CN1064988C - Diesel oil fraction hydrogenation converting process - Google Patents
Diesel oil fraction hydrogenation converting process Download PDFInfo
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- CN1064988C CN1064988C CN951174932A CN95117493A CN1064988C CN 1064988 C CN1064988 C CN 1064988C CN 951174932 A CN951174932 A CN 951174932A CN 95117493 A CN95117493 A CN 95117493A CN 1064988 C CN1064988 C CN 1064988C
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Abstract
The present invention discloses a method for hydrogenizing and converting poor ignition quality fuel and especially catalyzing diesel oil (LCO). The method comprises the following steps: a hydrogenating converting catalyst containing molecular sieves is adopted, and a one step hydrogenizing technological process, a one step of connection in series of hydrogenizing technological process and a two step hydrogenizing technological process are adopted to strip aroylation, desulfurize and improve the cetane number of diesel oil. The hydrogenizing and converting technology has the characteristic that special reaction conditions are selected to cause a molecular sieve catalyst to exert the performance of ring opening without cracking to obtain the purpose of substantially enhancing the quality of the diesel oil. Compared with hydrofining, the amplitude of the cetane value enhanced by the present invention can be about more than one time of that of a hydrofining technology when the same desulfurizing and denitrifying depth is obtained under similar operating conditions.
Description
The present invention relates to a kind of poor ignition quality fuel, particularly catalytic diesel oil (LCO) hydrocracking, improve cetane value purified method simultaneously.
Atrophy along with heavy oil market, the degree of depth transforming degree of heavy residual oil improves constantly, and makes the downgrade of secondary processing product such as catalytic diesel oil (LCO) etc., and the environmental law rule is strict more to the requirement of quality product, as sulphur content＜0.05wt%, cetane value 〉=45 etc.A lot of refineries are because FCC and RFCC ability are bigger, it is low to produce a large amount of cetane value, the LCO that aromaticity content is high be difficult to find competent high hexadecane value diesel component to be in harmonious proportion with it, so people is demanding developing the new process that can improve this class poor ignition quality fuel quality of similar LCO urgently.
The common method of processing poor ignition quality fuel is hydrofining at present, this technology investment is low, technology maturation, but the improvement to diesel oil has certain restriction, generally diesel-fuel cetane number can only be improved 3-5 unit, and to further improve cetane value, and then need increase refining depth, hydrogen consumption exponentially ground is increased.With U.S. Pat 5114562 and US5068025 is the two-stage method diesel oil hydrogenation treatment process of representative, one section adopts traditional Hydrobon catalyst with impurity removals such as the sulphur in the raw material, nitrogen, and the hydrogenation catalyst that second section use has high hydrogenation saturated activity carries out deeply de-aromatizing.Though this technology can be taken off the aromatic hydrocarbons in the diesel oil very low degree, the hydrogen consumption is big, and investment is high, and is less economical.
Fig. 1 has provided the cetane value distribution of various components in the diesel oil, its abscissa is an average carbon atom number, and ordinate zou is corresponding cetane value, and curve is then represented the relation that same class component cetane value changes with carbonatoms, a represents the n-paraffinic hydrocarbons, b-alkene, c-isomerization alkanes, d-single-ring naphthene, e-aromatic hydrocarbons, the f-perhydronaphthalene, g-naphthane, h-naphthalene.The cetane value of dicyclic compound is lower as can be seen from Figure 1, if therefore can make the dicyclic compound open loop, then can increase substantially the cetane value of its product.
Middle pressure hydrocracking or MHUG (as patent US4971680) are exactly to utilize hydrocracking catalyst with the aromatic hydrocarbons in the diesel oil, particularly double ring arene optionally is cracked into gasoline component, this method really can improve diesel-fuel cetane number ten more than the unit, but the low octane value gasoline of being produced still need further be processed with reforming.MObil.Akzo Nobel/Nippon Ketjen and M.W.Kellogg company have developed jointly a kind of MAK-LCO technology recently, the characteristics of this technology are on the basis of MHUG, with the special cracking catalyst of a kind of performance, its may command cracking does not take place further saturated to the aromatic hydrocarbons in the gasoline, thereby makes the octane value of gasoline reach the level that can directly go out product.But generally speaking the characteristics of this class technology are still to be cracked into the master, and general cracking transformation efficiency is all more than 40%, and this has aggravated diesel and gasoline ratio contradiction on the low side on the one hand, has also increased the consumption of hydrogen resource simultaneously.
As previously mentioned, if develop a kind of new hydrogenation technique and catalyst system can be with the aromatic hydrocarbons in the diesel raw material, the particularly saturated and open loop of double ring arene hydrogenation stops its further cracking simultaneously, will be the most cost-effective approach.From the reaction mechanism of hydrocracking process, realize that a kind of like this target is fully possible.On molecular sieve type dual-functional hydrogenation cracking catalyst, saturated reaction at first takes place in aromatic hydrocarbon molecule on hydrogenation sites, the reaction of the open loop of initial ring alkane and alkyl chain rupture in the heart in cracking activity then, in general the cycloalkanes ring-opening reaction needs more weak acidic site relatively.We find in number of research projects, organic nitrogen compound belongs to a kind of running balance in the supercentral toxic reaction of cracking activity and poisons, for the molecular sieve hydrogenation catalyst of some high anti-nitrogen, the dynamic cracking activity center that forms after the nitrogen poisoning through appropriateness has good cycloalkanes open loop ability and very weak alkylolysis ability.Hydrogenation technique of the present invention utilizes above-mentioned reaction principle that molecular sieve catalyst is introduced the hydroconversion process of poor ignition quality fuel just, the not cracked reaction by selecting appropriate reaction conditions to impel the generation open loop of molecular sieve hydrogenation catalyst.This technological process is compared with unifining process, improve (nearly doubling) except having better cetane value than general hydrofining amplitude, the ability of impurity such as its desulfurization, nitrogen, colloid is also equal or higher, because nitride, colloid etc. mainly also are made up of cyclic hydrocarbon, higher open loop ability also just means the higher ability that removes this class impurity, owing to only contain a spot of polynuclear compound in this hydrogenation technique product, so the light of diesel product, heat-resistant quality are better.
Method of the present invention is to be raw material with the poor ignition quality fuel, particularly is raw material with LCO, is keeping certain N+ α NH
3Under value and the hydrocracking condition, make stock oil by containing the hydrogenation conversion catalyst bed of molecular sieve, organosulfurs a large amount of in the raw material, nitrogen are deviate from, most of aromatic hydrocarbons, the particularly saturated and open loop of double ring arene hydrogenation reaches purpose refining and the raising cetane value.
" N+ α NH
3" in N represent to enter organonitrogen content in the stock oil of molecular sieve catalyst bed, NH
3The content of ammonia in the expression system, α ≈ 0.1 (coefficient).
The alleged hydrocracking condition of the present invention is:
Temperature: 340-420 ℃
Stagnation pressure: 6.0-13.5MPa hydrogen dividing potential drop: 3.0-10.0MPa
Total air speed (liquid): 1.0-4.0h
-1
Hydrogen-oil ratio (volume): 300: 1-1500: 1.More the suitable hydrogenation conversion condition is:
Temperature: 360-400 ℃
Stagnation pressure: 8.0-12.0MPa
Hydrogen dividing potential drop: 6.0-9.0MPa
Total air speed (liquid): 1.0-2.0h
-1
Hydrogen-oil ratio (volume): 500-1000: 1.
The hydrogenation conversion catalyst that contains molecular sieve that the present invention is alleged is meant general hydrocracking catalyst or is exclusively used in hydrogenation conversion catalyst of the present invention.General hydrocracking catalyst is by hydrogenation active metals components such as Wo, Mo, Co, Ni, Fe, formations such as molecular sieve component and alumina supporter.Being exclusively used in hydrogenation conversion catalyst of the present invention is a kind of WO of containing
3(or MoO
3) 13-25wt%, Ni (or CoO) 3-10wt%, molecular sieve 5-30wt%, aluminum oxide 5-30wt% hydrogenation conversion catalyst, wherein molecular sieve can be Y, β or ZSM type molecular sieve.
In the present invention, if the organonitrogen too high levels in the stock oil, during as N＞2000ppm, can be at stock oil by before containing the molecular sieve catalyst bed, in advance by a hydrofining (or hydrodenitrification) beds, carry out the part denitrogenation, make the contained N+ α of the material that enters on molecular sieve hydrogenation catalyst NH
3Value can obtain best effect within the scope an of the best, this effect both had been embodied on the harsh degree of operational condition, was also embodied in the raising of quality product.The optimum range of this value is between 100-500ppm.In general should be worth between 50-1200ppm.If enter the contained N+ α of the material NH on the molecular sieve hydrogenation catalyst
3Be worth very lowly, as＜100ppm, then diesel yield may descend, though can keep diesel yield by reducing temperature of reaction, the consequent is the decline of cetane value increase rate, and the reduction of taking off the aromatic hydrocarbons ability; If enter the contained N+ α of the raw material NH on the molecular sieve hydrogenation catalyst
3Be worth very highly, as＞1200ppm, will make catalyzer cross moderate intoxication, aromatic hydrocarbons saturability and open loop ability and desulfurization removing nitric ability will be affected, and not reach best effect.Thereby keep certain N+ α NH
3Value is very necessary.
This technology can be according to the different process schemes such as different choice one-stage process, series connection one-stage process and two-phase method of feedstock property and product requirement.
One-stage process is suitable for N+ α NH
3The hydroconversion process of the poor ignition quality fuel of value between 100-1000ppm, its principle technical process (Fig. 2) is: stock oil (1) mixes with the circulating hydrogen of hydrogen of making a fresh start (2) and circulating hydrogen compressor (3) after the feedstock pump pressurization, temperature required through being heated to reaction, enter reactor (4) reaction again, catalyst in reactor can be a bed or a plurality of bed, to the multistage bed, temperature can be controlled by cold hydrogen (5) between every bed, the gas-liquid mixture that is come out by reactor is through heat exchange, washing, enter high-pressure separator (6) after the cooling, liquid phase in the high score (7) enters the product separation system, gas phase goes circulating hydrogen compressor (8) to recycle, for the high-sulfur raw material (as S＞2wt%), recycle hydrogen can be carried out the sulphuring treatment of amine wash-out.Catalyst system therefor can be one or more, but a kind of molecular sieve type hydrogenation catalyst should be arranged at least.The one-stage process technical process is the simplest, and general hydro-refining unit only need be used part or all of catalyzer instead, and corresponding adjustment operational condition can realize.Table 2 is several examples of this technical process, and table 1 is the raw materials used oil properties of reaction.3912,3882 are the industrial hydrocracking catalyst that Fushun Petrochemical Company oil three factory's catalyst plants are produced in the table 2, FH-5 is the industrial Hydrobon catalyst that Shenyang Catalyst Plant produces, the dedicated molecular sieve used hydrogenation conversion catalyst that SS-1 develops for this technological process, WO
320%, NiO 6%Y type molecular sieve 15%, Al
2O
359%, can find out, adopt processing method of the present invention, handle the poor ignition quality fuel raw material, just can make cetane value improve 10-17 unit, while desulfurization, nitrogen, the level and the unifining process that reach aromatic hydrocarbons are suitable.Different catalyst reaction performances have certain difference, the nitrogen content of stock oil has bigger influence to the selectivity of reaction process, reaction conditions also influences bigger to product property, improve hydrogen pressure, reduce the raising that air speed helps cetane value, several catalyzer in the example are processed each raw material all might choose more suitable reaction conditions, thereby improves cetane value by a larger margin.
Series connection one-stage process diesel oil hydrogenation conversion process be under the hydrocracking condition with poor ignition quality fuel at first by the hydrofining bed, the N+ α NH of adjustment material
3Afterwards, again by containing the hydrogenation conversion catalyst bed of molecular sieve.Its principle technical process (Fig. 3) is: stock oil (9) mixes with the hydrogen of hydrogen of making a fresh start (10) and circulating hydrogen compressor after the raw oil pump pressurization, temperature required through being heated to reaction, enter reactor (12) reaction again, catalyst in reactor can be a bed or multistage bed, to the multistage bed, can come control reaction temperature by liquid hydrogen injection (13) between every bed.The gas-liquid mixture that is come out by first reactor makes it to reach the second reactor desired reaction temperature through heat exchange or through squeezing into cold hydrogen, enters second reactor (14) again.If third and fourth reactor is arranged, reactant flow then similar to the above transforms through these reactors successively.The reactant flow that the autoreactor system comes out enters high score (15) after heat exchange, washing cooling, the liquid phase (16) in the high score is gone to rear portion product separation system, and the compressed machine of gas phase (17) recycles as circulating hydrogen.For the high-sulfur raw material, can carry out amine wash-out sulphur place to recycle hydrogen
Reason.Catalyst system therefor can be one or more, but a kind of molecular sieve type hydrogenation catalyst should be arranged at least, by controlling the refining depth of first reactor (12), regulates the material that enters second reactor (14)
N+ α NH
3Value makes second reactor (14) be in good operational stage all the time.Compare with one-stage process, the series connection one-stage process is owing to can control reaction to first reactor, make the cracking catalyst of second reactor remain on the greater activity level, therefore the adaptability to raw material is better than one-stage process, but investment is high slightly by contrast, and table 3 has been listed several examples of this technology, can find out from this table, adopt the series connection one-stage process can under demulcent reaction conditions more, improve 15 of cetane value more than the unit, and the desulfurization removing nitric ability is stronger.Also can pack in second reactor as required has the hydrogenation catalyst of high aromatic hydrocarbons saturability, with the quality of further raising diesel oil.
Two-phase method diesel oil hydrogenation conversion process is, under the hydrofining condition with poor ignition quality fuel at first by the hydrofining section, product liquid again under the hydrocracking condition by containing the hydrogenation conversion catalyst bed of molecular sieve.Its principle technical process (Fig. 4) is: raw material (18) mixes with the hydrogen of hydrogen of making a fresh start (19) and first circulating hydrogen compressor (20) after the raw oil pump pressurization, through being heated to desired reaction temperature, enters first stage reactor (21) reaction again.Catalyst in reactor can be a bed or a plurality of bed, can come control reaction temperature by liquid hydrogen injection (22) between every bed, the reaction mass cooling of coming out by first stage reactor or directly advance high temperature flash tank (23), gas phase is advanced first high-pressure separator (24) through cooling, washing, high score liquid phase (25) is removed the rear portion reactive system, and gas phase is advanced first circulating hydrogen compressor and recycled.To the high-sulfur raw material, this recycle hydrogen can carry out the sulphuring treatment of amine wash-out.High temperature flash tank liquid phase (26) be heated to temperature required second recycle hydrogen (27) through process furnace and the new hydrogen (28) of part is mixed into second stage reactor (29) reaction, reaction effluent is through heat exchange, washing and cool off laggard second high-pressure separator (31), high score liquid phase (32) is gone the rear portion separation system, and gas phase is advanced second circulating hydrogen compressor (32) and recycled.Compare with one-stage process and series connection one-stage process, the two-phase method flow process is the most complicated, invest the highest, but with regard to the adaptability of raw material and satisfy high-quality product and require, two-phase method has maximum handiness, and it can produce the diesel oil (being aromatic hydrocarbons＜20%, sulphur＜0.05% and cetane value＞45) that meets diesel oil new spec index request, table 4 is several examples of this technology, can find out that the variation that a common ground is arranged is exactly cetane value of two-stage method and the one-stage process and the one-stage process of connecting is comparatively responsive to operational condition.Its difference is more preceding two kinds of methods under the identical operations condition, and the amplitude that cetane value improves is bigger, and reaching certain product cetane value in other words needs more demulcent operational condition.
From above example as can be seen, the maximum characteristics of this poor ignition quality fuel conversion technology are, reasonably utilized catalyzer special reaction performance under given conditions, be saturated open loop and not cracking, thereby the method for the enough very economicals of energy improves the quality of diesel product, diesel-fuel cetane number is improved 10 more than the unit keeping diesel yield to be not less than under 95% the condition, this processing method can be adapted to different process schemes simultaneously, to complicated two-phase method hydrogenation technique flow process, practical application can reasonably be selected wherein any one as required from the simplest one-stage process hydrofining flow process.
The various poor ignition quality fuel character of table 1
| Stock oil | LCO-Ⅰ | LCO-Ⅱ | LCO-Ⅲ |
| Density (20) ℃ g/cm 3 | 0.8815 | 0.8950 | 0.9123 |
| Boiling range ℃ | |||
| IBP | 218 | 199 | 222 |
| 10％ | 227 | 210 | 245.5 |
| 50％ | 285 | 269 | 283.2 |
| 90％ | 322 | 310 | 344.3 |
| EBP | 339 | 330 | |
| N/Sppm | 503/1043 | 333/1453 | 795/3028 |
| Aromatic hydrocarbons wt% | 48.8 | 90.8 | 62.5 |
| Cetane value | 40.5 | 26.0 | 30.9 |
Table 2 one-stage process hydrogenation technique example
| Numbering | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 |
| Stock oil | LCO-Ⅰ | LCO-Ⅱ | LCO-Ⅲ | LCO-Ⅲ | LCO-Ⅰ | LCO-Ⅱ | LCO-Ⅰ |
| Catalyzer | 3912 | 3882 | SS-1 | FH-/SS-1 | 3882 | 3882 | SS-1 |
| Reaction conditions | |||||||
| Hydrogen dividing potential drop (MPa) | 6.0 | 6.0 | 6.0 | 6.0 | 10.0 | 5.0 | 6.0 |
| Temperature (℃) | 370 | 380 | 380 | 380 | 370 | 385 | 420 |
| LHSV(h -1) | 2.0 | 2.0 | 2.0 | 2.0 | 1.0 | 2.0 | 4.0 |
| Hydrogen-oil ratio (V) | 1000 | 500 | 1000 | 1000 | 1500 | 500 | 1000 |
| Quality product | |||||||
| 20 ℃ of g/cm of density 3 | 0.8364 | 0.8479 | 0.8705 | 0.8687 | 0.8290 | 0.8508 | 0.8502 |
| N/Sppm | 2.5/- | 2.0/22.0 | 5.7/71.0 | 4.1/73.0 | 1.5/15 | 6.9/81 | 4.1/18 |
| Aromatic hydrocarbons wt% | 36.6 | 59.7 | 38.3 | ||||
| Cetane value | 53.0 | 41.8 | 41 | 43 | 58 | 38.0 | 49.0 |
| ＞180 ℃ of yield wt% | ＞95 | 95.5 | ＞98 | ＞98 | ＞98 | ＞98 | 96.0 |
Table 3 series connection one-stage process hydrogenation technique example
| Numbering | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 |
| Stock oil | LCO-Ⅰ | LCO-Ⅱ | LCO-Ⅲ | LCO-Ⅰ | LCO-Ⅱ |
| Catalyzer | 3936/SS-1 | 3936/SS-1 | 3936/SS-1 | 3936/SS-1 | 3936/SS-1 |
| Reaction conditions | |||||
| Hydrogen dividing potential drop (MPa) | 6.5 | 6.5 | 6.5 | 10.0 | 5.0 |
| Temperature (℃) | 360/360 | 360/370 | 360/370 | 352/356 | 365/370 |
| LHSV(h -1) | 1.5 | 1.5 | 1.5 | 1.0 | 1.5 |
| Hydrogen-oil ratio (V) | 500 | 500 | 500 | 1000 | 500 |
| Quality product | |||||
| 20 ℃ of g/cm of density 3 | 0.8344 | 0.8447 | 0.8687 | 0.8230 | 0.8500 |
| N/S ppm | 1.7/7.9 | ＜1/6.0 | 3.2/33.0 | ＜1/4.0 | 2.5/16.0 |
| Aromatic hydrocarbons wt% | 33.9 | 58.0 | 47.0 | 30.0 | 63.0 |
| Cetane value | 55 | 43 | 44 | 60 | 39 |
| ＞180 ℃ of yield wt% | ＞96 | 96 | ＞96 | ＞96 | ＞96 |
Table 4 two-phase method hydrogenation technique example
| Numbering | Example 13 | Example 14 | Example 15 | Example 16 | Example 17 |
| Stock oil | LCO-Ⅰ | LCO-Ⅱ | LCO-Ⅲ | LCO-Ⅰ | LCO-Ⅱ |
| Catalyzer | 3936/SS-1 | 3936/SS-1 | 3936/SS-1 | 3936/SS-1 | 3936/SS-1 |
| Reaction conditions | |||||
| Hydrogen dividing potential drop (MPa) | 6.5 | 6.5 | 6.5 | 10.0 | 5.0 |
| Temperature (℃) | 360/340 | 360/360 | 360/350 | 350/340 | 365/365 |
| LHSV(h-1) | 1.5 | 1.5 | 1.5 | 1.0 | 1.5 |
| Hydrogen-oil ratio (V) | 800 | 800 | 800 | 1500 | 500 |
| Quality product | |||||
| 20 ℃ of g/cm of density 3 | 0.8182 | 0.8233 | 0.8227 | 0.8120 | 0.8315 |
| N/S ppm | ＜1/＜1 | ＜1/＜1 | ＜1/＜1 | ＜1/＜1 | 2.0/4.2 |
| Aromatic hydrocarbons wt% | 18.0 | 23.0 | 20 | 16 | 27.0 |
| Cetane value | 60 | 53 | 57 | 64 | 47.0 |
| ＞180 ℃ of yield wt% | ＞96 | 96 | ＞96 | ＞98 | 96 |
Claims (8)
1. diesel oil fraction hydrogenation converting process, with the poor ignition quality fuel raw material under the hydrocracking condition by containing the hydrogenation conversion catalyst bed of molecular sieve, it is characterized in that by N+ α NH in the beds material
3Value between 100-1200ppm, " N+ α NH
3" in N represent to enter organonitrogen content in the stock oil of molecular sieve catalyst bed, NH
3The content of ammonia in the expression system, α ≈ 0.1, said hydrocracking condition is:
Temperature: 340-420 ℃
Stagnation pressure: 6.0-13.5MPa
Hydrogen dividing potential drop: 3.0-10.0MPa
Total air speed (liquid): 1.0-4.0h
-1
Hydrogen-oil ratio (volume): 300: 1-1500: 1.
2. according to the method for claim 1, it is characterized in that said N+ α NH
3Value is between 100-500ppm.
3. according to the method for claim 1, it is characterized in that said hydrocracking condition is:
Temperature: 360-400 ℃
Stagnation pressure: 8.0-12.0MPa
Hydrogen dividing potential drop: 6.0-9.0 MPa
Total air speed (liquid): 1.0-2.0 h-1
Hydrogen-oil ratio (volume): 500-1000: 1.
4. according to the method for claim 1, it is characterized in that said hydrogenation conversion catalyst is general hydrocracking catalyst, promptly by Wo, Mo, Co, Ni, Fe hydrogenation active metals component, the catalyzer that molecular sieve component and alumina supporter constitute.
5. according to the method for claim 1, it is characterized in that said hydrogenation conversion catalyst is a kind of W0 of containing
3Or MoO
313-25wt%, Ni or CoO 3-10wt%, molecular sieve 5-30wt%, aluminum oxide 5-30wt%, wherein molecular sieve can be Y, β or type ZSM 5 molecular sieve.
6. according to the method for claim 1, it is characterized in that adopting the one-stage process hydroconversion process, under the hydrocracking condition with poor ignition quality fuel directly by containing the hydrogenation conversion catalyst bed of molecular sieve.
7. according to the method for claim 1, it is characterized in that adopting one-stage serial method hydroconversion process, under the hydrocracking condition with poor ignition quality fuel at first by the hydrofining bed, adjust the N+ α NH of material
3After the value, again by containing the hydrogenation conversion catalyst bed of molecular sieve.
8. according to the method for claim 1, it is characterized in that adopting the two-phase method hydroconversion process, under the hydrofining condition with poor ignition quality fuel at first by the hydrofining section, product liquid under the hydrocracking condition again by containing the hydrogenation conversion catalyst bed of molecular sieve.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN951174932A CN1064988C (en) | 1995-11-22 | 1995-11-22 | Diesel oil fraction hydrogenation converting process |
| JP31052796A JP3291527B2 (en) | 1995-11-22 | 1996-11-21 | Method for hydroconversion of diesel oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN951174932A CN1064988C (en) | 1995-11-22 | 1995-11-22 | Diesel oil fraction hydrogenation converting process |
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| Publication Number | Publication Date |
|---|---|
| CN1156752A CN1156752A (en) | 1997-08-13 |
| CN1064988C true CN1064988C (en) | 2001-04-25 |
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ID=5081280
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN951174932A Expired - Lifetime CN1064988C (en) | 1995-11-22 | 1995-11-22 | Diesel oil fraction hydrogenation converting process |
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| JP (1) | JP3291527B2 (en) |
| CN (1) | CN1064988C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4036352B2 (en) * | 1998-08-31 | 2008-01-23 | 新日本石油株式会社 | Method for producing high cetane number low sulfur diesel diesel oil |
| CN100348311C (en) * | 2004-11-26 | 2007-11-14 | 中国石油天然气股份有限公司 | Hydrogenation desulfurized catalyst containing molecular screen |
| CN101412923B (en) * | 2007-10-18 | 2013-01-09 | 中国石油化工股份有限公司 | Hydro-upgrading combined method |
| CN101649221B (en) * | 2008-08-13 | 2012-12-12 | 中国石油天然气股份有限公司 | Method for producing reforming feedstock by light and medium gasoline distillates |
| EA024500B1 (en) * | 2010-09-30 | 2016-09-30 | Юоп Ллк | Apparatus and process for hydroprocessing hydrocarbonaceous feedstock |
| CN103122260B (en) * | 2013-01-29 | 2015-06-03 | 沈阳三聚凯特催化剂有限公司 | Hydrofining technique of mixture of heavy benzene and absorber oil |
| CN105413979A (en) * | 2015-10-28 | 2016-03-23 | 沈阳名华模塑科技有限公司 | Method for producing colored bumpers |
| CN106675638B (en) * | 2015-11-09 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of catalytic diesel oil hydroconversion process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4971680A (en) * | 1987-11-23 | 1990-11-20 | Amoco Corporation | Hydrocracking process |
| US5068025A (en) * | 1990-06-27 | 1991-11-26 | Shell Oil Company | Aromatics saturation process for diesel boiling-range hydrocarbons |
| CN1104678A (en) * | 1993-10-01 | 1995-07-05 | 巴西石油公司 | Process for producing lube base oils of high viscosity index and diesel oil of high cetane number |
| US5515439A (en) * | 1993-12-03 | 1996-05-07 | International Business Machines Corporation | Exchange certificate for one way validation of information |
-
1995
- 1995-11-22 CN CN951174932A patent/CN1064988C/en not_active Expired - Lifetime
-
1996
- 1996-11-21 JP JP31052796A patent/JP3291527B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4971680A (en) * | 1987-11-23 | 1990-11-20 | Amoco Corporation | Hydrocracking process |
| US5068025A (en) * | 1990-06-27 | 1991-11-26 | Shell Oil Company | Aromatics saturation process for diesel boiling-range hydrocarbons |
| CN1104678A (en) * | 1993-10-01 | 1995-07-05 | 巴西石油公司 | Process for producing lube base oils of high viscosity index and diesel oil of high cetane number |
| US5515439A (en) * | 1993-12-03 | 1996-05-07 | International Business Machines Corporation | Exchange certificate for one way validation of information |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09188883A (en) | 1997-07-22 |
| CN1156752A (en) | 1997-08-13 |
| JP3291527B2 (en) | 2002-06-10 |
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