desulfurization, denitrogenation and aromatic hydrocarbons.
Diesel deep desulfurization of the present invention, take off aromatic hydrocarbons technology and comprise conventional gas and liquid flowing hydrofining reactor and deep hydrodesulfurizationof, take off the aromatic hydrocarbons reactor, concrete technical scheme is as follows:
(1) stock oil and hydrogen with and stream mode carry out hydrogenation reaction by hydrofining reactor, reaction effluent enters high-pressure separator and carries out gas-liquid separation.Decide the liquid phase separation amount of high-pressure separator according to desired product character.
(2) liquid phase material of the high-pressure separator in the step (1) mixes the back with new hydrogen and enters deep hydrodesulfurizationof from the top, takes off the aromatic hydrocarbons reactor.Deep hydrodesulfurizationof, to take off aromatic hydrocarbons reactor top be gas and liquid flowing reaction, and reacting rear material separates in gas-liquid separation zone, contains the H that responds and produce
2S, NH
3Hydrogen and the gaseous phase materials of vaporization draw, the hydrofining reactor that enters in the step (1) carries out hydrogenation reaction.
(3) the isolated not material of vaporization of gas-liquid separation zone continues to flow downward in the step (2), at deep hydrodesulfurizationof, take off the aromatic hydrocarbons reactor lower part and carry out hydrogenation reaction with the new hydrogen counter current contact of introducing from reactor bottom, upwards the material of mobile hydrogen and vaporization in the vapor-liquid separation district with and the gas phase that flows Reaction Separation draw reactor jointly, the liquid phase that flows downward is discharged by the bottom of reactor and is obtained cleaning product.
The inventive method with conventional unifining process and deep hydrodesulfurizationof, take off the aromatic hydrocarbons process and combine, increased desulfurization and taken off the aromatic hydrocarbons degree of depth on the one hand, can effectively reduce the counter-flow reaction zone loaded catalyst on the other hand, improve the handiness and the stability of counter-current operation greatly.Technology of the present invention solved deep hydrodesulfurizationof in the existing technology, take off in the aromatic hydrocarbons reactive system impurity such as hydrogen sulfide to the influence of aromatic hydrocarbons saturated reaction, and the new hydrogen resource of the system that made full use of has improved the reactive behavior of system.Technical process of the present invention is flexible, can process the stock oil of various character, has improved the suitability of this technology.
Description of drawings
Fig. 1 is that a kind of process flow diagram of the present invention and Fig. 2 are in addition two kinds of process flow diagrams of the present invention, and Fig. 3 is the process flow diagram of the countercurrent hydrogenation that adopted in the comparative example of the present invention.
Embodiment
Conventional in the technology of the present invention and to flow the catalyzer that loads in the hydrogenator be the catalyzer with stronger hydrogenating desulfurization, hydrodenitrification, the saturated aromatic hydrocarbons of hydrogenation and/or hydrocracking function.This class catalyzer generally all is with porous inorganic oxide such as aluminum oxide, silicon oxide, aluminium oxide-silicon oxide and/or zeolite molecular sieve, is carrier as super steady Y, β, X type, Y type and mordenite etc., also can be the mixture of aforementioned substances.Active ingredient is group vib and/or VIII family metal such as W, Mo, Co, Ni etc., also can optionally add the catalyzer of other various auxiliary agents such as P, Ti, elements such as F, B.
Deep hydrodesulfurizationof, the catalyzer that takes off aromatic hydrocarbons reactor middle and upper part and flow conversion zone filling are the catalyzer with hydrogenating desulfurization, hydrodenitrification, the saturated aromatic hydrocarbons of hydrogenation and/or hydrocracking function.This class catalyzer generally all is with porous inorganic oxide such as aluminum oxide, silicon oxide, aluminium oxide-silicon oxide and/or zeolite molecular sieve, is carrier as super steady Y, β, X type, Y type and mordenite etc., also can be the mixture of aforementioned substances.Active ingredient is the metal of group vib and/or VIII family such as W, Mo, Co, Ni etc., and its existence form is mainly oxide morphology.
Deep hydrodesulfurizationof, the catalyzer that takes off aromatic hydrocarbons reactor lower part gas-liquid counter current conversion zone filling are the catalyzer with hydrogenating desulfurization, hydrodenitrification, the saturated aromatic hydrocarbons of hydrogenation and/or hydrocracking function.This class catalyzer generally all is with porous inorganic oxide such as aluminum oxide, silicon oxide, aluminium oxide-silicon oxide and/or zeolite molecular sieve, is carrier as super steady Y, β, X type, Y type and mordenite etc., also can be the mixture of aforementioned substances.Active ingredient is the metal of precious metals such as Pt, Pd or group vib and/or VIII family, its existence form can be they go back ortho states, sulfide, nitride or carbide etc.
Operational condition of the present invention is the processing condition that are fit to hydrocarbons hydrogenation.Operation condition conventional and that flow hydrofining reactor is generally: 240～427 ℃ of temperature of reaction; Reaction pressure is 1.0～20.0MPa; Hydrogen to oil volume ratio is 100～1000; Volume space velocity is 0.1-7.5h during liquid
-1Be preferably: 280～395 ℃ of temperature of reaction; Reaction pressure is 3.0～12.0MPa; Hydrogen to oil volume ratio is 300～800; Volume space velocity is 0.5-4.5h during liquid
-1
Deep hydrodesulfurizationof, the operational condition of taking off the gas and liquid flowing conversion zone on aromatic hydrocarbons top are generally: 240～427 ℃ of temperature of reaction; Reaction pressure is 1.0～20.0MPa; Hydrogen to oil volume ratio is 100～1000; Volume space velocity is 0.1-10.0h during liquid
-1Be preferably: 240～390 ℃ of temperature of reaction; Reaction pressure is 3.0～12.0MPa; Hydrogen to oil volume ratio is 100～500; Volume space velocity is 0.5-7.5h during liquid
-1
Deep hydrodesulfurizationof, the operational condition of taking off the gas-liquid counter current conversion zone of aromatic hydrocarbons bottom are generally: 200～427 ℃ of temperature of reaction; Reaction pressure is 1.0～20.0MPa; Hydrogen to oil volume ratio is 50～1000; Volume space velocity is 0.1-10.0h during liquid
-1Be preferably: 200～380 ℃ of temperature of reaction; Reaction pressure is 3.0～12.0MPa; Hydrogen to oil volume ratio is 50～500; Volume space velocity is 0.5-7.5h during liquid
-1
Above-mentioned catalyzer and processing condition are the general selection in this field, and concrete catalyzer and operational condition can be adjusted according to concrete stock oil boiling range scope, character and processing purpose.Temperature, pressure, the hydrogen-oil ratio of general light ends hydrotreatment are lower, and air speed is bigger, and the temperature of heavy ends hydrotreatment, pressure, hydrogen-oil ratio are higher, and air speed is less.In addition, the concrete selection of catalyzer also can be determined according to the sulphur content in the raw material, aromaticity content, product property requirement etc.
Because reaction of the present invention all is a strong exothermal reaction, therefore, should squeeze into refrigerant, to reduce the reaction temperature difference in the reactor in the differential responses section of device for the quiet run of assurance device.Conventional hydrofining reactor in the step (1) can use cold hydrogen to lower the temperature, deep hydrodesulfurizationof in the step (2), take off the aromatic hydrocarbons reactor and flow reaction zone and can use cold hydrogen or quenching oil cooling, counter-flow reaction zone is preferably used the quenching oil cooling.Quenching oil of the present invention can be the various diesel cut, but the reaction overhead product of hydrogenation unit of the present invention preferably.
The present invention be applicable to all kinds of diesel oil deep hydrodesulfurizationof, take off virtue, as catalytic cracking diesel oil, coker gas oil, straight-run diesel oil etc. and their mixture.
The present invention is described in detail below in conjunction with drawings and Examples.
The process flow diagram particular case of countercurrent hydrogenation described in the embodiment of the invention is as follows: the new hydrogen that comes from compressor is divided into three the tunnel 1,2,3, and wherein 3 is hydrogen make-up of recycle hydrogen, just uses in case of necessity.Stock oil 4 with at first enter routine and flow hydrogenator B after recycle hydrogen 10 mixes.After this reactor reaction finishes, reactant flow enters separator 9 through pipeline 8 and carries out gas-liquid separation, hydrogen-rich gas uses as recycle hydrogen after purifying treatment, and the liquid phase hydro carbons after separating via pipeline 6 enter deep hydrodesulfurizationof again with after new hydrogen 1 mixes, take off in the aromatic hydrocarbons reactor A and flow reaction zone C continuation hydrogenation reaction.Reaction finishes the back H that contains the generation that responds of autoreaction district C in the future
2S, NH
3Hydrogen and the hydro carbons of vaporization draw through pipeline 5, enter conventional hydrofining reactor B with stock oil 4 and proceed hydrogenation reaction.And and flow the effusive liquid phase hydro carbons of reaction zone C and continue to flow downward, enter the counter-flow reaction zone D of deep hydrodesulfurizationof, denitrification reactor A and the new hydrogen counter current contact of reactor bottom introducing and carry out catalyzed reaction, materials such as sulphur that further deep removal is residual and aromatic hydrocarbons.Final cleaning product via deep hydrodesulfurizationof, take off aromatic hydrocarbons reactor A bottom line 7 and discharge, the gas phase hydro carbons remix of telling with separator 9 is formed full cut together.
Certainly the present invention can change to the flow process of Fig. 1 the flow process of Fig. 2 according to arts demand.
Fig. 2 is that the refinery is when needing, separator among Fig. 19 can be divided into two 9,11, wherein separator 11 is used to isolate lighter hydro carbons 12, it can return counter-current reactor A's and flow reaction zone C, also can be used as the counter-flow reaction zone D that cold oil returns counter-current reactor A.
Following embodiment further specifies of the present invention, and embodiment uses technical process shown in Figure 1, and comparative example uses technical process shown in Figure 3.
The main hydrogenation effect of investigating hydrogenation technique of the present invention and existing countercurrent hydrogenation technology of this test.With diesel fuel desulfurization, to take off virtue be example.In this test the catalyst system therefor physico-chemical property see Table～1, stock oil character sees Table～2.Hydrogenation reaction is all carried out in this test on the long run test device.Embodiment sees Table～and 3, comparative example sees Table～and 4.
Table～1 catalyzer physico-chemical property
| The catalyzer numbering | CAT1 | CAT2 | ????CAT3 |
| Catalytic active component | Mo, W (sulfide) (atomic ratio 1: 1) | Pt, Pd (atomic ratio 1: 1) | CoMoN x(Co and Mo atomic ratio 1: 3) |
| Shape | Trifolium | Bar shaped | Bar shaped |
| Diameter, mm | 3.08 | 1.9 | ????1.9 |
| Specific surface area, m 2/g | 125 | 140 | ????158 |
| Metal component, w% | 29 | 0.8 | ????26 |
| Carrier | Aluminum oxide | The USY molecular sieve | Contain silicon-dioxide 4w% aluminum oxide |
Table～2 stock oil main character
| Density, g/cm 3 | ????0.8824 |
| S，μg/g | ????6979 |
| N，μg/g | ????1014 |
| Aromatic hydrocarbons, w% | ????48.6 |
| Boiling range, ℃ | ????185～373 |
Table～3 embodiment experimental results
| Embodiment | ????????????????1 | ??????????????2 | ????????????????3 | ||||||
| Reaction zone | ??B | ????C | ??D | ??B | ??C | ?D | ????B | ????C | ????D |
| Catalyzer | ??CAT1 | ????CAT1 | ??CAT2 | ??CAT1 | ??CAT1 | ?CAT2 | ????CAT1 | ????CAT1 | ????CAT2 |
| Operational condition | |||||||||
| Reaction pressure, MPa | ????????????????4.0 | ??????????????6.0 | ?????????????????8.0 | ||||||
| Temperature of reaction, ℃ | ??340 | ????350 | ??340 | ??360 | ??340 | ??340 | ????380 | ?????360 | ??350 |
| Air speed, h -1 | ??1.8 | ????4.0 | ??2.0 | ??1.8 | ??4.0 | ??2.0 | ????1.8 | ?????4.0 | ??2.0 |
| Hydrogen to oil volume ratio | ??300 | ????200 | ??200 | ??400 | ??200 | ??200 | ????500 | ?????150 | ??150 |
| Generate oil nature | |||||||||
| Density, g/cm 3 | ????0.8358 | ??0.8358 | ????0.8359 | ||||||
| ?S，μg/g | ????2.2 | ??1.6 | ????1.0 | ||||||
| ?N，μg/g | ????1.0 | ??1.0 | ????1.0 | ||||||
| Aromatic hydrocarbons, w% | ????11.3 | ??10.1 | ????9.8 | ||||||
Table～4 comparative example experimental results
| Comparative example | ????????????????1 | ????????????????2 | ????????????????3 | ||||||
| Reaction zone | ????B | ????C | ????D | ????B | ????C | ????D | ????B | ????C | ????D |
| Catalyzer | ????CAT1 | ????CAT1 | ?CAT2 | ????CAT1 | ????CAT1 | ????CAT2 | ????CAT1 | ????CAT1 | ????CAT2 |
| Operational condition | |||||||||
| Pressure, MPa | ????????????????4.0 | ????????????????6.0 | ????????????????8.0 | ||||||
| Temperature of reaction, ℃ | ????340 | ????350 | ????340 | ????360 | ????340 | ????340 | ????380 | ????360 | ????350 |
| Air speed, h -1 | ????1.8 | ????4.0 | ????2.0 | ????1.8 | ????4.0 | ????2.0 | ????1.8 | ????4.0 | ????2.0 |
| Hydrogen to oil volume ratio | ????300 | ????200 | ????200 | ????400 | ????200 | ????200 | ????500 | ????150 | ????150 |
| Generate oil nature | |||||||||
| Density, g/cm 3 | ????0.8356 | ????0.8356 | ????0.8357 | ||||||
| ?S，μg/g | ????19.9 | ????18.7 | ????15.9 | ||||||
| ?N，μg/g | ????1.0 | ????1.0 | ????1.0 | ||||||
| Aromatic hydrocarbons, w% | ????16.8 | ????14.6 | ????13.8 | ||||||
By experimental result as seen, hydrogenation effect of the present invention is greater than existing countercurrent hydrogenation technology.
The main hydrogenation effect of investigating hydrogenation technique of the present invention and existing countercurrent hydrogenation technology of this test.With diesel fuel desulfurization, to take off virtue be example.In this test the catalyst system therefor physico-chemical property see Table～1, stock oil character sees Table～2.Hydrogenation reaction is all carried out in this test on the long run test device.Embodiment sees Table～and 5, comparative example sees Table～and 6.
Table～5 embodiment experimental results
| Embodiment | ????4 | ????????????????5 | ????????????????6 | ||||||
| Reaction zone | ????B | ????C | ????D | ????B | ????C | ????D | ????B | ????C | ????D |
| Catalyzer | ????CAT1 | ????CAT1 | ????CAT3 | ????CAT1 | ????CAT1 | ????CAT3 | ???CAT1 | ????CAT1 | ????CAT3 |
| Operational condition | |||||||||
| Pressure .MPa | ????????????????4.0 | ????6.0 | ????????????????8.0 | ||||||
| Temperature, ℃ | ????340 | ????350 | ????340 | ????360 | ????340 | ????340 | ????380 | ????360 | ????350 |
| Air speed, h -1 | ????1.8 | ????4.0 | ????2.0 | ????1.8 | ????4.0 | ????2.0 | ????1.8 | ????4.0 | ????2.0 |
| Hydrogen-oil ratio | ????300 | ????200 | ????200 | ????400 | ????200 | ????200 | ????500 | ????150 | ????150 |
| Generate oil nature | |||
| Density, g/m 3 | ????0.8358 | ????0.8358 | ????0.8359 |
| ?S，μg/g | ????12.5 | ????11.9 | ????11.3 |
| ?N，μg/g | ????1.0 | ????1.0 | ????1.0 |
| Aromatic hydrocarbons, w% | ????11.7 | ????10.8 | ????10.2 |
Table～6 comparative example experimental results
| Comparative example | ????????????????4 | ????????????????5 | ????????????????6 | ||||||
| Reaction zone | ????B | ????C | ????D | ????B | ????C | ????D | ????B | ????C | ????D |
| Catalyzer | ????CAT1 | ????CAT1 | ????CAT3 | ????CAT1 | ????CAT1 | ????CAT3 | ????CAT1 | ????CAT1 | ????CAT3 |
| Operational condition | |||||||||
| Reaction pressure | ????????????????4.0 | ????????????????6.0 | ????????????????8.0 | ||||||
| Temperature of reaction | ????340 | ????350 | ????340 | ????360 | ????340 | ????340 | ????380 | ????360 | ????350 |
| Air speed | ????1.8 | ????4.0 | ????2.0 | ????1.8 | ????4.0 | ????2.0 | ????1.8 | ????4.0 | ????2.0 |
| Hydrogen-oil ratio | ????300 | ????200 | ????200 | ????400 | ????200 | ????200 | ????500 | ????150 | ????150 |
| Generate oil nature | |||||||||
| Density, g/cm 3 | ????0.8356 | ????0.8352 | ????0.8359 | ||||||
| ?S，μg/g | ????20.5 | ????17.2 | ????17.5 | ||||||
| ?N，μg/g | ????3.8 | ????2.4 | ????1.0 | ||||||
| Aromatic hydrocarbons, w% | ????18.2 | ????16.6 | ????15.2 | ||||||
By experimental result as seen, hydrogenation effect of the present invention is greater than existing countercurrent hydrogenation technology.
Claims (10)
1, a kind of diesel deep desulfurization, take off aromatic hydrocarbons technology, comprise gas and liquid flowing hydrofining reactor and deep hydrodesulfurizationof, take off the aromatic hydrocarbons reactor, it is characterized in that adopting following technical scheme:
(1) stock oil and hydrogen with and stream mode carry out hydrogenation reaction by hydrofining reactor, reaction effluent enters high-pressure separator and carries out gas-liquid separation;
(2) liquid phase material of the high-pressure separator in the step (1), mixing the back with new hydrogen enters deep hydrodesulfurizationof, takes off the aromatic hydrocarbons reactor from the top, deep hydrodesulfurizationof, to take off aromatic hydrocarbons reactor top be gas and liquid flowing reaction, and reacting rear material separates in gas-liquid separation zone, contains the H that responds and produce
2S, NH
3Hydrogen and the gaseous phase materials of vaporization draw, enter the hydrofining reactor in the step (1);
(3) the isolated not material of vaporization of gas-liquid separation zone continues to flow downward in the step (2), at deep hydrodesulfurizationof, take off the aromatic hydrocarbons reactor lower part and carry out hydrogenation reaction with the new hydrogen counter current contact of introducing from reactor bottom, upwards the material of mobile hydrogen and vaporization in gas-liquid separation zone with and the gas phase that flows Reaction Separation draw reactor jointly, the liquid phase that flows downward is discharged by the bottom of reactor and is obtained cleaning product.
2, according to the described technology of claim 1, it is characterized in that operation condition described and the stream hydrofining reactor is: 240～427 ℃ of temperature of reaction, reaction pressure is 1.0～20.0MPa, and hydrogen to oil volume ratio is 100～1000, and volume space velocity is 0.1～7.5h during liquid
～1
3, according to the described technology of claim 2, it is characterized in that operation condition described and the stream hydrofining reactor is: 280～395 ℃ of temperature of reaction, reaction pressure is 3.0～12.0MPa, and hydrogen to oil volume ratio is 300～800, and volume space velocity is 0.5～4.5h during liquid
～1
4, according to the described technology of claim 1, the operational condition of it is characterized in that described deep hydrodesulfurizationof, taking off the gas and liquid flowing conversion zone on aromatic hydrocarbons top is: 240～427 ℃ of temperature of reaction, reaction pressure is 1.0～20.0MPa, hydrogen to oil volume ratio is 100～1000, and volume space velocity is 0.1～10.0h during liquid
～1
5, according to the described technology of claim 4, the operational condition of it is characterized in that described deep hydrodesulfurizationof, taking off the gas and liquid flowing conversion zone on aromatic hydrocarbons top is: 240～390 ℃ of temperature of reaction, reaction pressure is 3.0～12.0MPa, hydrogen to oil volume ratio is 100～500, and volume space velocity is 0.5～7.5h during liquid
～1
6, according to the described technology of claim 1, the operational condition of it is characterized in that described deep hydrodesulfurizationof, taking off the gas-liquid counter current conversion zone of aromatic hydrocarbons bottom is: 200～427 ℃ of temperature of reaction, reaction pressure is 1.0～20.0MPa, hydrogen to oil volume ratio is 50～1000, and volume space velocity is 0.1～10.0h during liquid
～1
7, according to the described technology of claim 6, the operational condition of it is characterized in that described deep hydrodesulfurizationof, taking off the gas-liquid counter current conversion zone of aromatic hydrocarbons bottom is: 200～380 ℃ of temperature of reaction, reaction pressure is 3.0～12.0MPa, hydrogen to oil volume ratio is 50～500, and volume space velocity is 0.5～7.5h during liquid
～1
8, according to the described technology of claim 1, the alumina catalyst, silicon oxide, aluminum oxide～silicon oxide and/or the zeolite molecular sieve that it is characterized in that described deep hydrodesulfurizationof, take off aromatic hydrocarbons reactor lower part gas-liquid counter current conversion zone filling are carrier, active ingredient is Pt, Pd precious metal or group vib and/or VIII family metal, its existence form be they go back ortho states, sulfide, nitride or carbide.
9, according to the described technology of claim 1, the counter-flow reaction zone use quenching oil cooling that it is characterized in that described deep hydrodesulfurizationof, takes off the aromatic hydrocarbons reactor, quenching oil is the reaction overhead product.
10,, it is characterized in that described stock oil comprises catalytic cracking diesel oil, coker gas oil, straight-run diesel oil or their mixture according to the described technology of claim 1.
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| CN102876364B (en) * | 2011-07-11 | 2014-12-31 | 中国石油化工股份有限公司 | Hydrotreatment method |
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| US5183556A (en) * | 1991-03-13 | 1993-02-02 | Abb Lummus Crest Inc. | Production of diesel fuel by hydrogenation of a diesel feed |
| JP4785250B2 (en) * | 1998-12-08 | 2011-10-05 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | Production of low sulfur / low aromatic distillate |
| US6514403B1 (en) * | 2000-04-20 | 2003-02-04 | Abb Lummus Global Inc. | Hydrocracking of vacuum gas and other oils using a cocurrent/countercurrent reaction system and a post-treatment reactive distillation system |
| CN1173012C (en) * | 2001-10-30 | 2004-10-27 | 中国石油化工股份有限公司 | Method of desulfurizing and dearomatizing diesel oil deeply |
| CN1175090C (en) * | 2001-10-30 | 2004-11-10 | 中国石油化工股份有限公司 | Method for producing the clean diean diesel oil with low sulfur and low arene |
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