CN103102895B - Hydro-upgrading method for production of low-condensation point motor fuel from biolipid - Google Patents
Hydro-upgrading method for production of low-condensation point motor fuel from biolipid Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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Abstract
The invention relates to a hydro-upgrading method for production of a low-condensation point motor fuel from biolipid. The method comprises the following steps that: biolipid is used as raw oil, and the raw oil and hydrogen pass through a first-stage hydrogenation reaction zone under hydrogenation operation conditions, wherein the first-stage hydrogenation reaction zone comprises at least two hydrogenation reactors, and the raw oil and hydrogen pass through one reactor operated at a low temperature at first and then pass through the other reactor operated at a high temperature; a material flow generated in hydrogenation is separated, obtained hydrogen-rich gas is recycled, and obtained liquid enters into a second-stage hydro-upgrading reaction zone; and a material flow generated in hydro-upgrading is separated, obtained side hydrogen is recycled, and an obtained liquid product is subjected to fractionation so as to obtain naphtha and low-condensation point diesel oil; wherein in a reaction state, the active component of a hydrogenation catalyst used in a first stage and a second stage is one or more selected from the group consisting of W, Mo, Ni and Co in a reduction state. Compared with the prior art, the method provided by the invention can effectively improve storage stability of biolipid as a fuel oil and can effectively prolong stability of a hydrogenation apparatus.
Description
Technical field
The present invention relates to a kind of method of hydrotreating, particularly one take bio-oil as the hydrogenation modification method of stock oil, direct production automotive fuel.
Background technology
The energy in current global range is mainly derived from fossil energy, and its PetroChina Company Limited. is the main source of automotive fuel.Oil belongs to Nonrenewable energy resources, not only resource is day by day exhausted, and heaviness and in poor quality aggravation, and world economy sustainable development, environmental regulation increasingly stringent need to produce a large amount of light clean fuel, these increase new oil substitutes while all requiring to improve existing oil Refining Technologies, produce satisfactory product with minimum cost.
Bio-oil, as renewable resources, obtains the extensive attention in the world, and each research unit and enterprise are all making great efforts to carry out its research as clean energy.The method production biofuel (being generally fatty acid methyl ester) utilizing transesterify has been proven technique, but because fatty acid methyl ester oxygen level is high, although many countries and regions have put into effect the standard of biofuel successively, and are not suitable for all oil engines.Bio-oil produces automotive fuel by the method for hydrogenation, and all remove by oxygen or partly remove the product produced and meet automotive fuel standard, this method directly can meet the requirement of existing market.
Existing animal-plant oil hydrogenation method produces the processing technology of automotive fuel, US20060186020, EP1693432, CN101321847A, CN200710012090.6, CN200680045053.9, CN200710065393.4, CN200780035038.0, CN200710012208.5, CN200780028314.0 and CN101029245A etc. disclose vegetables oil hydroconversion process, adopt coker naphtha, diesel oil distillate (straight-run diesel oil, LCO and coker gas oil), the petroleum hydrocarbon cuts such as wax oil cut and bio-oil are mixed into hydrogenation catalyst bed, produce diesel product or preparing ethylene by steam cracking raw material etc.US5705722 discloses the diesel oil blending component producing diesel oil distillate scope containing the vegetables oil such as unsaturated fatty acids, fat and animal oil mixing back end hydrogenation.
EP1741767 and EP1741768 discloses a kind of method of producing diesel oil distillate with animal-plant oil, be mainly animal-plant oil first through hydrotreatment, then by isomerization catalyst bed layer, obtain low freezing point diesel fuel component, but owing to generating water in hydroprocessing processes, cause very adverse influence to isomerization catalyst, device can not long-period stable operation.
Comprise in the bio-oil hydrogenation process of aforesaid method, one of subject matter run into is the less stable of catalyzer, and running period shortens, and needs more catalyst changeout of often stopping work.Particularly independent with bio-oil be raw material or bio-oil blending ratio higher time, the running period of hydrogenation catalyst is more subject to obvious impact, cannot meet the requirement of industrial application.
In prior art, bio-oil hydrogenation produces the method for automotive fuel, the petroleum fractions hybrid process of general needs and larger proportion, otherwise can not running period be ensured, or directly by hydrofining-catalyst for hydro-upgrading bed, the component poor stability of cracking catalyst activity.The present invention is by optimizing the grating technology and operational condition that use catalyzer, first paragraph hydrofining (operational condition of optimization and the hydrogenation catalyst of composition grating), second segment hydro-upgrading, it can be directly raw material production high-grade low-freezing point automotive fuel with bio-oil, solving bio-oil hydrogenation unit can not the problem of long period steady running, significantly can reduce the condensation point of diesel oil distillate simultaneously.
Summary of the invention
For the deficiencies in the prior art, the invention provides the hydrogenation modification method that a kind of bio-oil produces low condensation point automotive fuel, can be separately stock oil with animal-plant oil, the method of direct production automotive fuel under the condition of hydrogenation, can the high-quality diesel oil blending product of direct production, the situation that diesel product can not be occurred biofuel that conventional animal-plant oil obtains is gone mouldy, can ensure that hydrogenation catalyst has longer running period simultaneously, be suitable for industrial application.
The hydrogenation modification method that bio-oil of the present invention produces low condensation point automotive fuel comprises following content:
A one or more in () bio-oil are stock oil;
B () is under Hydroprocessing conditions, stock oil and hydrogen pass through the first paragraph reaction zone of at least two hydrogenators, hydrogenation catalyst is loaded in hydrogenator, stock oil and hydrogen are first by the hydrogenator of cold operation, then by the hydrogenator of high-temperature operation, under response behaviour, the active ingredient of hydrogenation catalyst is one or more in W, Mo, Ni and Co of reduction-state;
C () first paragraph reaction zone hydrogenation effluent is separated into gas phase and liquid phase, gas-phase dehydration process Posterior circle uses, the second segment reaction zone using catalyst for hydro-upgrading is entered after liquid phase mixes with circulation gas, under response behaviour, the active metal component of catalyst for hydro-upgrading is one or more in W, Mo, Ni and Co of reduction-state;
D the gas phase of () second segment reaction zone reaction effluent recycles, liquid phase fractionation in separation column of second segment reaction zone reaction effluent obtains petroleum naphtha and low freezing point diesel fuel.
In the inventive method step (a), the bio-oil raw material used can comprise vegetables oil or animal grease, vegetables oil comprises one or more in soybean oil, peanut oil, Viscotrol C, rapeseed oil, Semen Maydis oil, sweet oil, plam oil, Oleum Cocois, tung oil, oleum lini, sesame oil, Oleum Gossypii semen, sunflower seed oil and rice bran wet goods, and animal grease comprises one or more in butter, lard, sheep oil and fish oil etc.
In the inventive method step (b), the Hydroprocessing conditions of the hydrotreating reactor of cold operation is generally reaction pressure 3.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h
-1~ 6.0h
-1, average reaction temperature 120 DEG C ~ 280 DEG C; The operational condition of the hydrotreating reactor of high-temperature operation is reaction pressure 3.0MPa ~ 20.0MPa, hydrogen to oil volume ratio 200:1 ~ 3000:1, volume space velocity 0.3h
-1~ 6.0h
-1, average reaction temperature is higher than the hydrotreating reactor of cold operation 50 DEG C ~ 300 DEG C, preferably high 80 ~ 220 DEG C.Process furnace or interchanger are set between the hydrotreating reactor of cold operation and the hydrotreating reactor of high-temperature operation, to adjust the temperature of reaction of the hydrotreating reactor of high-temperature operation.
Reaction mass first by the hydrotreating reactor of cold operation, the active ingredient of the hydrotreating catalyst of use with the weight content of oxide basis for 3% ~ 20%.Reaction mass continues through the hydrotreating reactor of high-temperature operation, and the active ingredient of the hydrotreating catalyst used in the hydrotreating reactor of high-temperature operation counts 15% ~ 40% with oxide weight.In the hydrotreating reactor of preferred high-temperature operation, the active component content of catalyzer is higher than the catalyzer in cold operation hydrotreating reactor, preferably high 5 ~ 25 percentage points (with active ingredients with oxide basis).Reactor generally can arrange 2 ~ 5, is preferably 2.A kind of catalyzer can be loaded in each hydrotreating reactor, also can load multiple catalysts.
The carrier of hydrotreating catalyst is generally aluminum oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc., can contain other auxiliary agent, as P, Si, B, Ti, Zr etc. simultaneously.Can commercial catalyst be adopted, also can by the existing method preparation in this area.Hydrogenation active component is the catalyzer of oxidation state, carries out conventional reduction treatment before the use, makes hydrogenation active component be converted into reduction-state.
Business hydrogenation catalyst mainly contains, as Fushun Petrochemical Research Institute (FRIPP) develop 3926, 3936, CH-20, FF-14, FF-18, FF-24, FF-26, FF-36, FH-98, FH-UDS, the hydrogenation catalysts such as FZC-41, the HR-416 of Inst Francais Du Petrole, the hydrogenation catalysts such as HR-448, the ICR174 of CLG company, ICR178, the hydrogenation catalysts such as ICR179, Uop Inc. is newly developed HC-P, HC-K UF-210/220, the TK-525 of Topsor company, TK-555, the hydrogenation catalysts such as TK-557, the KF-752 of AKZO company, KF-840, KF-848, KF-901, the hydrogenation catalysts such as KF-907.
The hydrogenation catalyst of business hydrogenation catalyst or preparation is generally oxidation state, uses hydrogen 200 DEG C ~ 500 DEG C temperature before use, is reduced to reduction-state under preferably 220 DEG C ~ 450 DEG C conditions.Whenever forbid in system, inject sulfur-bearing, nitrogenous medium, avoid poisoning of catalyst.
In the inventive method step (c), the Hydroprocessing conditions of second segment reaction zone is generally reaction pressure 3.0MPa ~ 20.0MPa, usually (pressure rating that identical finger herein identical identical with first paragraph reaction zone, due to the Pressure Drop of Flow of Goods and Materials, second segment reaction zone reaction pressure can a little less than first paragraph reaction zone), hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h
-1~ 6.0h
-1, average reaction temperature 180 DEG C ~ 465 DEG C; Preferred operational condition is hydrogen to oil volume ratio 300:1 ~ 2500:1, volume space velocity 0.4h
-1~ 4.0h
-1, average reaction temperature 200 DEG C ~ 445 DEG C.
In the inventive method step (c), the catalyst for hydro-upgrading of second reaction zone has isomery function, as containing beta-molecular sieve, and the components such as SAPO-11 molecular sieve, SAPO-41, NU-10 molecular sieve or ZSM-22 molecular sieve.The hydrogenation active metals component of catalyst for hydro-upgrading is generally 10% ~ 40% with the weight content of oxide basis.The massfraction of catalyst for hydro-upgrading Middle molecule sieve is generally 5% ~ 40%.Other component in catalyst for hydro-upgrading is generally the porous refractory oxide such as aluminum oxide, silicon oxide, amorphous aluminum silicide.The commercial catalysts that second reaction zone uses mainly contains, as FC-14, FC-16, FC-20 etc. that Fushun Petrochemical Research Institute (FRIPP) develops.
The hydrogenation catalyst of business hydrogenation catalyst or preparation is generally oxidation state, uses hydrogen 200 DEG C ~ 500 DEG C temperature before use, is reduced to reduction-state under preferably 220 DEG C ~ 450 DEG C conditions.Whenever forbid in system, inject sulfur-bearing, nitrogenous medium, avoid poisoning of catalyst.
Accompanying drawing explanation
Fig. 1 is the hydrogenation modification method principle flow chart that bio-oil of the present invention produces low condensation point automotive fuel.
Embodiment
Method of the present invention is specific as follows: with the mixing oil of one or more in bio-oil for stock oil, under Hydroprocessing conditions, stock oil and hydrogen pass through low temperature and the high temperature hydrogenation reactor of loading catalyst, the hydrogenated oil obtained is separated in high-pressure separator (abbreviation high score) gas circulation obtained and uses, also system can be gone out, the liquid fractionation obtained and hydrogen are mixed into the second segment reaction zone comprising and have isomery performance catalyst for hydro-upgrading, obtain hydro-upgrading logistics and be separated the gas circulation use obtained in high-pressure separator (abbreviation high score), also system can be gone out, liquid fractionation obtains following products: gas, petroleum naphtha, one or more in low freezing point diesel fuel, if improve the character of diesel product further or extend the cycle of operation, also consider that a part of diesel oil and/or unconverted oil loop back reactive system.The bio-oil that embodiment uses is commercially available prod, uses front filtering solid impurity.
Further illustrate particular case of the present invention below by embodiment, before formally reacting, catalyzer uses hydrogen reducing 10 hours at 380 DEG C.
The main composition of table 1 hydrogenation catalyst and character.
| Catalyzer | Catalyzer 1 | Catalyzer 2 | Catalyzer 3 | Modifying catalyst |
| Catalyzer forms | ||||
| MoO 3，wt% | 7.0 | 15.7 | 24.5 | 18.0 |
| NiO，wt% | 2.0 | 3.8 | 2.5 | |
| CoO，wt% | 2.4 | |||
| Beta-molecular sieve, wt% | 10.6 | |||
| Alumina supporter, wt% | Surplus | Surplus | Surplus | Surplus |
| The main character of catalyzer | ||||
| Specific surface, m 2/g | >160 | >160 | >160 | >160 |
| Pore volume, ml/g | >0.30 | 0.32 | 0.33 | >0.34 |
Table 2 embodiment processing condition and test-results.
| First paragraph reaction zone processing condition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Stock oil | Soybean oil | Rapeseed oil | Oleum Gossypii semen | Oleum Gossypii semen |
| Cold operation reactor | ||||
| Catalyzer | Catalyzer 1 | Catalyzer 1/ catalyzer 2 | Catalyzer 1/ catalyzer 2 | Catalyzer 2 |
| Catalyst volume ratio | 100 | 20:80 | 50:50 | 100 |
| Reaction pressure, MPa | 17.0 | 5.0 | 10.0 | 12.0 |
| Entrance hydrogen to oil volume ratio | 2000:1 | 300:1 | 1000:1 | 800:1 |
| Cumulative volume air speed, h -1 | 2.0 | 1.5 | 0.8 | 0.4 |
| Average reaction temperature, DEG C | 240 | 180 | 200 | 150 |
| High-temperature operation reactor | ||||
| Catalyzer | Catalyzer 3 | Catalyzer 3 | Catalyzer 3 | Catalyzer 3 |
| Reaction pressure, MPa | 17.0 | 5.0 | 10.0 | 12.0 |
| Entrance hydrogen to oil volume ratio | 2000:1 | 300:1 | 1000:1 | 1000:1 |
| Cumulative volume air speed, h -1 | 2.0 | 1.8 | 0.5 | 0.5 |
| Average reaction temperature, DEG C | 380 | 350 | 360 | 320 |
| Second segment reaction zone processing condition | ||||
| Catalyzer | Modifying catalyst | Modifying catalyst | Modifying catalyst | Modifying catalyst |
| Reaction pressure, MPa | 17.0 | 5.0 | 10.0 | 12.0 |
| Entrance hydrogen to oil volume ratio | 1500 | 500 | 800 | 1000 |
| Volume space velocity, h -1 | 2.0 | 4.5 | 1.5 | 3.0 |
| Average reaction temperature, DEG C | 320 | 360 | 310 | 290 |
| Diesel product | ||||
| Density, g/cm 3 | 0.780 | 0.778 | 0.781 | 0.782 |
| Sulphur content, μ g/g | <5 | <5 | <5 | <5 |
| Condensation point, DEG C | -25 | -30 | -10 | -5 |
| Cetane value | >80 | >80 | >80 | >80 |
Table 3 embodiment processing condition and test-results.
| First paragraph processing condition | Embodiment 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Stock oil | Oleum Gossypii semen | Oleum Gossypii semen | Oleum Gossypii semen | Oleum Gossypii semen |
| Cold operation reactor | ||||
| Catalyzer | Catalyzer 1 | |||
| Reaction pressure, MPa | 10.0 | |||
| Entrance hydrogen to oil volume ratio | 2000:1 | |||
| Cumulative volume air speed, h -1 | 2.0 | |||
| Average reaction temperature, DEG C | 200 | |||
| High-temperature operation reactor | ||||
| Catalyzer | Catalyzer 3 | Catalyzer 3/ modifying catalyst | Catalyzer 3/ modifying catalyst | Catalyzer 3/ modifying catalyst |
| Reaction pressure, Mpa | 10.0 | 10.0 | 10.0 | 10.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1000:1 | 1000:1 |
| Cumulative volume air speed, h -1 | 0.8 | 0.46 | 0.46 | 0.46 |
| Average reaction temperature, DEG C | 330 | 330 | 330 | 340 |
| Second segment processing condition | ||||
| Catalyzer | Modifying catalyst | |||
| Reaction pressure, MPa | 10.0 | |||
| Entrance hydrogen to oil volume ratio | 1000:1 | |||
| Cumulative volume air speed, h -1 | 2.5 | |||
| Average reaction temperature, DEG C | 330 | |||
| Runtime, h | 1000 | 200 | 300 | 500 |
| Pressure Drop, MPa | 0 | 0.1 | 0.3 | 0.6 |
| Diesel product | ||||
| Density, g/cm 3 | 0.779 | 0.781 | 0.812 | 0.865 |
| Sulphur content, μ g/g | <5 | <5 | <5 | <5 |
| Condensation point, DEG C | -20 | -20 | -10 | 10 |
| Cetane value | >80 | >80 | 78 | 70 |
Comparative example catalyzer 3 consumption is identical with the total consumption of embodiment 5 catalyzer 1 and catalyzer 3, and comparative example modifying catalyst consumption is identical with embodiment 5 modifying catalyst consumption.As can be seen from embodiment, bio-oil can direct production low freezing point diesel fuel product by the method for hydrotreating of this technology, or fine-quality diesel oil blending component, and can long-time steady operation.
Claims (8)
1. bio-oil produces a hydrogenation modification method for low condensation point automotive fuel, it is characterized in that comprising following content:
A one or more in () bio-oil are stock oil;
B () is under Hydroprocessing conditions, stock oil and hydrogen pass through the first paragraph reaction zone of at least two hydrogenators, hydrogenation catalyst is loaded in hydrogenator, stock oil and hydrogen are first by the hydrogenator of cold operation, then by the hydrogenator of high-temperature operation, under response behaviour, the active ingredient of hydrogenation catalyst is one or more in W, Mo, Ni and Co of reduction-state;
C () first paragraph reaction zone hydrogenation effluent is separated into gas phase and liquid phase, gas-phase dehydration process Posterior circle uses, the second segment reaction zone using catalyst for hydro-upgrading is entered after liquid phase mixes with circulation gas, under response behaviour, the active metal component of catalyst for hydro-upgrading is one or more in W, Mo, Ni and Co of reduction-state;
D the gas phase of () second segment reaction zone reaction effluent recycles, liquid phase fractionation in separation column of second segment reaction zone reaction effluent obtains petroleum naphtha and low freezing point diesel fuel;
Wherein in step (b), the reaction pressure of the hydrotreating reactor of cold operation is 3.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h
-1~ 6.0h
-1, average reaction temperature is 120 DEG C ~ 280 DEG C; The reaction pressure of the hydrotreating reactor of high-temperature operation is 3.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h
-1~ 6.0h
-1, average reaction temperature is higher than the hydrotreating reactor of cold operation 50 DEG C ~ 300 DEG C;
Wherein in step (b), in the cold operation hydrotreating reactor that first reaction mass passes through, the active ingredient of the hydrotreating catalyst of use with the weight content of oxide basis for 3% ~ 20%; Reaction mass continues through the hydrotreating reactor of high-temperature operation, and the active ingredient of the hydrotreating catalyst used in the hydrotreating reactor of high-temperature operation counts 15% ~ 40% with oxide weight.
2. in accordance with the method for claim 1, it is characterized in that: the bio-oil raw material in step (a) comprises vegetables oil or animal grease.
3. in accordance with the method for claim 1, it is characterized in that: in step (b), the average reaction temperature of the hydrotreating reactor of high-temperature operation is higher than the hydrotreating reactor of cold operation 80 ~ 220 DEG C.
4. in accordance with the method for claim 1, it is characterized in that: with active ingredient with oxide basis, in the hydrotreating reactor of high-temperature operation, the active component content of catalyzer is higher than the catalyzer in cold operation hydrotreating reactor 5 ~ 25 percentage points.
5. in accordance with the method for claim 1, it is characterized in that: in step (c), the catalyst for hydro-upgrading of second reaction zone contains beta-molecular sieve, SAPO-11 molecular sieve, SAPO-41, NU-10 molecular sieve or ZSM-22 molecular sieve.
6. according to the method described in claim 1 or 5, it is characterized in that: in step (c), the hydrogenation active metals component of the catalyst for hydro-upgrading of second reaction zone with the weight content of oxide basis for 10% ~ 40%.
7. in accordance with the method for claim 1, it is characterized in that: in step (c), second segment reaction zone for reaction pressure be 3.0MPa ~ 20.0MPa, hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h
-1~ 6.0h
-1, average reaction temperature is 180 DEG C ~ 465 DEG C.
8. in accordance with the method for claim 1, it is characterized in that: in step (c), the hydrogen to oil volume ratio of second segment reaction zone is 300:1 ~ 2500:1, and volume space velocity is 0.4h
-1~ 4.0h
-1, average reaction temperature is 200 DEG C ~ 445 DEG C.
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| EP1693432A1 (en) * | 2005-02-18 | 2006-08-23 | Petroleo Brasileiro S.A. - Petrobras | Vegetable oil hydroconversion process |
| CN101321847A (en) * | 2005-11-30 | 2008-12-10 | 新日本石油株式会社 | Hydrorefining process and hydrorefined oil |
| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the method for paraffinic hydrocarbons |
| CN102041023A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Method for improving residual oil hydrogenation by blending biological grease |
-
2011
- 2011-11-10 CN CN201110353355.5A patent/CN103102895B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1693432A1 (en) * | 2005-02-18 | 2006-08-23 | Petroleo Brasileiro S.A. - Petrobras | Vegetable oil hydroconversion process |
| CN101321847A (en) * | 2005-11-30 | 2008-12-10 | 新日本石油株式会社 | Hydrorefining process and hydrorefined oil |
| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the method for paraffinic hydrocarbons |
| CN102041023A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Method for improving residual oil hydrogenation by blending biological grease |
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