CN103102905B - Bio-oil produces the two-stage method method of hydrotreating of high-grade low-freezing point automotive fuel - Google Patents
Bio-oil produces the two-stage method method of hydrotreating of high-grade low-freezing point automotive fuel Download PDFInfo
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- CN103102905B CN103102905B CN201110353666.1A CN201110353666A CN103102905B CN 103102905 B CN103102905 B CN 103102905B CN 201110353666 A CN201110353666 A CN 201110353666A CN 103102905 B CN103102905 B CN 103102905B
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Abstract
The present invention relates to the two-stage method method of hydrotreating that a kind of bio-oil produces high-grade low-freezing point automotive fuel, 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 hydro-upgrading reaction zone.The secondary hydrogen of hydro-upgrading recycles at second segment, and liquid product fractionation obtains petroleum naphtha and low freezing point diesel fuel.Under response behaviour, Pt and/or Pd that the active ingredient of hydrogenation catalyst that first paragraph uses is reduction-state, in W, Mo, Ni and Co that the hydrogenation active component of the hydrogenation catalyst that second segment uses is sulphided state one or more.Compared with prior art, the inventive method can ensure activity stability and the device long-period stable operation of catalyzer while producing low condensation point automotive fuel.
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-grade low-freezing point 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.
Summary of the invention
For the deficiencies in the prior art, the invention provides the two-stage method method of hydrotreating that a kind of bio-oil produces high-grade low-freezing point automotive fuel, first paragraph uses noble metal catalyst, second segment uses sulphided state non-precious metal catalyst, can be separately stock oil with animal-plant oil, the method of the low condensation point automotive fuel of direct production 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 two-stage method method of hydrotreating that bio-oil of the present invention produces high-grade low-freezing 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 Pt and/or Pd of reduction-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, 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 sulphided 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 petroleum naphtha and low freezing point diesel fuel;
E () supplements S-contained substance in second segment reaction mass, to maintain hydrogen sulfide content in the circulation gas of second segment 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.
Reaction mass is first by the hydrogenator of cold operation, and the active ingredient of the hydrogenation catalyst of use is in the element quality of precious metals pt and/or Pd, and the content of noble metal hydrogenation active ingredient is 0.01% ~ 0.50%.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 is in the element of precious metals pt and/or Pd, and the content of noble metal hydrogenation active ingredient is 0.10% ~ 3.50%.In the hydrogenator of preferred high-temperature operation, the active component content of catalyzer is higher than the catalyzer in cold operation hydrogenator, preferably high 0.1 ~ 3 percentage point (in element quality).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.Noble metal catalyst such as Fushun Petrochemical Research Institute (FRIPP) develops HDO-18 catalyzer, also can by described method preparations such as CN00123141.3.
In the inventive method step (b), 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 first paragraph 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, 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.
In the inventive method step (c), the catalyst for hydro-upgrading of second segment reaction zone has isomery function, as containing components such as beta-molecular sieve, SAPO-11 molecular sieve, SAPO-41, NU-10 molecular sieve or ZSM-22 molecular sieves.The hydrogenation active metals component of catalyst for hydro-upgrading is generally 10% ~ 40% with the weight content of oxide basis, and the weight content of molecular sieve in catalyst for hydro-upgrading is generally 5% ~ 60%.The commercial catalysts that second segment reaction zone uses mainly contains, as FC-14, FC-16, FC-20 etc. that Fushun Petrochemical Research Institute (FRIPP) develops.
In the inventive method step (c), second segment 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.
The sulfur-containing medium supplemented in reaction mass (optimum is dosed in the liquid phase feeding of second segment 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 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 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 noble metal 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.
Accompanying drawing explanation
Fig. 1 is the two-stage method method of hydrotreating principle flow chart of bio-oil production high-quality automotive fuel of the present invention.
Fig. 2 is the another one principle flow chart that bio-oil of the present invention produces the two-stage method method of hydrotreating of high-grade low-freezing 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 are by loading low temperature and the high temperature hydrogenation reactor of noble metal catalyst, 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 isomery performance catalyst for hydro-upgrading, obtain hydro-upgrading 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 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 can consider that a part of diesel oil and unconverted oil loop back first paragraph reaction zone reactive system.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 | Modifying catalyst |
| Catalyzer forms | ||||
| Pt，wt% | 0.4 | 1.2 | 0.05 | |
| Pd，wt% | 0.1 | 0.1 | ||
| MoO 3，wt% | 18.9 | |||
| NiO，wt% | 3.0 | |||
| Beta-molecular sieve, wt% | 18.0 | |||
| 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 | 0.33 | 0.32 | 0.35 | 0.34 |
Table 2 embodiment processing condition and test-results.
| Processing condition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Stock oil | Soybean oil | Rapeseed oil | Tung oil | Oleum Gossypii semen+15% turning oil |
| First paragraph reaction zone operational condition | ||||
| Cold operation reactor | ||||
| Catalyzer | Catalyzer 3 | Catalyzer 3/ catalyzer 1 | Catalyzer 3/ catalyzer 1 | Catalyzer 3 |
| Catalyst volume ratio | 100 | 20:80 | 50:50 | 100 |
| Reaction pressure, MPa | 17.0 | 8.0 | 4.0 | 12.0 |
| Entrance hydrogen to oil volume ratio | 2000:1 | 300:1 | 1000:1 | 800:1 |
| Volume space velocity, h -1 | 2.0 | 1.5 | 0.8 | 0.4 |
| Average reaction temperature, DEG C | 150 | 190 | 130 | 100 |
| High-temperature operation reactor | ||||
| Catalyzer | Catalyzer 1 | Catalyzer 1 | Catalyzer 2 | Catalyzer 2 |
| Reaction pressure, MPa | 17.0 | 8.0 | 4.0 | 12.0 |
| Entrance hydrogen to oil volume ratio | 2000:1 | 300:1 | 1000:1 | 1000:1 |
| Volume space velocity, h -1 | 1.0 | 1.8 | 0.5 | 2.5 |
| Average reaction temperature, DEG C | 360 | 320 | 340 | 380 |
| Second segment reaction zone operational condition | ||||
| Catalyzer | Modifying catalyst | Modifying catalyst | Modifying catalyst | Modifying catalyst |
| Reaction pressure, MPa | 17.0 | 8.0 | 4.0 | 6.0 |
| Entrance hydrogen to oil volume ratio | 1000 | 500 | 800 | 2000 |
| Volume space velocity, h -1 | 2.0 | 4.5 | 1.5 | 3.5 |
| Average reaction temperature, DEG C | 320 | 370 | 310 | 290 |
| Sulfur-containing medium | DMDS | DMDS | CS 2 | CS 2 |
| Hydrogen sulfide content in circulation gas, μ L/L | 100 | 1000 | 60 | 9000 |
| Diesel product | ||||
| Density, g/cm 3 | 0.781 | 0.779 | 0.784 | 0.780 |
| Sulphur content, μ g/g | <5 | <5 | <5 | <5 |
| Condensation point, DEG C | -20 | -35 | -10 | -28 |
| Cetane value | >80 | >80 | >80 | >80 |
Table 3 embodiment processing condition and test-results.
| 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 3 | |||
| Reaction pressure, MPa | 10.0 | |||
| Entrance hydrogen to oil volume ratio | 1000:1 | |||
| Volume space velocity, h -1 | 3.0 | |||
| Average reaction temperature, DEG C | 180 | |||
| High-temperature operation reactor | ||||
| Catalyzer | Catalyzer 2 | Catalyzer 2/ modifying catalyst | Catalyzer 2/ modifying catalyst | Catalyzer 2/ 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 |
| Volume space velocity, h -1 | 1.0 | 0.6 | 0.6 | 0.6 |
| Average reaction temperature, DEG C | 320 | 320 | 320 | 320 |
| Two step process condition | — | — | — | |
| Catalyzer | Modifying catalyst | |||
| Reaction pressure, MPa | 10.0 | |||
| Entrance hydrogen to oil volume ratio | 1000:1 | |||
| Cumulative volume air speed, h -1 | 3.0 | |||
| Average reaction temperature, DEG C | 330 | |||
| Sulfur-containing medium | DMDS | |||
| Hydrogen sulfide content in circulation gas, μ L/L | 500 | |||
| Runtime, h | 1000 | 200 | 400 | 600 |
| Diesel product | ||||
| Density, g/cm 3 | 0.782 | 0.782 | 0.799 | 0.859 |
| Condensation point, DEG C | -24 | -24 | -6 | 10 |
| Sulphur content, μ g/g | <5 | <5 | <5 | <5 |
| Cetane value | >80 | >80 | 78 | 70 |
Comparative example catalyzer 2 consumption is identical with the total consumption of embodiment 5 catalyzer 2 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 high-grade low-freezing point diesel product by the two-stage method method of hydrotreating of this technology, or fine-quality diesel oil blending component, and can long-time steady operation.
Claims (9)
1. bio-oil produces a two-stage method method of hydrotreating for high-grade low-freezing 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 Pt and/or Pd of reduction-state, in the hydrogenator of cold operation, the active ingredient of the hydrogenation catalyst used is in the element quality of precious metals pt and/or Pd, the content of noble metal hydrogenation active ingredient is 0.01% ~ 0.50%, the active ingredient of the hydrogenation catalyst used in the hydrogenator of high-temperature operation is in the element quality of precious metals pt and/or Pd, the content of noble metal hydrogenation active ingredient is 0.10% ~ 3.50%, in the hydrogenator of high-temperature operation, the active component content of catalyzer is in element quality, higher than the catalyzer in cold operation hydrogenator 0.1 ~ 3 percentage point, 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, recycle in first paragraph reaction zone after gas-phase dehydration process, 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 sulphided 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 petroleum naphtha and low freezing point diesel fuel;
E () supplements S-contained substance in second segment reaction mass, to maintain hydrogen sulfide content in the circulation gas of second segment reaction zone.
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 hydrotreatment reaction of cold operation
Reaction pressure 3.0MPa ~ the 20.0MPa of device, 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.
4. according to the method described in claim 1 or 3, 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.
5. according to the method described in claim 1 or 3, it is characterized in that: the first paragraph reaction zone in step (b) arranges 2 ~ 5 reactors.
6. 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 ~ 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.
7. in accordance with the method for claim 6, 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 catalyst for hydro-upgrading of second segment reaction zone has isomery function, catalyst for hydro-upgrading contains beta-molecular sieve, 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 with the weight content of oxide basis for 10% ~ 40%.
9. in accordance with the method for claim 1, it is characterized in that: the sulfur-containing medium supplemented in second segment reaction mass is the compound of sulfur-bearing, or the oil light-end products of sulfur-bearing, and in circulation gas, hydrogen sulfide content is not less than 0.005v%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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