CN1488712A - Diesel oil hydrotreating method - Google Patents
Diesel oil hydrotreating method Download PDFInfo
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Abstract
The present invention relates to a gas-liquid counter-current diesel oil hydrogenation process. It adopts two or more than two catalyst bed layers whose catalyst activity can be progressively raised along liquid folloiwng direction and void volume of the catalyst bed layer is progressively increased, in which the high activity hydrogenation treatment catalyst is one or several kinds selected from reducing metal catalyst, noble metal catalyst, nitride or carbide catalyst of molybdenum, nickel and tungsten and non-noble metal sulfide catalyst in which the sulfur is not easy to be lost, and the void volume of the catalyst bed layer positioned in top of reactor is 0.25-0.55, and the void volume of the catalyst bed layer positioned in the bottom portion of the reactor is 0.35-0.90. Said invention can utilize diesel oil to produce clean fuel.
Description
1, technical field
The present invention relates to a kind of hydrocarbon hydroprocessing technique, a kind of specifically gas, liquid, solid three-phase diesel oil hydrogenation improved technological process.
2, background technology
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, but identical with other existing counter-current operation device, the countercurrent reaction section all adopts single catalyzer, or non-noble metal sulfide catalyst or noble metal catalyst.This catalyst loading scheme is not suitable for the deep desulfuration of stock oil, the processing treatment of taking off virtue.Reason is: the big more speed that it further reacts of stock oil reaction depth is more little, certainly will need highly active catalyzer in order to reach product requirement, as the saturated noble metal catalyst that preferably uses of aromatic hydrocarbons, if but in the whole beds of counter-current operation, used high activated catalyst such as noble metal catalyst, the catalyzer on countercurrent reaction section top could easily make catalyst deactivation because of the high hydrogen sulfide dividing potential drop.Otherwise, can reduce because of the low in hydrogen sulphide dividing potential drop easily makes catalyzer lose the sulphur activity in the bottom of countercurrent reaction section, until there not being activity if whole adverse current beds uses conventional base metal sulfide catalyst.
In addition, diesel deep desulfurization, to take off arylation reaction be to carry out under liquid phase state, in order to guarantee the efficiency factor of catalyzer, generally can only adopt catalyst particle, this type of beds voidage of industrial application is generally 0.35-0.45, and is more much smaller than the voidage (＞0.95) of the counter-current operation of routine.Reactor at so big or small bed voidage carries out counter-current operation, easily produces liquid flooding, causes the device running unstable.USP5,985,131, propose have the catalyst loading method of gas bypassing to avoid liquid flooding among the USP 6,007,787.Though this invention can reduce the liquid holdup of reactor, suitably increased the scope of reactor gas-liquid operation, but it does not have to associate with the gas-liquid distribution of whole reactor, still be easy to generate liquid flooding, the utilization ratio of reactor is not high yet in addition, hydrocarbons hydrogenation is handled so large-scale reactor, and operability is lower.
3, summary of the invention
In order to improve the deficiency of existing hydrocarbon raw material gas-liquid counter current hydrogenation technique, the present invention provides a kind of gas-liquid counter current hydrogenation technique of catalyzer grading loading from catalyzer and catalyst loading aspect, technology of the present invention has the saturated function of higher desulfurization, denitrogenation and aromatic hydrocarbons.
Concrete technical scheme of the present invention is as follows: under the diesel oil fraction hydrogenating treatment condition, hydrogen and diesel raw material oil are reverse by beds, and promptly recycle hydrogen is entered by reactor bottom, discharges from reactor head, liquid phase from top to bottom with the recycle hydrogen countercurrent flow, discharge from reactor bottom.Wherein whole beds is divided into plural beds at least by voidage and hydrogenation activity different, and the voidage of beds reduces gradually along the flow direction of liquid phase, and activity of such catalysts improves gradually along the liquid phase flow direction.(1) loads the highly active catalyzer of easy sulfur poisoning in the bottom of gas, liquid counter-current operation reactor, as in the nitride of as-reduced metal catalyzer, noble metal catalyst, molybdenum nickel tungsten etc. or the carbide catalyst etc. one or more, also can be the base metal sulfide catalyst that is difficult for losing sulphur.Its granularity is regular particle size, low voidage, can certainly make the catalyzer of big voidage, preferentially selects regular particle size, low voidage, form low voidage, the high activated catalyst bed.Voidage is generally 0.25～0.55, and preferred 0.30～0.50.
(2) from the diesel raw material oil-in, conversion zone along the paramount active catalyst bed of liquid phase feed oil flow direction loads conventional base metal sulfurized high voidage thing catalyzer, is used to form to be difficult for beds sulfur poisoning, high voidage, low catalytic activity.Voidage is generally 0.35～0.90, and preferred 0.45～0.80.
The present invention is by investigating the factor that impurities concentration distribution such as hydrogen sulfide in diesel oil gas, the liquid countercurrent reaction procedures system and variation and liquid flooding produce, use catalyzer of different nature in different zones, optimized the service area of different activities catalyzer, different catalysts is moved under its top condition, also optimized the device turndown ratio, both improve the activity of whole beds, the more important thing is the stability that has prolonged the catalyst life cycle and increased device.
4, embodiment
The present invention has increased the whole catalytic activity and the device run stability of counter-current operation device by the hydrogenation activity and the voidage grating of catalyzer.Have stronger hydrogenating desulfurization, hydrodenitrification, the saturated aromatic hydrocarbons of hydrogenation and/or hydrocracking function at the catalyzer described in (1).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.Active ingredient is the nitride of the as-reduced metal of group vib and/or VIII family or its sulfide, precious metals such as Pt, Pd, molybdenum nickel tungsten etc. or carbide etc.
Be conventional catalyst than low activity catalyst described in (2) 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.The oxide compound of group vib and/or VIII family metal oxide such as W, Mo, Co, Ni etc. is an active ingredient, optionally adds the catalyzer of other various auxiliary agents such as P, Si, elements such as F, B.
The catalyzer voidage from top to bottom reduces gradually with the enhancing of catalyst hydrogenation activity, can select two or more different voidages.The voidage of low voidage, high hydrogenation activity beds is generally 0.25～0.55, preferred 0.30～0.50, big voidage, low hydrogenation activity beds voidage are generally 0.35～0.90, preferred 0.45～0.80, the centre can be provided with the beds of voidage between upper strata and bottom voidage as required.
Different beds voidages need adopt the catalyzer of different shapes and granularity, and the catalyzer of low voidage, high hydrogenation activity beds can be selected the catalyzer of regular particle size, shape for use, as sphere, bar shaped, trifolium, Herba Galii Bungei etc.Spherical diameter is generally 1.0mm～3.0mm, and the diameter of bar shaped, trifolium, Herba Galii Bungei is generally 1.0mm～2.5mm, and length is 3.0～8.0mm.Big voidage, low hydrogenation activity beds catalyzer adopt special-shaped catalyst, as the bar shaped of annular, wheel shape, sphere with holes or volume particle size, trifolium, Herba Galii Bungei etc., spherical diameter is generally 1.5mm～6.0mm, the diameter of bar shaped, trifolium, Herba Galii Bungei is generally 1.5mm～4.5mm, length is 3.0～8.0mm, the general diameter 8～50mm of annular, and length is 8～50mm, the general diameter of wheel shape is 8～50mm, and length is 8～30mm.The voidage that increases beds can adopt the catalyzer of different grain size and shape, also can obtain the high beds of voidage by catalyzer or the inert filler mixed packing with big voidage.The different catalysts of mixed packing only is meant that granularity is different with shape, other, all identical as active metal component etc.Described inert filler is meant the especially short Raschig ring of short grained Raschig ring.The reason of mixed packing is the uniform mixing between different grain size catalyzer or the filler, can produce a kind of uniform bed structure, promptly one or several catalyzer are separated by the catalyzer of a high voidage or inert filler, can produce the high voidage on the particle scale.
Catalyzer can be single a kind of catalyzer in above-mentioned (1) and (2), also can be according to the catalyzer gradation composition by several different performances of the difference of sulphur content in the logistics.
The present invention can adopt two beds, and low voidage, high hydrogenation activity beds account for 20～95% of catalyzer cumulative volume, preferred 30～80%.The size of its volume mainly is provided with according to the character and the reactivity worth of reaction raw materials.Come out if stock oil is difficult for stripping at the gases such as hydrogen sulfide that generate than the low activity catalyst bed, poison for avoiding the high activated catalyst bed, the catalyzer that can load one section inert filler between two beds or be difficult for inactivation is as transition layer.Operational condition is the processing condition that are fit to hydrocarbons hydrogenation, and operation condition is generally: temperature of reaction 240-427 ℃; Reaction pressure is 1.0-20.0MPa; Hydrogen to oil volume ratio is more than 50, to be generally 100～1000; Volume space velocity is 0.1-7.5h during liquid
-1Concrete scope is relevant with stock oil boiling range scope, character and the processing purpose of being processed.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.
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.
Following embodiment further specifies of the present invention, and it does not limit use range of the present invention.
Embodiment 1～6 and comparative example 1～4
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.The catalyst system therefor physico-chemical property sees Table-1 in this test, and stock oil character sees Table-2.Hydrogenation reaction is all carried out in this test on the long run test device.Operational condition is a hydrogen to oil volume ratio: 300, and reaction pressure: 6.0MPa, temperature of reaction: 360 ℃, air speed: 1.5h
-1Catalyzer among the embodiment is: non-precious metal catalyst (A): and noble metal catalyst (B) (V: V)=V1: V2.Embodiment sees Table-3, and comparative example sees Table-4.
Table-1 catalyzer physico-chemical property
Project is than the low activity catalyst high activated catalyst
Numbering A B C
Mo, W (sulfide) (former Pt, Pd (atomic ratio CoMoN
x(Co and Mo
Catalytic active component
Son was than 1: 1) 1: 1) 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
Contain silicon-dioxide
Alumina catalyst support USY molecular sieve
The 4w% aluminum oxide
Table-2 stock oil main character
Density, kg/m
30.8824
S，w％????????????????????6979
N，w％????????????????????1014
Aromatic hydrocarbons, w% 48.6
Boiling range, ℃
IBP～EBP??????????????????185～373
Table-3 embodiment experimental results
Embodiment 123456
V1∶V2????????8∶2??????7∶3??????6∶4??????5∶5??????4∶6??????3∶7
Generate oil nature
Density, kg/m
30.8356 0.8356 0.8357 0.8358 0.8358 0.8359
S，w％????????19.4??????18.2??????15.5??????12.2??????11.6??????10.9
N，w％????????1.0???????1.0???????1.0???????1.0???????1.0???????1.0
Aromatic hydrocarbons, w% 16.2 14.2 13.2 11.3 10.1 9.8
Boiling range ℃
IBP～EBP??????204～362??205～363??207～364??208～364??209～366??211～368
Table-4 comparative example experimental results
Comparative example 1234
Temperature of reaction, ℃ 350 360 360 370
Catalyst B B A A
Generate oil nature
Density, kg/m
30.8361 0.8359 0.8356 0.8352
S，w％??????????14.3???????10.2??????20.5??????17.2
N，w％??????????1.0????????1.0???????3.8???????2.4
Aromatic hydrocarbons, w% 11.6 9.2 18.2 16.6
Boiling range, ℃
IBP～EBP????????214～371???212～369??204～362??201～357
By experimental result as seen, hydrogenation effect of the present invention is far longer than single base metal sulfide catalyst effect, and is suitable with single noble metal catalyst.
Embodiment 7～12 and comparative example 4～8
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.The catalyst system therefor physico-chemical property sees Table-1 in this test, and stock oil character sees Table-2.Hydrogenation reaction is all carried out in this test on the long run test device.Operational condition is a hydrogen to oil volume ratio: 300, and reaction pressure: 6.0MPa, temperature of reaction: 360 ℃, air speed: 1.5h
-1Catalyzer among the embodiment is: non-precious metal catalyst (A): and metal nitride catalyst agent (C) (V: V)=V1: V2.Embodiment sees Table-5, and comparative example sees Table-6.
Table-5 embodiment experimental results
Embodiment 789 10 11 12
V1∶V2????????8∶2??????7∶3??????6∶4??????5∶5??????4∶6??????3∶7
Generate oil nature
Density, kg/m
30.8356 0.8356 0.8357 0.8358 0.8358 0.8359
S，w％????????19.9??????18.7??????15.9??????12.5??????11.9??????11.3
N，w％????????1.0???????1.0???????1.0???????1.0???????1.0???????1.0
Aromatic hydrocarbons, w% 16.8 14.6 13.8 11.7 10.8 10.2
Boiling range ℃
IBP～EBP??????204～362??205～363??207～364??208～365??209～367??211～368
Table-6 comparative example experimental results
Comparative example 5678
Temperature of reaction, ℃ 350 360 360 370
Catalyzer C C A A
Generate oil nature
Density, kg/m
30.8360 0.8359 0.8356 0.8352
S，w％??????????14.7??????10.9??????20.5??????17.2
N，w％??????????1.0???????1.0???????3.8???????2.4
Aromatic hydrocarbons, w% 12.3 9.7 18.2 16.6
Boiling range, ℃
IBP～EBP????????213～370??212～369??204～362??201～357
By experimental result as seen, hydrogenation effect of the present invention is far longer than single base metal sulfide catalyst effect, and is suitable with single metal nitride catalyst agent.
Embodiment 13～14 and comparative example 9～11
The main catalyst stability of investigating existing countercurrent hydrogenation technology and hydrogenation technique of the present invention of this test.The kind of catalyzer is embodiment 1～12 and comparative example 1～8 roughly the same, and catalyst loading of the present invention is: A: B=6: 4, and A: C=6: 4.Temperature of reaction is 360 ℃, and air speed is 1.5h
-1, hydrogen pressure is 6.0MPa, hydrogen-oil ratio is 300.Device running 500 hours.Test-results sees Table-7.
Table-7 stability test results
Embodiment 13 embodiment 14 comparative examples 9 comparative examples 10 comparative examples 11
Catalyzer A B of the present invention C
Generate oil nature
Density, kg/m
30.8357 0.8359 0.8543 0.8581 0.8554
S，w％????????15.5?????????17.5????????350????????482?????????378
N，w％????????1.0??????????1.0?????????58?????????72??????????64
Aromatic hydrocarbons, w% 13.2 15.2 43.3 40.4 43.9
Boiling range ℃
IBP～EBP??????207～364?????206～363????185～369???187～370????185～370
By the result as seen, catalyst activity stability of the present invention is far longer than single catalyst loading scheme.
Embodiment 15～20 and comparative example 12
The main operational condition scope 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.Stock oil character sees Table-2, and this test catalyst system therefor sees Table-8.By test, if make its quality product qualified, the little voidage beds in bottom accounts for the catalyzer cumulative volume and is not less than 40% for the stock oil of this experiment, so this test is got the little voidage beds in bottom and accounted for 45% of catalyzer cumulative volume.Test-results sees Table-9.
Table-8 catalyzer physico-chemical properties
The project high activated catalyst is than low activity catalyst
Numbering D E F
Pt, Pd (atomic ratio 1: Mo, W (sulfide) Mo, W (sulfide)
Catalytic active component
1) (atomic ratio 1: 1) (atomic ratio 1: 1)
Shape bar shaped trifolium Raschig ring
Diameter, mm 1.9 3.08 16 * 16
Voidage 0.45 0.52 0.751
Metal component, w% 0.8 29 29
Contain silicon-dioxide
Carrier USY molecular sieve aluminum oxide
The 5w% aluminum oxide
Table-9 experimental results
| Embodiment | Comparative example 12 | ????15 | ????16 | ????17 |
| High voidage bed (1) | ????E | ??F∶E＝2∶8 | ??F∶E＝3∶7 | ??F∶E＝4∶6 |
| (1) voidage | ????0.48 | ??0.557 | ??0.606 | ??0.653 |
| Low voidage bed (2) | ????D | ??D | ??D | ??D |
| The maximum feed hydrogen to oil volume ratio | ????325 | ??412 | ??490 | ??565 |
Continuous table-9 experimental results
| Embodiment | ????????18 | ???????19 | ????20 |
| High voidage bed (1) | ????F∶E＝5∶5 | ????F∶E＝7∶3 | ????F |
| (1) voidage | ????0.701 | ????0.728 | ????0.750 |
| Low voidage bed (2) | ????D | ????D | ????D |
| The maximum hydrogen oil ratio | ????723 | ????830 | ????900 |
By experimental result as seen, voidage of the present invention and grain size distribution filling, the hydrogen-oil ratio operating restraint under certain air speed is far longer than the filling scheme of existing regular particle size and voidage catalyzer, has increased the operability of counter-current operation device.(illustrate: the exercisable maximum hydrogen to oil volume ratio of liquid flooding does not promptly take place in the maximum hydrogen oil ratio, and it is wide more that the big more explanation of this value can be adjusted the operating space)
Claims (10)
1, a kind of diesel oil hydrotreating method, under diesel oil distillate raw material hydroprocessing condition, hydrogen and diesel raw material are reverse by the catalyst for hydrogenation treatment of diesel oil bed, it is characterized in that whole beds is divided into two or more beds, the voidage of each beds reduces gradually along the flow direction of liquid phase, and activity of such catalysts improves gradually along the liquid phase flow direction; The highly active hydrotreating catalyst of easy sulfur poisoning is loaded in bottom at gas, liquid counter-current operation reactor, and the voidage of bed is 0.25～0.55; From the diesel raw material oil-in, along the high voidage hydrotreating catalyst of the conversion zone of the paramount active catalyst bed of liquid phase feed oil flow direction filling base metal sulfide, the voidage of the beds of low catalytic activity is 0.35～0.90.
2, in accordance with the method for claim 1, it is characterized in that described highly active hydrotreating catalyst is selected from the nitride of as-reduced metal catalyzer, noble metal catalyst, molybdenum nickel tungsten or carbide catalyst and is difficult for losing in the base metal sulfide catalyst of sulphur one or more.
3, according to the described method of claim 1 or 2, the bed voidage that it is characterized in that described high-activity hydrogenation catalyst is 0.30～0.50.
4, in accordance with the method for claim 1, the voidage that it is characterized in that described low activity hydrotreating catalyst bed is 0.45～0.80.
5, according to claim 1 or 2 described methods, it is characterized in that described high-activity hydrogenation catalyst is sphere, bar shaped, cloverleaf pattern or Herba Galii Bungei shape, spherical diameter is 1.0mm～3.0mm, the diameter of bar shaped, trifolium, Herba Galii Bungei is 1.0mm～2.5mm, and length is 3.0～8.0mm.
6, according to claim 1 or 4 described methods, it is characterized in that described low activity hydrotreating catalyst is annular, wheel shape, sphere with holes or bar shaped, trifolium, the Herba Galii Bungei of volume particle size, spherical diameter is 1.5mm～6.0mm, the diameter of bar shaped, trifolium, Herba Galii Bungei is 1.5mm～4.5mm, length is 3.0～8.0mm, annular diameter 8～50mm, and length is 8～50mm, wheel shape diameter is 8～50mm, and length is 8～30mm.
7, in accordance with the method for claim 1, it is characterized in that described beds is two, wherein the high-activity hydrogenation catalyst bed accounts for 20～95% of catalyzer cumulative volume.
8, in accordance with the method for claim 7, it is characterized in that described high-activity hydrogenation catalyst bed accounts for 30～80% of catalyzer cumulative volume.
9, in accordance with the method for claim 1, it is characterized in that described hydroprocessing condition is: temperature of reaction 240-427 ℃, reaction pressure is 1.0-20.0MPa, and hydrogen to oil volume ratio is 50～1000, and volume space velocity is 0.1-7.5h during liquid
-1
10, in accordance with the method for claim 6, it is characterized in that described low activity hydrotreating catalyst bed adopts the catalyzer of different grain size and shape.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02133121 CN1277906C (en) | 2002-10-10 | 2002-10-10 | Diesel oil hydrotreating method |
| US10/682,593 US7435336B2 (en) | 2002-10-10 | 2003-10-09 | Process for carrying out gas-liquid countercurrent processing |
| AU2003275512A AU2003275512A1 (en) | 2002-10-10 | 2003-10-10 | A method for a process of a countercurrent gas/liquid contact |
| JP2004542154A JP5259047B2 (en) | 2002-10-10 | 2003-10-10 | Countercurrent gas / liquid contact treatment method |
| KR1020057006162A KR100998512B1 (en) | 2002-10-10 | 2003-10-10 | A method for a process of a countercurrent gas/liquid contact |
| CA2501827A CA2501827C (en) | 2002-10-10 | 2003-10-10 | A method for a process of a countercurrent gas/liquid contact |
| PCT/CN2003/000854 WO2004033085A1 (en) | 2002-10-10 | 2003-10-10 | A method for a process of a countercurrent gas/liquid contact |
| EP03757635.2A EP1550503B1 (en) | 2002-10-10 | 2003-10-10 | Process for carrying out gas-liquid countercurrent processing |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02133121 CN1277906C (en) | 2002-10-10 | 2002-10-10 | Diesel oil hydrotreating method |
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| Publication Number | Publication Date |
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| CN1488712A true CN1488712A (en) | 2004-04-14 |
| CN1277906C CN1277906C (en) | 2006-10-04 |
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| CN 02133121 Expired - Lifetime CN1277906C (en) | 2002-10-10 | 2002-10-10 | Diesel oil hydrotreating method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942319A (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 | Method for hydrotreating poor diesel |
| CN102041065A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Method for hydrotreating coking distillate |
| CN102206511A (en) * | 2011-04-26 | 2011-10-05 | 神华集团有限责任公司 | Method for producing diesel fuel by using coal direct liquefication oil and delayed coking heavy diesel fuel fraction and application of method |
| CN101492605B (en) * | 2008-01-23 | 2012-11-21 | 中国石油化工股份有限公司 | Shale oil hydrogenation process |
| CN102851070A (en) * | 2011-06-30 | 2013-01-02 | 中国石油化工股份有限公司 | Method for production of ultralow-sulfur diesel oil |
| US10717939B2 (en) | 2016-10-21 | 2020-07-21 | China Petroleum & Chemical Corporation | Desulfurization catalyst for hydrocarbon oils, its preparation, and use thereof |
| WO2022083714A1 (en) | 2020-10-22 | 2022-04-28 | 中国石油化工股份有限公司 | Multi-phase combination reaction system and reaction method |
-
2002
- 2002-10-10 CN CN 02133121 patent/CN1277906C/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101492605B (en) * | 2008-01-23 | 2012-11-21 | 中国石油化工股份有限公司 | Shale oil hydrogenation process |
| CN101942319A (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 | Method for hydrotreating poor diesel |
| CN102041065A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Method for hydrotreating coking distillate |
| CN102041065B (en) * | 2009-10-21 | 2014-07-23 | 中国石油化工股份有限公司 | Method for hydrotreating coking distillate |
| CN102206511A (en) * | 2011-04-26 | 2011-10-05 | 神华集团有限责任公司 | Method for producing diesel fuel by using coal direct liquefication oil and delayed coking heavy diesel fuel fraction and application of method |
| CN102206511B (en) * | 2011-04-26 | 2014-07-09 | 神华集团有限责任公司 | Method for producing diesel fuel by using coal direct liquefication oil and delayed coking heavy diesel fuel fraction and application of method |
| CN102851070A (en) * | 2011-06-30 | 2013-01-02 | 中国石油化工股份有限公司 | Method for production of ultralow-sulfur diesel oil |
| CN102851070B (en) * | 2011-06-30 | 2014-10-29 | 中国石油化工股份有限公司 | Method for production of ultralow-sulfur diesel oil |
| US10717939B2 (en) | 2016-10-21 | 2020-07-21 | China Petroleum & Chemical Corporation | Desulfurization catalyst for hydrocarbon oils, its preparation, and use thereof |
| WO2022083714A1 (en) | 2020-10-22 | 2022-04-28 | 中国石油化工股份有限公司 | Multi-phase combination reaction system and reaction method |
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| CN1277906C (en) | 2006-10-04 |
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