CN103102911B - Bio-oil produces the method for hydrotreating of low aromatic solvent naphtha - Google Patents
Bio-oil produces the method for hydrotreating of low aromatic solvent naphtha Download PDFInfo
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- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The present invention relates to the method for hydrotreating that a kind of bio-oil produces low aromatic solvent naphtha, comprise: take bio-oil as stock oil, under Hydroprocessing conditions, stock oil and hydrogen are by the first paragraph hydroconversion reaction zone at least containing two hydrogenators, stock oil and hydrogen are first by the reactor of cold operation, then by the reactor of high-temperature operation, hydrogenation resultant flow point is from the hydrogen-rich gas recycle obtained, be separated the liquid obtained and enter second segment hydrocracking reaction district, hydrocracking resultant flow point recycles from the secondary hydrogen obtained, be separated the liquid product fractionation obtained and obtain various low aromatic solvent oil production.S-contained substance is supplemented, to maintain hydrogen sulfide content in circulation gas in reaction mass.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 invention belongs to the production method of renewable energy source, relate to a kind of method of hydrotreating, particularly one take bio-oil as the method for hydrotreating of stock oil, direct production low aromatic solvent naphtha.
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.
Summary of the invention
For the deficiencies in the prior art, the invention provides the method for hydrotreating that a kind of bio-oil produces low aromatic solvent naphtha, can take bio-oil as stock oil separately, the method for direct production low aromatic solvent naphtha under the condition of hydrogenation, there is hydrogenation process stablize, the features such as running period is long.
The method of hydrotreating that bio-oil of the present invention produces low aromatic solvent naphtha 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, gas-phase dehydration process Posterior circle uses, the second segment reaction zone using hydrocracking catalyst is entered after liquid phase mixes with circulation gas, under response behaviour, the active metal component of hydrocracking catalyst is one or more in W, Mo, Ni and Co of sulphided 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 low aromatic solvent oil distillate;
E () supplements S-contained substance in reaction mass, to maintain hydrogen sulfide content in circulation gas.
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 hydrogenator of cold operation is generally reaction pressure 2.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and cumulative volume air speed is 0.3h
-1~ 6.0h
-1, average reaction temperature 120 DEG C ~ 280 DEG C; The operational condition of the hydrogenator of high-temperature operation is reaction pressure 2.0MPa ~ 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 hydrogenator of cold operation 50 DEG C ~ 300 DEG C, preferably high 80 ~ 220 DEG C.Process furnace or interchanger are set between the hydrogenator of cold operation and the hydrogenator of high-temperature operation, to adjust the temperature of reaction of the hydrogenator 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-KUF-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.
In the inventive method step (c), the operational condition of second segment reaction zone is generally reaction pressure 2.0MPa ~ 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 hydrocracking catalyst of second segment reaction zone has cracking function, as containing the component such as Y zeolite and/or ZSM-5 molecular sieve.The hydrogenation active metals component of hydrocracking catalyst is generally 5% ~ 40% with the weight content of oxide basis.The weight content of molecular sieve component in hydrocracking catalyst is generally 5% ~ 60%.Other refractory inorganic oxides can be contained in hydrocracking catalyst simultaneously.Second segment reaction zone use commercial catalysts mainly contain, as Fushun Petrochemical Research Institute (FRIPP) develop 3971,3976, FC-12, FC-18, FC-24, FC-26, FC-32, FC-46, FC-50, FDW-1 etc.
In the inventive method step (d), the low aromatic solvent naphtha obtained is mixed solvent oil distillate, can continue fractionation obtains in vegetable oil extraction solvent, No. 90 solvent oils, No. 120 solvent oils, No. 200 trade mark such as solvent oil, D30, D40 low aromatic solvent naphthas one or more according to the actual requirements.Specifically can determine according to the boiling range of mixed solvent oil.
In the inventive method step (d), at low conversion rate in 100% time, the unconverted oil fractionated out in separation column can loop back first paragraph reaction zone or second segment reaction zone, preferred cycle goes back to second segment reaction zone, and the quality looping back the unconverted oil of reactive system is 5% ~ 50% of fresh feed (referring to the raw material of the first reaction zone).
In the inventive method, first paragraph reaction zone (refining reaction district) and second segment reaction zone (cracking reaction district) hydrogenation active component are the catalyzer of oxidation state, carry out conventional sulfidizing before the use, make hydrogenation active component be converted into sulphided state, or use the catalyzer that ex situ presulfiding is good.
In the inventive method, the sulfur-containing medium supplemented in reaction mass (optimum is dosed in stock oil) can be the compound of sulfur-bearing, as DMDS, CS
2deng, also can be the oil light-end products of sulfur-bearing, as the boat coal, diesel oil etc. of sulfur-bearing.Supplementing by sulphur, can ensure that the hydrogen sulfide content in circulation gas is not less than 0.005v%, preferred 0.01v% ~ 2.0v%.
In the inventive method, Hydrobon catalyst can be supplemented in right amount, by material hydrogenation such as issuable a small amount of rare hydrocarbon in hydrocracking process finally arranging of hydrocracking catalyst bed.
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 is by optimizing the grating technology and operational condition that use catalyzer, and first paragraph hydrofining (hydrogenation catalyst of grating), second segment hydrocracking can be directly raw material production low aromatic solvent naphtha with bio-oil.Extend the raw material sources of high added value low aromatic solvent naphtha, and production cost is low, added value of product can be improved further.
Accompanying drawing explanation
Fig. 1 is the method for hydrotreating principle flow chart that bio-oil of the present invention produces low aromatic solvent naphtha.
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 cold operation and the high-temperature operation hydrogenation first paragraph reaction zone of loading catalyst, the hydrogenated oil obtained is separated the dehydration obtained in high-pressure separator (abbreviation high score) after, gas circulation uses, also system can be gone out, the liquid fractionation obtained and hydrogen are mixed into the second segment reaction zone comprising and have cracking performance hydrocracking catalyst, obtain hydrocracking 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 all kinds of SOLVENTS oil production, during low conversion rate, unconverted oil is circulated to second segment 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 1 | Cracking catalyst 2 |
| Catalyzer forms | |||||
| MoO 3，wt% | 7.0 | 15.7 | 24.5 | 10.0 | 20.0 |
| NiO，wt% | 2.0 | 3.8 | 2.1 | 4.6 | |
| CoO，wt% | 2.4 | ||||
| ZSM-5 molecular sieve, wt% | 13.6 | ||||
| Y molecular sieve, wt% | 20.5 | ||||
| Alumina supporter, wt% | Surplus | Surplus | Surplus | Surplus | Surplus |
| The main character of catalyzer | |||||
| Specific surface, m 2/g | >160 | >160 | >160 | >160 | >160 |
| Pore volume, ml/g | >0.30 | 0.32 | 0.33 | >0.34 | >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 | 4.0 | 12.0 | 8.0 |
| 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 | 4.0 | 14.0 | 8.0 |
| 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 | ||||
| Stock oil | First paragraph product liquid | First paragraph product liquid | First paragraph product liquid | First paragraph product liquid+15% unconverted oil |
| Catalyzer | Cracking catalyst 1 | Cracking catalyst 1 | Cracking catalyst 2 | Cracking catalyst 2 |
| Reaction pressure, MPa | 17.0 | 4.0 | 12.0 | 8.0 |
| 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 |
| Sulfur-containing medium | DMDS | DMDS | CS 2 | CS 2 |
| Hydrogen sulfide content in circulation gas, μ L/L | 20000 | 400 | 4000 | 1000 |
| Spirit fraction | ||||
| Yield, quality % | 88 | 82 | 89 | 88 |
| Aromaticity content | Do not detect | Do not detect | Do not detect | Do not detect |
| Sulphur content, μ g/g | <0.5 | <0.5 | <0.5 | <0.5 |
| Boiling range scope, DEG C | 65～174 | 63～153 | 62～126 | 60～95 |
Table 3 embodiment processing condition and test-results.
| First paragraph reaction zone 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/ cracking catalyst 1 | Catalyzer 3/ cracking catalyst 1 | Catalyzer 3/ cracking catalyst 1 |
| 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 reaction zone processing condition | ||||
| Catalyzer | Cracking catalyst 1 | |||
| 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 | |||
| Sulfur-containing medium | CS 2 | CS 2 | CS 2 | CS 2 |
| Hydrogen sulfide content in circulation gas, μ L/L | 500 | 500 | 500 | 500 |
| Runtime, h | 1000 | 200 | 300 | 500 |
| Pressure Drop, MPa | 0 | 0.1 | 0.3 | 0.6 |
| Spirit fraction | ||||
| Yield, quality % | 86 | 86 | 61 | 38 |
| Aromaticity content | Do not detect | Do not detect | Do not detect | Do not detect |
| Sulphur content, μ g/g | <0.5 | <0.5 | <0.5 | <0.5 |
| Boiling range scope, DEG C | 61～170 | 65～170 | 65～170 | 65～170 |
Yield with second segment reaction zone feeds for benchmark.Comparative example catalyzer 3 consumption is identical with the total consumption of embodiment 5 catalyzer 1 and catalyzer 3, and comparative example cracking catalyst 1 consumption is identical with embodiment 5 cracking catalyst 1 consumption.
As can be seen from embodiment, bio-oil can the various low aromatic solvent oil production of direct production by the method for hydrotreating of this technology, by selecting different bio-oils, can produce high-quality low aromatic solvent naphtha, and running is stable.
Claims (11)
1. bio-oil produces a method of hydrotreating for low aromatic solvent naphtha, it is characterized in that comprising following process:
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, in the hydrogenator of cold operation, the active ingredient of the hydrogenation catalyst of use with the weight content of oxide basis for 3% ~ 20%; In the hydrogenator of high-temperature operation, the active ingredient of the hydrogenation catalyst used counts 15% ~ 40% with oxide weight, 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, and the average reaction temperature of the hydrogenator of high-temperature operation is higher than the hydrogenator of cold operation 50 DEG C ~ 300 DEG C;
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 hydrocracking catalyst is entered after liquid phase mixes with circulation gas, under response behaviour, the active metal component of hydrocracking catalyst is one or more in W, Mo, Ni and Co of sulphided 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 low aromatic solvent oil distillate;
E () supplements S-contained substance in reaction mass, to maintain hydrogen sulfide content in circulation gas.
2. in accordance with the method for claim 1, it is characterized in that: the bio-oil described 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 reaction pressure of the hydrogenator of cold operation is 2.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and cumulative volume air speed is 0.3h
-1~ 6.0h
-1, average reaction temperature is 120 DEG C ~ 280 DEG C; The reaction pressure of the hydrogenator of high-temperature operation is 2.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h
-1~ 6.0h
-1.
4. in accordance with the method for claim 1, it is characterized in that: in step (b), the average reaction temperature of the hydrogenator of high-temperature operation is higher than the hydrogenator of cold operation 80 ~ 220 DEG C.
5. 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 2.0MPa ~ 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.
6. in accordance with the method for claim 1, it is characterized in that: in step (c), the operational condition of second segment reaction zone 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.
7. in accordance with the method for claim 1, 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, the hydrogenation active metals component of hydrocracking catalyst is with the weight content of oxide basis for 5% ~ 40%, and the weight content of molecular sieve component in hydrocracking catalyst is 5% ~ 60%.
8. in accordance with the method for claim 1, it is characterized in that: in step (d), unconverted oil is circulated to first paragraph reaction zone, or is circulated to second segment reaction zone, and turning oil accounts for 5% ~ 50% of fresh feed quality.
9. in accordance with the method for claim 1, it is characterized in that: in step (e), the sulfur-containing medium supplemented in reaction mass is the compound of sulfur-bearing, the oil light-end products of sulfur-bearing.
10. according to the method described in claim 1 or 9, it is characterized in that: in step (e), the hydrogen sulfide content in circulation gas is not less than 0.005v%.
11. in accordance with the method for claim 10, it is characterized in that: in step (e), and the hydrogen sulfide content in circulation gas is 0.01v% ~ 2.0v%.
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| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the method for paraffinic hydrocarbons |
| CN101802145A (en) * | 2007-09-20 | 2010-08-11 | 环球油品公司 | Make diesel-fuel by biological renewable raw materials |
| CN101952392A (en) * | 2007-12-21 | 2011-01-19 | 环球油品公司 | Prepare aviation fuel from biological renewable raw materials |
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| CN101595203A (en) * | 2006-12-01 | 2009-12-02 | 北卡罗来纳州立大学 | The method of conversion of biomass to fuel |
| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the method for paraffinic hydrocarbons |
| CN101802145A (en) * | 2007-09-20 | 2010-08-11 | 环球油品公司 | Make diesel-fuel by biological renewable raw materials |
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