CN103102920B - The two-stage method method of hydrotreating of production high-quality solvent oil - Google Patents
The two-stage method method of hydrotreating of production high-quality solvent oil Download PDFInfo
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Abstract
The present invention relates to a kind of two-stage method method of hydrotreating producing high-quality solvent oil, comprise: bio-oil raw material and hydrogen are by the first paragraph hydroconversion reaction zone at least containing two hydrogenators, first by the reactor of cold operation, then by the reactor of high-temperature operation, hydrogen-rich gas is in first paragraph recycle, and liquid enters second segment hydrocracking reaction district.The secondary hydrogen of hydrocracking recycles at second segment, and liquid product fractionation obtains all kinds of SOLVENTS oil production.Under response behaviour, in W, Mo, Ni and Co that the active ingredient of hydrogenation catalyst that first paragraph uses is sulphided state one or more, Pt and/or Pd that the hydrogenation active component of the hydrogenation catalyst that second segment uses is reduction-state.Compared with prior art, the inventive method adds the production method of low aromatic solvent naphtha, and can ensure activity stability and the device long-period stable operation of catalyzer.
Description
Technical field
The present invention relates to a kind of method of hydrotreating, particularly a kind of is stock oil with bio-oil, the two-stage method method of hydrotreating of direct production high-quality solvent oil.
Background technology
World economy sustainable development, in current global range, the main source of Chemicals is fossil energy, wherein most importantly oil and coal.These two kinds of fossil energies all belong to Nonrenewable energy resources, not only resource is day by day exhausted, and heaviness and in poor quality aggravation, difficulty of processing and tooling cost increase gradually, new oil substitutes is found except carrying out existing oil Refining Technologies improving, produce satisfactory product with minimum cost, especially the development and utilization of renewable resources obtains paying attention to more and more widely.
Bio-oil is as renewable resources, and main composition is carbon, hydrogen and oxygen, very similar to the composition of alkane, alcohol, ether etc., 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 low freezing point diesel fuel cut with animal-plant oil.
Comprise in the bio-oil hydrogenation process of aforesaid method, one of subject matter run into is that bed carbon distribution causes shorten running period, needs more catalyst changeout of often stopping work, and the main purpose product of these technology is automotive fuel.
Solvent oil is important petroleum products, and its added value is higher than fuel product, and particularly the added value of high-grade low aromatic solvent naphtha is higher.The low aromatic solvent naphtha raw materials for production of current top grade are limited (is generally only limitted to gasoline fraction or the kerosene(oil)fraction of paraffinic crude, or reforming raffinate oil etc.), owing to requiring aromaticity content lower (some solvent oil index request aromaticity content is lower than 0.1%), therefore need to adopt complicated processing route, condition is harsh, production cost is high, limits the production of high-grade low aromatic solvent naphtha.
In prior art, bio-oil usually passes through separately or produces the method for automotive fuel with the method for other petroleum products mixing back end hydrogenations.The present invention uses grating technology and operational condition by optimizing, and first paragraph hydrotreatment (sulfurized hydrogenation catalyst of grating), second segment hydrocracking (noble metal catalyst) can be directly raw material production low aromatic solvent naphtha with bio-oil.The present invention extends the raw material sources of high added value low aromatic solvent naphtha, and production cost is low, can improve added value of product further.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of two-stage method method of hydrotreating producing high-quality solvent oil, take bio-oil as stock oil, under the condition of hydrogenation, first by using sulfide type catalyst first paragraph reaction zone, then by using the second segment reaction zone of Nobel metal hydrogen cracking catalyst, direct production solvent oil, there is hydrogenation process stablize, the features such as running period is long.
The two-stage method method of hydrotreating of production high-quality solvent oil of the present invention 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 sulphided state;
C () first paragraph reaction zone hydrogenation effluent is separated into gas phase and liquid phase, recycle in first paragraph reaction zone after gas-phase dehydration process, liquid phase enters the second segment reaction zone using hydrocracking catalyst after mixing with second segment reaction zone circulation gas, under response behaviour, the active metal component of hydrocracking catalyst is Pt and/or Pd of reduction-state;
D gas phase that the reaction effluent gas-liquid separation of () second segment reaction zone obtains recycles in second segment reaction zone, and liquid phase fractionation in separation column that the reaction effluent gas-liquid separation of second segment reaction zone obtains obtains all kinds of SOLVENTS oil distillate;
E () supplements S-contained substance in first paragraph reaction mass, to maintain hydrogen sulfide content in the circulation gas of first paragraph reaction zone.
In the inventive method step (a), the bio-oil 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.
In the inventive method step (b), reaction mass first by the hydrogenator of cold operation, the active ingredient of the hydrogenation catalyst of use with the weight content of oxide basis for 3% ~ 20%.Reaction mass continues through the hydrogenator of high-temperature operation, and the active ingredient of the hydrogenation catalyst used in the hydrogenator of high-temperature operation counts 15% ~ 40% with oxide weight.In the hydrogenator of preferred high-temperature operation, the active component content of catalyzer is higher than catalyzer in cold operation hydrogenator 3 ~ 25 percentage points.Reactor generally can arrange 2 ~ 5, is preferably 2.A kind of catalyzer can be loaded in each hydrogenator, also can load multiple catalysts.The carrier of hydrogenation 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 sulfidizing before the use, makes hydrogenation active component be converted into sulphided 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.First paragraph reaction zone hydrogenation effluent is separated can comprise fractionating system, also can not comprise fractionating system (only comprising Separate System of Water-jet).When comprising fractionating system, the middle runnings (i.e. diesel oil distillate) fractionating system fractionation obtained enters second segment reaction zone.
In the inventive method step (b), first paragraph reaction zone hydrogenation active component is the catalyzer of oxidation state, carries out conventional sulfidizing before the use, makes hydrogenation active component be converted into sulphided state, or use the catalyzer that ex situ presulfiding is good.
In the inventive method step (c), the Hydroprocessing conditions of second segment reaction zone 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 180 DEG C ~ 465 DEG C; Preferred operational condition is reaction pressure 3.0MPa ~ 18.0MPa, 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.The working pressure of second segment reaction zone can be identical with first paragraph reaction zone, also can be different.The liquid phase entering second segment reaction zone can be the liquid phase material after the gas-liquid separation of first paragraph reaction zone, also can be the intermediate oil that the liquid phase material after the gas-liquid separation of first paragraph reaction zone obtains through separation column fractionation.The working pressure of second segment reaction zone can be identical with first paragraph, also can be different.
In the inventive method step (c), the hydrocracking catalyst of second segment reaction zone has cracking function, as containing the component such as Y zeolite and/or ZSM-5 molecular sieve.Hydrocracking catalyst is in the element of precious metals pt and/or Pd, and the content of noble metal hydrogenation active ingredient is 0.01% ~ 1.50%.The massfraction of hydrocracking catalyst 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.
In the inventive method step (c), catalyzer uses hydrogen 200 DEG C ~ 500 DEG C temperature before use, reduces under preferably 220 DEG C ~ 450 DEG C conditions.Whenever forbid in second segment system, inject sulfur-bearing, nitrogenous medium, avoid poisoning of catalyst.
In the inventive method step (d), the low aromatic solvent naphtha obtained is mixed solvent oil distillate, can continue fractionation according to the actual requirements and obtain vegetable oil extraction solvent, No. 90 solvent oils, No. 120 solvent oils, No. 200 solvent oils, D30, D40 etc. trade mark low aromatic solvent naphthas.Specifically specifically can determine according to the boiling range of mixed solvent oil.If there is unconverted oil, unconverted oil can go out system, also capable of circulation time reactive system.
The sulfur-containing medium supplemented in first paragraph reaction mass (optimum is dosed in the liquid phase feeding of first paragraph reaction zone) in the inventive method step (e) can be the compound of sulfur-bearing, as DMDS, CS
2deng, also can be the oil light-end products of sulfur-bearing, as the petroleum naphtha, boat coal etc. of sulfur-bearing.Supplementing by sulphur, can ensure that the hydrogen sulfide content in the circulation gas of first paragraph reaction zone is not less than 0.005v%, preferred 0.01v% ~ 2.0v%.
Accompanying drawing explanation
Fig. 1 is the two-stage method method of hydrotreating principle flow chart of production high-quality solvent oil of the present invention.
Fig. 2 is the another one principle flow chart of the two-stage method method of hydrotreating of production high-quality solvent oil of the present invention.
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 are by loading low temperature and the high temperature hydrogenation reactor of sulphided state catalyzer, the hydrogenated oil obtained is separated in high-pressure separator (abbreviation high score) gas obtained and recycles in first paragraph reaction zone after processed, the liquid fractionation obtained and hydrogen are mixed into the second segment reaction zone comprising and have cracking performance Nobel metal hydrogen cracking catalyst, obtain hydrocracking logistics to be separated in high-pressure separator (abbreviation high score) gas obtained and to recycle in second segment reaction zone, the liquid fractionation obtained obtains all kinds of SOLVENTS oil production, also consider, at first paragraph, a part of last running and unconverted oil are looped back first paragraph reaction zone.The bio-oil that embodiment uses is commercially available prod, uses front filtering solid impurity.
Particular case of the present invention is further illustrated below by embodiment.
The main composition of table 1 hydrogenation catalyst and character.
| Catalyzer | Catalyzer 1 | Catalyzer 2 | Catalyzer 3 | Cracking catalyst |
| Catalyzer forms | ||||
| MoO 3，wt% | 6.0 | 13.4 | 26.3 | |
| NiO，wt% | 1.8 | 4.7 | ||
| CoO，wt% | 2.6 | |||
| Pt，wt% | 1.05 | |||
| Pd，wt% | 0.03 | |||
| Y molecular sieve, wt% | 25.6 | |||
| 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 | >0.30 | >0.30 | >0.34 |
Table 2 embodiment processing condition and test-results.
| Processing condition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Stock oil | Tung oil | Cocounut oil | Peanut oil | Oleum Gossypii semen+5% turning oil |
| First paragraph reaction zone operational condition | ||||
| Cold operation reactor | ||||
| Catalyzer | Catalyzer 1 | Catalyzer 1/ catalyzer 2 | Catalyzer 1/ catalyzer 2 | Catalyzer 1 |
| Catalyst volume ratio | 100 | 30:70 | 50:50 | 100 |
| Reaction pressure, MPa | 15.0 | 8.0 | 4.0 | 12.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 600:1 | 1500:1 | 300:1 |
| Volume space velocity, h -1 | 1.2 | 0.4 | 0.9 | 3.0 |
| Average reaction temperature, DEG C | 190 | 240 | 280 | 300 |
| High-temperature operation reactor | ||||
| Catalyzer | Catalyzer 3 | Catalyzer 3 | Catalyzer 3 | Catalyzer 2/ catalyzer 3 |
| Catalyst volume ratio | 100 | 100 | 100 | 50:50 |
| Reaction pressure, MPa | 15.0 | 8.0 | 4.0 | 12.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 800:1 | 2000:1 | 1000:1 |
| Volume space velocity, h -1 | 1.0 | 1.5 | 3.0 | 0.8 |
| Average reaction temperature, DEG C | 260 | 280 | 340 | 360 |
| Sulfur-containing medium | DMDS | DMDS | CS 2 | CS 2 |
| Hydrogen sulfide content in circulation gas, μ L/L | 10000 | 2000 | 100 | 900 |
| Second segment reaction zone operational condition | ||||
| Catalyzer | Cracking catalyst | Cracking catalyst | Cracking catalyst | Cracking catalyst |
| Reaction pressure, MPa | 15.0 | 16.0 | 4.0 | 6.0 |
| Entrance hydrogen to oil volume ratio | 1000 | 500 | 800 | 2000 |
| Volume space velocity, h -1 | 3.0 | 2.5 | 2.0 | 1.5 |
| Average reaction temperature, DEG C | 310 | 270 | 260 | 280 |
| Spirit fraction | ||||
| Yield, quality % | 82 | 86 | 87 | 85 |
| Aromaticity content | Do not detect | Do not detect | Do not detect | Do not detect |
| Sulphur content, μ g/g | Do not detect | Do not detect | Do not detect | Do not detect |
| Boiling range scope, DEG C | 61～160 | 63～175 | 61～145 | 61～145 |
Table 3 embodiment processing condition and test-results.
| Processing condition | Embodiment 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Stock oil | Oleum lini | Oleum lini | Oleum lini | Oleum lini |
| Cold operation reactor | ||||
| Catalyzer | Catalyzer 1 | |||
| Reaction pressure, MPa | 8.0 | |||
| Entrance hydrogen to oil volume ratio | 1000:1 | |||
| Volume space velocity, h -1 | 3.0 | |||
| Average reaction temperature, DEG C | 220 | |||
| High-temperature operation reactor | ||||
| Catalyzer | Catalyzer 3 | Catalyzer 3 | Catalyzer 3 | Catalyzer 3 |
| Reaction pressure, MPa | 8.0 | 8.0 | 8.0 | 8.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1000:1 | 1000:1 |
| Volume space velocity, h -1 | 1.0 | 0.75 | 0.75 | 0.75 |
| Average reaction temperature, DEG C | 320 | 320 | 320 | 330 |
| Sulfur-containing medium | CS 2 | CS 2 | CS 2 | CS 2 |
| Hydrogen sulfide content in circulation gas, μ L/L | 300 | 300 | 300 | 300 |
| Two step process condition | ||||
| Catalyzer | Cracking catalyst | Cracking catalyst | Cracking catalyst | Cracking catalyst |
| Reaction pressure, MPa | 8.0 | 8.0 | 8.0 | 8.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1000:1 | 1000:1 |
| Cumulative volume air speed, h -1 | 3.5 | 3.5 | 3.5 | 3.5 |
| Average reaction temperature, DEG C | 330 | 330 | 330 | 330 |
| Runtime, h | 1000 | 200 | 400 | 800 |
| Spirit fraction | ||||
| Yield, quality % | 85 | 85 | 58 | 20 |
| Aromaticity content | Do not detect | Do not detect | Do not detect | Do not detect |
| Sulphur content, μ g/g | Do not detect | Do not detect | Do not detect | Do not detect |
| Boiling range scope, DEG C | 61～170 | 61～170 | 61～170 | 61～170 |
Yield with second segment reaction zone feeds for benchmark.
As can be seen from embodiment, bio-oil can direct production various high-quality low aromatic solvent oil production by the method for hydrotreating of this technology, by selecting different bio-oils, can production high-quality low aromatic solvent naphtha, and running is stable.
Claims (9)
1. produce a two-stage method method of hydrotreating for solvent oil, 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 sulphided state;
C () first paragraph reaction zone hydrogenation effluent is separated into gas phase and liquid phase, recycle in first paragraph reaction zone after gas-phase dehydration process, liquid phase enters the second segment reaction zone using hydrocracking catalyst after mixing with second segment reaction zone circulation gas, under response behaviour, the active metal component of hydrocracking catalyst is Pt and/or Pd of reduction-state;
D gas phase that the reaction effluent gas-liquid separation of () second segment reaction zone obtains recycles in second segment reaction zone, and liquid phase fractionation in separation column that the reaction effluent gas-liquid separation of second segment reaction zone obtains obtains spirit fraction;
E () supplements S-contained substance in first paragraph reaction mass, to maintain hydrogen sulfide content in the circulation gas of first paragraph reaction zone;
Wherein in step (b), the reaction pressure 3.0MPa ~ 20.0MPa of the hydrotreating reactor of cold operation, 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;
Wherein in step (c), the reaction pressure of second segment reaction zone 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 180 DEG C ~ 465 DEG C.
2. in accordance with the method for claim 1, it is characterized in that: in step (a), the bio-oil of use 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: step (b) reaction mass first by the hydrogenator of cold operation, the active ingredient of the hydrogenation catalyst of use with the weight content of oxide basis for 3% ~ 20%; Reaction mass continues through the hydrogenator of high-temperature operation, and the active ingredient of the hydrogenation catalyst used in the hydrogenator of high-temperature operation counts 15% ~ 40% with oxide weight.
5. in accordance with the method for claim 4, it is characterized in that: in the hydrogenator of high-temperature operation, the active component content of catalyzer is higher than the catalyzer in cold operation hydrogenator 3 ~ 25 percentage points.
6. in accordance with the method for claim 1, it is characterized in that: the first paragraph reaction zone in step (b) arranges 2 ~ 5 reactors.
7. in accordance with the method for claim 1, it is characterized in that: in step (c), the reaction pressure of second segment reaction zone is 3.0MPa ~ 18.0MPa, and hydrogen to oil volume ratio 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.
8. according to the method described in claim 1 or 7, it is characterized in that: in step (c), the hydrocracking catalyst of second segment reaction zone has cracking function, hydrocracking catalyst contains Y zeolite and/or ZSM-5 molecular sieve component, hydrocracking catalyst is in the element quality of precious metals pt and/or Pd, and the content of noble metal hydrogenation active ingredient is 0.01% ~ 1.50%.
9. in accordance with the method for claim 1, it is characterized in that: the sulfur-containing medium supplemented in first paragraph reaction mass is the compound of sulfur-bearing, or the oil light-end products of sulfur-bearing, and in the circulation gas of first paragraph reaction zone, hydrogen sulfide content is not less than 0.005v%.
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Citations (3)
| 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 |
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| 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 |
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