CN102041064A - Deep-desulfurization method of diesel distillate - Google Patents
Deep-desulfurization method of diesel distillate Download PDFInfo
- Publication number
- CN102041064A CN102041064A CN2009102042455A CN200910204245A CN102041064A CN 102041064 A CN102041064 A CN 102041064A CN 2009102042455 A CN2009102042455 A CN 2009102042455A CN 200910204245 A CN200910204245 A CN 200910204245A CN 102041064 A CN102041064 A CN 102041064A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- beds
- filling
- catalyst
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses a deep-desulfurization method of diesel distillate, which comprises the steps: leading a diesel oil raw material and hydrogen to sequentially pass through three catalyst bed layers, filling a catalyst with strong hydrogenation performance into the first catalyst bed layer, filling a catalyst with strong desulfurization performance into the second catalyst bed layer, and filling a catalyst with strong hydrogenation performance into the third catalyst bed layer. Compared with the prior art, the method gives full play to the performances of metal type catalysts with different activities, can be used for producing the product with the sulphur content less than the standard of 10 mu g/g, and is high in flexibility of operation and treatment capacity, thus reducing the device investment, adjusting the operation parameters according to the product requirement, and reducing the operating cost.
Description
Technical field
The invention belongs to the method that obtains the fuel for cleaning vehicle refined diesel oil under a kind of hydro condition, more particularly, is the method for a kind of diesel oil fraction hydrogenating deep desulfuration production sulphur content less than 10 μ g/g diesel oil.
Background technology
Along with the reinforcement of environmental consciousness, for reducing vehicle exhaust to atmospheric pollution, people are to the increasingly stringent that requires of foreign matter content such as sulphur, nitrogen in the diesel oil distillate.For example, it is 50 μ g/g that European countries carried out the diesel oil maximum sulfur on June 1st, 2005, and by 2011, sulphur content was less than the standard of 10 μ g/g.In the automobile-used clean diesel standard of Environmental Protection Agency (EPA), the world fuel council promulgation sulphur content is required tighter, simultaneously to diesel oil density, do, aromatic hydrocarbons and polycyclic aromatic hydrocarbons be all restricted.The sulphur content that California, USA resource management office (CARB) and U.S. environment management association (EMA) have also proposed oneself is less than 10 μ g/g diesel oil indexs.China in January, 2008 carry out in Beijing that sulphur content is no more than 50 μ g/g be equivalent to Europe IV diesel oil standard, and plan in the end of the year 2009 carry out in the whole nation that sulphur content is no more than 350 μ g/g be equivalent to Europe III diesel oil standard.Therefore, in the near future, the diesel oil specification of China also can resemble the content of impurity such as further restriction sulphur Europe, the U.S., nitrogen, and the sulphur content that requires diesel product is less than 10 μ g/g.For this reason, each oil refining enterprise all will face the problem of improving diesel quality.
Adopt conventional hydrofinishing process and highly active Hydrobon catalyst, though also can reach the purpose of desulfurization, along with the intensification of the hydrogenation degree of depth, it is more and more harsher that operational conditions such as the air speed of hydrogenation unit become, to oil refining enterprise, be disadvantageous economically.So a main difficult point of research is how to solve the operating severity that reduces device when reducing the hydrogenated products sulphur content at present.
Existing ultra-deep hydrodesulfuration technology mostly is to adopt two reactors, removes the sulphur that more easily removes at first reactor, improves the reaction environment of second reactor then, removes the sulphur that difficulty is taken off part, reaches the purpose of deep desulfuration.As increase separation system, and promptly between two reactors, increase a high-pressure separator, remove the hydrogen sulfide in first reactor product, the hydrogen purity that enters second reactor is improved, reach the purpose of deep desulfuration with this.
Introduced a kind of method of above-mentioned hydrogenating desulfurization among the USP5114562.At least adopt two reaction zones in this method, load non-precious metal catalyst in first reaction zone, second reaction zone generally loads noble metal catalyst, and the hydrogen dividing potential drop is than the high 500kPa of first reaction zone, and temperature of reaction is lower than first reaction zone.A high temperature stripper plant is arranged, to remove the hydrogen sulfide in first reaction zone product between two reactors.Though this method can obtain the diesel product of low-sulfur, low aromatic hydrocarbons, owing to the facility investment and the process cost of the pressure of two reaction zones interpolation different and stripping apparatus having increased device.
CN1355273A has proposed a kind of process for deeply desulfurizing fractional oil of low hydrogen consumption, and diesel raw material and hydrogen are at hydrogen dividing potential drop 2.0～8.0MPa, 320 ℃～440 ℃ of temperature, liquid hourly space velocity 2h
-1～7h
-1, hydrogen to oil volume ratio 200～700 condition under contact with Hydrobon catalyst, reaction effluent is 200～290 ℃, liquid hourly space velocity 4h without separation in temperature of reaction
-1～10h
-1Condition under contact with Hydrobon catalyst, the separating reaction effluent, wherein product liquid enters fractionating system, rich hydrogenous hydrogen recycle is returned reactor.The chemical hydrogen consumption of this method is low, and the sulphur content of diesel product can be reduced to below the 300 μ g/g.But if produce ultra-low-sulphur diesel (＜10 μ g/g) with it, the desulfurization depth of this technology is not enough to reach.
Sulfocompound can be divided into two classes according to its hydrogenating desulfurization difficulty or ease in the diesel oil distillate: a class is chain sulfocompound, thiophenes, contain the benzothiophenes of one or two aromatic ring, this compounds reaction steric hindrance is less, is easy to remove wherein sulphur with the hydrofining means of routine; An other class contains a plurality of aromatic rings exactly, and substituent many benzothiophenes are arranged on the aromatic ring, for example 4,6-dimethyl Dibenzothiophene (4,6-DMDBT), 4,6,8-trimethylammonium dibenzothiophene (4,6,8-TMDBT) etc., there is substituting group in the characteristics of this compounds near sulphur atom, the reaction compartment steric hindrance is bigger, and sulphur atom contacts difficulty with the catalyst activity position, and has very high boiling point (generally greater than 350 ℃), these compounds are biggest obstacles of ultra-deep desulfurization, studies show that such sulfide generally is earlier the C-S bond rupture to take place again and desulfurization after containing the benzene ring hydrogenation that sulfur heteroatom closes on.
Organic nitrogen compound is the poisonous substance of hydrogenation catalyst, and hydrodenitrification, hydrogenating desulfurization and hydrogenation dearomatization reaction are had the obvious suppression effect.This restraining effect mainly is because some nitride and the intermediate reaction product of most of nitride and the hydrogenation reaction active centre of catalyzer have very strong sorptive power, has suppressed the carrying out of other hydrogenation reactions from the angle of competitive adsorption.Research thinks, heterocyclic nitrogen is before C-N key hydrogenolysis, and it is saturated to carry out the heterocyclic hydrogenation, even the non-heterocyclic nitrogen compound of phenyl amines, before the C-N key hydrogenolysis, aromatic ring is also saturated in advance.Therefore,, need the coupling of dissimilar catalyzer, could obtain best reaction effect at the characteristics of ultra-deep desulfurization.
Typical Hydrobon catalyst, being carrier with aluminum oxide or siliceous aluminum oxide often, is active ingredient with VIII family and group vib metallic element, in order to improve activity of such catalysts and stability, normal adopt multiple improving one's methods, as to support modification, optimize the preparation method, add auxiliary agent etc.Auxiliary agent commonly used has P, F, B, Ti, Zr etc.
For hydrodesulfurization reaction, the active order of different metal combination of components is Co-Mo＞Ni-Mo ≈ Ni-W＞Co-W; And for hydrogenation activity, the active order of metal component combination is Ni-W＞Ni-Mo＞Co-Mo＞Co-W.Thiophene-based is not during the HDS of presence bit inhibition effect sulfide, the Co-Mo catalyzer is better than the Ni-Mo catalyzer, and for ultra-deep hydrodesulfuration, when desulfurization degree＞99%, need remove 4,6-dimethyl Dibenzothiophene class sulfide, this class sulfide is because the influence of steric effect, desulphurization reaction speed is much larger than the speed of reaction of direct hydrogenating desulfurization behind elder generation's hydrogenation, and in such cases, Ni-Mo or W-Ni-Mo catalyzer are better than the Co-Mo catalyzer.
For hydrodenitrification reaction, the similar and ultra-deep hydrodesulfuration of reaction mechanism, denitrogenation behind the general first hydrogenation, in such cases, Ni-Mo or W-Ni-Mo catalyzer are better than the Co-Mo catalyzer.
Therefore how to mate Mo-Ni or W-Ni-Mo and Mo-Co catalyst combination technology, the combination of this different activities component catalyst of effectively collaborative performance simultaneously, ultra-low-sulphur diesel is very crucial for producing.
Summary of the invention
Purpose of the present invention promptly is on the basis of analyzing the diesel deep desulfurization reaction mechanism, provides a kind of diesel fraction deep desulfurization method on the basis in conjunction with existing hydrogen addition technology, with the diesel product of production sulphur content less than 10 μ g/g.
Method provided by the invention is: diesel raw material and hydrogen are successively by three beds, the strong catalyzer of first beds filling hydrogenation performance, the strong catalyzer of second beds filling desulfurization performance, the strong catalyzer of the 3rd beds filling hydrogenation performance.Reaction conditions is: hydrogen dividing potential drop 2.0MPa～10.0MPa, 320 ℃～420 ℃ of temperature, liquid hourly space velocity 2h
-1～10h
-1, hydrogen to oil volume ratio 200～1000.
The catalyzer of first beds filling is a loaded catalyst, loaded metal is VIB and group VIII base metal Mo-Ni type catalyzer or W-Mo-Ni type catalyzer, raw material and hydrogen is main hydrodenitrification reaction and the small part hydrodesulfurization reaction of taking place on this layer catalyzer, removing of nitrogenous compound, create more favourable reaction conditions for the reaction of lower bed layer, give full play to the performance of lower floor's catalyzer; The catalyzer of second beds filling is a loaded catalyst, loaded metal is VIB and group VIII base metal Mo-Co type catalyzer, desulphurization reaction mainly takes place in second beds, particularly chain sulfocompound, thiophenes, contain the benzothiophenes of one or two aromatic ring; The catalyzer of the 3rd beds filling is a loaded catalyst, loaded metal is VIB and group VIII base metal Mo-Ni type catalyzer or W-Mo-Ni type catalyzer, and the deep desulfuration reaction mainly takes place the 3rd beds, particularly contains a plurality of aromatic rings, and substituent many benzothiophenes are arranged on the aromatic ring, for example 4, and the 6-dimethyl Dibenzothiophene (4,6-DMDBT), 4,6,8-trimethylammonium dibenzothiophene (4,6,8-TMDBT) hydrodesulfurization reaction.Therefore, the reactive behavior of effectively collaborative simultaneously performance different activities component catalyst satisfies the needs that the distillate ultra-deep hydrodesulfuration reacts.
First beds can be different with the used Hydrobon catalyst of the 3rd beds, also can be identical.The catalyzer of first beds and the filling of the 3rd beds is a loaded catalyst, loaded metal is VIB and group VIII non-precious metal catalyst, as Mo, Ni and W etc., it generally is the combination between them, preferred Mo-Ni combination and W-Mo-Ni combination, metal content (in oxide compound) is at 8.0wt%～35.0wt%, preferred 10.0wt%～30.0wt%; Preferred carrier is silicon oxide, aluminum oxide, silica-alumina, silica-alumina phosphoric acid salt, titanium oxide, zirconium white, vanadium oxide and other III-th family, IV family, VA family and VI family oxide compound, and one or more the mixture in the Y zeolite.This kind catalyzer should have stronger hydrogenation sites.
The catalyzer of second beds filling also is a loaded catalyst, loaded metal is VIB and group VIII non-precious metal catalyst, preferred Mo-Co metallic combination, metal content (in oxide compound) be at 8.0wt%～35.0wt%, preferred 10.0wt%～30.0wt%; Preferred carrier has silicon oxide, aluminum oxide, silica-alumina, silica-alumina phosphoric acid salt, titanium oxide, zirconium white, vanadium oxide and other III-th family, IV family, VA family and VI family oxide compound, and Y zeolite equimolecular sieve, or the mixture of two or more carrier wherein.This kind catalyzer should have stronger direct desulfurization active centre.
When carbon residue in the diesel raw material or metal content are higher; for preventing that the beds coking from causing bed pressure drop too fast; can add a certain amount of hydrogenation protecting agent at the Hydrobon catalyst top of first beds; its add-on is generally the 1v%～20v% of the-beds hydrogenation catalyst; normally bring into play with the catalyst activity performance that guarantees beds, and prolong operating period.The hydrogenation protecting agent is made up of the gamma-aluminium oxide carrier with diplopore distribution of 1.0～5.0wt% nickel oxide, 5.5～10.0wt% molybdenum oxide and surplus, preferably the FZC-10 of Fushun Petrochemical Research Institute series residual hydrogenation protective material.
The inventive method can be used for various straight-run diesel oils, catalytic cracking diesel oil, coker gas oil or its mixture.The boiling range scope of diesel raw material is 140 ℃～400 ℃, is preferably 170 ℃～380 ℃, and sulphur content is 0.1～3.0wt%.Reaction effluent enters high-pressure separator through cooling, and isolated product liquid enters fractionating system, and hydrogen-containing gas is through removing H
2Loop back reactor behind the S.
20%～40%, the second beds catalyzer that first beds accounts for the total catalyst volume accounts for 20%～30% of total catalyst volume.Each catalyzer can be selected the commercial goods on demand, also can prepare by this area ordinary method.Concrete processing condition and each beds catalyst ratio can require to be determined by the technician according to feedstock property and quality product.
The invention has the advantages that: the effective coupling that contains different activities metal catalyst and different catalysts consumption, the reactive behavior of effectively collaborative simultaneously performance different activities component catalyst, each bed catalyzer is in the own performance of performance, also created the reaction environment that more has, satisfied the needs of distillate ultra-deep hydrodesulfuration reaction for next bed catalyst performance performance.
Three beds of the present invention can be placed in the reactor, also can be placed on two or three reactors are set separately, has bigger flexibility of operation, can adjust operating parameters according to product requirement, produce the product of different sulphur content specifications, especially be used for producing ultra-low-sulphur diesel (sulphur content＜10 μ g/g), or utilize existing apparatus to carry out appropriate reconstruction and can implement; And working pressure is relatively low, thereby has reduced plant investment, has reduced process cost.
Embodiment
Following embodiment further specifies of the present invention, and it does not limit use range of the present invention.
Embodiment 1～4 and comparative example 1
Hydrogenating desulfurization effect of the present invention is mainly investigated in test below.With the straight-run diesel oil of middle-eastern crude and the hydrogenating desulfurization of catalytic cracking diesel oil mixing oil (weight ratio of straight-run diesel oil and catalytic cracking diesel oil is 70: 30) is example.The raw material oil properties sees Table 1 in this test, and catalyst system therefor is seated in the reactor, and physico-chemical property sees Table 2.Hydrogenation reaction is all carried out in this test on the continuous isothermal testing apparatus, its processing condition and test-results see Table 3.Comparative example 1 only uses the Co-Mo catalyzer of second beds in the table 2, and other processing condition are identical with embodiment 4.
Table 1 stock oil main character
| Density, kg/m 3 | 0.8699 |
| S，μg/g | 8500 |
| N，μg/g | 360 |
| Aromatic hydrocarbons, wt% | 43.2 |
| Boiling range, ℃ | |
| IBP～EBP | 186～378 |
Table 2 catalyzer physico-chemical property
The processing condition of each embodiment of table 3 and experimental result thereof
| Embodiment | 1 | 2 | 3 | 4 | Comparative example 1 |
| The catalyst volume ratio, v% | 40/30/30 | 40/30/30 | 40/30/30 | 40/30/30 | -/100/- |
| Processing condition | |||||
| The hydrogen dividing potential drop, MPa | 3.2 | 3.2 | 6.4 | 6.4 | 6.4 |
| Temperature of reaction, ℃ | 350 | 360 | 340 | 350 | 350 |
| Liquid hourly space velocity, h -1 | 1.5 | 1.5 | 2.5 | 2.5 | 2.5 |
| Hydrogen to oil volume ratio | 500 | 500 | 350 | 350 | 350 |
| Product property | |||||
| Boiling range, ℃ | 184～375 | 184～374 | 182～374 | 186～373 | 184～376 |
| ?S，μg/g | 9.5 | 8.2 | 5.1 | 3.5 | 315 |
| ?N，μg/g | 1.0 | 1.0 | 1.0 | 1.0 | 35 |
| Aromatic hydrocarbons, wt% | 33.2 | 31.2 | 29.2 | 27.1 | 42.3 |
Embodiment 5～8 and comparative example 2
Hydrogenating desulfurization effect of the present invention is mainly investigated in test below.With the coker gas oil of middle-eastern crude and the hydrogenating desulfurization of catalytic cracking diesel oil mixing oil (weight ratio of coker gas oil and catalytic cracking diesel oil is 50: 50) is example.The raw material oil properties sees Table 4 in this test, and catalyst system therefor is seated in the reactor, and physico-chemical property sees Table 5.Hydrogenation reaction is all carried out in this test on the continuous isothermal testing apparatus, its processing condition and test-results see Table 6.Comparative example 2 uses the Mo-Ni catalyzer of first beds in the table 5 and the Co-Mo catalyzer of second beds, both volume ratios are 1: 1, by first beds and second beds, other processing condition are identical with embodiment 8 successively for reaction mass.
Table 4 stock oil main character
| Density, kg/m 3 | 0.8912 |
| S，μg/g | 5600 |
| N，μg/g | 500 |
| Aromatic hydrocarbons, wt% | 59 |
| Boiling range, ℃ | |
| IBP～EBP | 170～396 |
Table 5 catalyzer physico-chemical property
The processing condition of each embodiment of table 6 and experimental result thereof
| Embodiment | 5 | 6 | 7 | 8 | Comparative example 2 |
| The catalyst volume ratio, v% | 45/30/25 | 45/30/25 | 45/30/25 | 45/30/25 | 50/50/- |
| Processing condition | |||||
| The hydrogen dividing potential drop, MPa | 5.2 | 5.2 | 8.4 | 8.4 | 8.4 |
| Temperature of reaction, ℃ | 355 | 365 | 250 | 360 | 360 |
| Liquid hourly space velocity, h -1 | 1.8 | 1.8 | 2.5 | 2.5 | 2.5 |
| Hydrogen to oil volume ratio | 500 | 500 | 350 | 350 | 350 |
| Product property | |||||
| Boiling range, ℃ | 169～389 | 168～388 | 165～385 | 186～384 | 169～392 |
| ?S，μg/g | 9.8 | 8.5 | 6.1 | 4.5 | 50 |
| ?N，μg/g | 7.0 | 5.2 | 4.0 | 2.0 | 32 |
| Aromatic hydrocarbons, wt% | 48 | 46 | 46 | 45 | 56 |
Claims (10)
1. the method for diesel oil distillate oil deep desulfuration, it is characterized in that: diesel raw material and hydrogen are successively by three beds, the strong catalyzer of first beds filling hydrogenation performance, the strong catalyzer of second beds filling desulfurization performance, the strong catalyzer of the 3rd beds filling hydrogenation performance; Reaction conditions is: hydrogen dividing potential drop 2.0MPa～10.0MPa, 320 ℃～420 ℃ of temperature, liquid hourly space velocity 2h
-1～10h
-1, hydrogen to oil volume ratio 200～1000.
2. in accordance with the method for claim 1, it is characterized in that: the catalyzer of first beds filling is Mo-Ni type catalyzer or W-Mo-Ni type catalyzer, the catalyzer of second beds filling is a Mo-Co type catalyzer, and the catalyzer of the 3rd beds filling is Mo-Ni type catalyzer or W-Mo-Ni type catalyzer.
3. according to claim 1 or 2 described methods, it is characterized in that: the used Hydrobon catalyst of first beds and the 3rd beds is different or identical, and the first beds catalyzer and the 3rd beds catalyzer are 8.0wt%～35.0wt% in the metal content of oxide compound.
4. it is characterized in that in accordance with the method for claim 3: the first beds catalyzer and the 3rd beds catalyzer are 10.0wt%～30.0wt% in the metal content of oxide compound.
5. according to claim 1 or 2 described methods, it is characterized in that: the used catalyzer of second beds is 8.0wt%～35.0wt% in the metal content of oxide compound.
6. it is characterized in that in accordance with the method for claim 5: the used catalyzer of second beds is 10.0wt%～30.0wt% in the metal content of oxide compound.
7. according to claim 1 or 2 described methods, it is characterized in that: first beds accounts for 20%～40% of total catalyst volume.
8. according to claim 1 or 2 described methods, it is characterized in that: the second beds catalyzer accounts for 20%～30% of total catalyst volume.
9. it is characterized in that in accordance with the method for claim 1: diesel raw material is straight-run diesel oil, catalytic cracking diesel oil, coker gas oil or its mixture; Reaction effluent enters high-pressure separator through cooling, and isolated product liquid enters fractionating system, and hydrogen-containing gas is through removing H
2Loop back reactor behind the S.
10. it is characterized in that in accordance with the method for claim 1: the Hydrobon catalyst top at first beds adds the hydrogenation protecting agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102042455A CN102041064A (en) | 2009-10-21 | 2009-10-21 | Deep-desulfurization method of diesel distillate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102042455A CN102041064A (en) | 2009-10-21 | 2009-10-21 | Deep-desulfurization method of diesel distillate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102041064A true CN102041064A (en) | 2011-05-04 |
Family
ID=43907613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009102042455A Pending CN102041064A (en) | 2009-10-21 | 2009-10-21 | Deep-desulfurization method of diesel distillate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102041064A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102876374A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Inferior diesel oil hydrodesulfurization method |
| CN104419462A (en) * | 2013-08-30 | 2015-03-18 | 中国石油天然气股份有限公司 | Technique for producing clean diesel |
| CN105542850A (en) * | 2014-10-28 | 2016-05-04 | 中国石油化工股份有限公司 | Method for producing ultra low sulfur diesel oil through hydrorefining |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1088153A (en) * | 1996-09-11 | 1998-04-07 | Nippon Oil Co Ltd | Production of low-sulfur diesel light oil |
| CN1417301A (en) * | 2001-10-30 | 2003-05-14 | 中国石油化工股份有限公司 | Method of desulfurizing and dearomatizing diesel oil deeply |
| CN101092573A (en) * | 2006-06-22 | 2007-12-26 | 中国石油化工股份有限公司 | A hydrogenation method for producing diesel oil in low sulphur |
| CN101376839A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Diesel fraction deep hydrogenation method |
-
2009
- 2009-10-21 CN CN2009102042455A patent/CN102041064A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1088153A (en) * | 1996-09-11 | 1998-04-07 | Nippon Oil Co Ltd | Production of low-sulfur diesel light oil |
| CN1417301A (en) * | 2001-10-30 | 2003-05-14 | 中国石油化工股份有限公司 | Method of desulfurizing and dearomatizing diesel oil deeply |
| CN101092573A (en) * | 2006-06-22 | 2007-12-26 | 中国石油化工股份有限公司 | A hydrogenation method for producing diesel oil in low sulphur |
| CN101376839A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Diesel fraction deep hydrogenation method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102876374A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Inferior diesel oil hydrodesulfurization method |
| CN104419462A (en) * | 2013-08-30 | 2015-03-18 | 中国石油天然气股份有限公司 | Technique for producing clean diesel |
| CN105542850A (en) * | 2014-10-28 | 2016-05-04 | 中国石油化工股份有限公司 | Method for producing ultra low sulfur diesel oil through hydrorefining |
| CN105542850B (en) * | 2014-10-28 | 2017-05-24 | 中国石油化工股份有限公司 | Method for producing ultra low sulfur diesel oil through hydrorefining |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101519603B (en) | Method for hydrotreating high-sulfur and high-metal residual oil | |
| US5316658A (en) | Process for the production of low-sulfur diesel gas oil | |
| CN101117594B (en) | Hydrogenation method for producing clean diesel oil | |
| CN102876377B (en) | Hydrotreatment and catalytic cracking combined method of heavy hydrocarbon raw material | |
| KR20020068369A (en) | Process for removing sulfur from a hydrocarbon feed | |
| CN102899081B (en) | Wax oil hydrotreating method | |
| CN101591566A (en) | A kind of grading method of catalyst of deep hydrodesulfurizationof of diesel oil | |
| CN1986748B (en) | Diesel oil fraction overhydrogenating modification process | |
| CN105273745B (en) | Low-grade diesel oil selective hydrogenation aromatic hydrocarbon removing method | |
| CN101280221A (en) | Hydrogenation conversion method for poor ignition quality fuel distillate | |
| CN103059960B (en) | Flexible hydrocracking method | |
| CN103059983B (en) | Hydrofining catalyst combined filling method | |
| CN102465034B (en) | Processing method of inferior residuum | |
| CN102041064A (en) | Deep-desulfurization method of diesel distillate | |
| CN102041063B (en) | The method of deep hydrodesulfurizationof of diesel oil | |
| CN101942331A (en) | Gasoline and diesel oil combined hydrogenation method | |
| CN1102452C (en) | Method of delaying service life of catalyst | |
| CN102465011A (en) | Hydrotreatment method of heavy distillate oil | |
| CN1313573C (en) | Process for deep desulfating of diesel oil fractional oil | |
| CN102041083A (en) | Hydrogenation modification method for coking gasoline/diesel fractions | |
| CN1986747B (en) | Diesel oil fraction hydrogenating modification process | |
| CN102465014A (en) | Hydrocracking method for processing low-sulfur raw material | |
| CN103059993B (en) | Catalytic conversion method of petroleum hydrocarbon | |
| JP4217336B2 (en) | Fuel oil desulfurization method and fuel oil desulfurization system | |
| CN102876374B (en) | Inferior diesel oil hydrodesulfurization method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20110504 |