CN102911698B - Hydrogenation method for producing high-quality motor fuels with biological oil and fat - Google Patents
Hydrogenation method for producing high-quality motor fuels with biological oil and fat Download PDFInfo
- Publication number
- CN102911698B CN102911698B CN201110217557.7A CN201110217557A CN102911698B CN 102911698 B CN102911698 B CN 102911698B CN 201110217557 A CN201110217557 A CN 201110217557A CN 102911698 B CN102911698 B CN 102911698B
- Authority
- CN
- China
- Prior art keywords
- oil
- hydrogenation
- hydrogenator
- catalyzer
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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 invention discloses a hydrogenation method for producing high-quality motor fuels by hydrogenation of biological oil and fat. The method comprises the steps of (a) selecting one or more of the biological oil and fat as raw oil; (b) under the condition of hydrogenation operations, passing the raw oil and hydrogen through at least two hydrogenation reactors, wherein hydrogenation catalysts are loaded in the hydrogenation reactors; the raw oil and hydrogen firstly passes through a low temperature-operated hydrogenation reactor; the low temperature-operated hydrogenation reactor employs an upward flowing operation mode of co-current flow gas and liquid flowing upward; effluent after the reaction from the low temperature-operated hydrogenation reactor is introduced into a high temperature-operated hydrogenation reactor; and in a reacting state, active components of the hydrogenation catalysts are reduced noble metal or reduced non-noble metal; and (c) separating hydrogenation reaction effluents from the high temperature-operated hydrogenation reactor. Compared with a conventional method, the method provided by the invention can guarantee that a hydrogenation apparatus of the biological oil and fat runs stably in a long period.
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 method for hydrotreating of direct production high-quality 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, and 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 is shorter, 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, and in reaction process, catalyzer coking produces pressure drop, can not ensure running period.The present invention adopts upflowing hydroprocessing mode by optimizing the hydrogenator using the grating technology of catalyzer and the optimisation technique of operational condition and cold operation, reactor pressure decrease can be reduced, be directly raw material production high-quality automotive fuel with bio-oil, solving bio-oil hydrogenation unit can not the problem of long period steady running.In addition, diesel oil distillate after partial reaction and unconverted oil are looped back hydrogenation reaction system, the stable operation of bio-oil hydrogenation unit can be improved further.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method of hydrotreating of bio-oil production high-quality automotive fuel, separately with bio oil, fat for stock oil, the method of direct production automotive fuel under the condition of upflowing hydrogenation, reduce reactor pressure decrease, 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, hydrogenation process is stablized, and running period is long.
The method of hydrotreating of bio-oil production high-quality automotive fuel 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 are by least two hydrogenators, hydrogenation catalyst is loaded in hydrogenator, stock oil and hydrogen are first by the hydrogenator of cold operation, the upper reaches operating method that the hydrogenator of cold operation adopts gas and liquid flowing upwards to flow, the reaction effluent of the hydrogenator of cold operation enters the hydrogenator of high-temperature operation, under response behaviour, the active ingredient of hydrogenation catalyst is precious metal or the base metal of reduction-state;
C the hydrogenation reaction effluent of the hydrogenator of () high-temperature operation is separated into gas phase and liquid phase, gas phase recycles, and liquid phase enters separation column;
D () fractionation in separation column obtains petroleum naphtha and diesel oil.
In the inventive method, in reactive system, be prohibited from entering the material of sulfur-bearing, the impurity such as nitrogenous.
In the inventive method, described upper reaches operating method, refers to that reaction mass enters reactor from reactor bottom, and reacted material discharges the operating method of reactor from reactor head.In the inventive method, the hydrogenator of high-temperature operation can adopt upper reaches operating method, preferably adopts the operating method that gas and liquid flowing flows downward.
The bio-oil that the inventive method uses can comprise vegetables oil and/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.
The Hydroprocessing conditions of the hydrogenator 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 50 DEG C ~ 280 DEG C; The operational condition of the hydrogenator 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 hydrogenator of cold operation 50 DEG C ~ 300 DEG C, preferably high 80 ~ 220 DEG C.Between the hydrogenator of cold operation and the hydrogenator of high-temperature operation, the heating installations such as process furnace are set, with the temperature of reaction needed for the hydrogenator adjusting high-temperature operation.Volume space velocity refers to the volume space velocity of liquid phase feed, i.e. volume space velocity during liquid.
If catalyzer adopts non-noble metal hydrogenation catalyst, 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.
If catalyzer adopts noble metal catalyst, reaction mass is first by 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, 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 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.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, in step (d), when stock oil does not transform completely, the unconverted oil that fractionating system obtains can loop back reactive system, also part diesel cycle can be returned reactive system simultaneously, circulation material be fresh feed weight of oil≤50%, be preferably fresh feed oil≤35%, fresh feed oil is the bio-oil raw material do not mixed with recycle stock.
In the inventive method, 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 system, inject sulfur-bearing, nitrogenous medium, avoid poisoning of catalyst.
Accompanying drawing explanation
Fig. 1 is the method for hydrotreating principle flow chart that bio-oil of the present invention produces 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 1 and hydrogen 2 enter from reactor bottom, by the low temperature hydrogenation reactor 3 of loading catalyst, generate oil 4 and flow out the high temperature hydrogenation reactor 5 entering loading catalyst after heating from reactor head from reactor head, the hydrogenated oil 6 obtained is called for short high score at high-pressure separator 7() be separated the gas 8 that obtains and recycle, also system can be gone out, the liquid 9 obtained enters separation column 14 and obtains following products: gas 10, petroleum naphtha 11, one or more in diesel oil 12, 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 13 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, embodiment low temperature hydrogenation reactor adopts upflowing operating method, and high temperature hydrogenation reactor adopts downflow operation mode.Comparative example 1 and comparative example 4 adopt upflowing to operate, and other comparative example all adopts conventional downflow system hydroprocessing operations.
The main composition of table 1 noble metal catalyst and character.
| Catalyzer | Catalyzer 1 | Catalyzer 2 | Catalyzer 3 |
| Catalyzer forms | |||
| Pt，wt% | 0.4 | 1.2 | 0.05 |
| Pd，wt% | 0.1 | 0.1 | |
| Alumina supporter, wt% | Surplus | Surplus | Surplus |
| The main character of catalyzer | |||
| Specific surface, m 2/g | >160 | >160 | >160 |
| Pore volume, ml/g | 0.33 | 0.32 | 0.35 |
The main composition of table 2 non-precious metal catalyst and character.
| Catalyzer | Catalyzer 4 | Catalyzer 5 | Catalyzer 6 |
| Catalyzer forms | |||
| MoO 3，wt% | 7.0 | 15.7 | 24.5 |
| NiO，wt% | / | 2.4 | 3.8 |
| CoO，wt% | 2.0 | / | / |
| Alumina supporter, wt% | Surplus | Surplus | Surplus |
| The main character of catalyzer | |||
| Specific surface, m 2/g | >160 | >160 | >160 |
| Pore volume, ml/g | 0.30 | 0.32 | 0.33 |
Table 3 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 |
| Cold operation reactor operating condition | ||||
| Catalyzer (by reaction mass flowing direction filling) | 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 | 5.0 | 10.0 | 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 | 145 | 180 | 125 | 90 |
| High-temperature operation reactor operating condition | ||||
| Catalyzer | Catalyzer 1 | Catalyzer 1 | Catalyzer 2 | Catalyzer 2 |
| 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 |
| Volume space velocity, h -1 | 1.0 | 1.8 | 0.5 | 2.5 |
| Average reaction temperature, DEG C | 360 | 320 | 340 | 380 |
| Per pass conversion, quality % | 90 | 75 | 85 | 100 |
| Diesel product | ||||
| Density, g/cm 3 | 0.786 | 0.785 | 0.784 | 0.782 |
| Sulphur content, μ g/g | <5 | <5 | <5 | <5 |
| Cetane value | >80 | >80 | >80 | >80 |
Table 4 embodiment processing condition and test-results.
| Processing condition | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Stock oil | Soybean oil | Rapeseed oil | Tung oil | Oleum Gossypii semen |
| Cold operation reactor operating condition | ||||
| Catalyzer (by reaction mass flowing direction filling) | Catalyzer 4 | Catalyzer 4/ catalyzer 5 | Catalyzer 4/ catalyzer 5 | Catalyzer 5 |
| 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 |
| Volume space velocity, h -1 | 2.0 | 1.5 | 0.8 | 0.4 |
| Average reaction temperature, DEG C | 180 | 230 | 160 | 140 |
| High-temperature operation reactor operating condition | ||||
| Catalyzer | Catalyzer 5 | Catalyzer 6 | Catalyzer 6 | Catalyzer 6 |
| 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 |
| Volume space velocity, h -1 | 1.0 | 1.8 | 0.5 | 2.5 |
| Average reaction temperature, DEG C | 360 | 320 | 340 | 380 |
| Per pass conversion, quality % | 90 | 75 | 85 | 100 |
| Diesel product | ||||
| Density, g/cm 3 | 0.786 | 0.785 | 0.784 | 0.782 |
| Sulphur content, μ g/g | <5 | <5 | <5 | <5 |
| Cetane value | >80 | >80 | >80 | >80 |
Table 5 embodiment and comparative example processing condition and test-results.
| Processing condition | Embodiment 9 | 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 operating condition | ||||
| Catalyzer | Catalyzer 3 | |||
| Reaction pressure, MPa | 10.0 | |||
| Entrance hydrogen to oil volume ratio | 2000:1 | |||
| Volume space velocity, h -1 | 2.0 | |||
| Average reaction temperature, DEG C | 175 | |||
| High-temperature operation reactor operating condition | ||||
| Catalyzer | Catalyzer 2 | Catalyzer 2 | Catalyzer 2 | Catalyzer 2 |
| 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 | 0.67 | 0.5 | 0.5 |
| Average reaction temperature, DEG C | 310 | 310 | 310 | 320 |
| Runtime, h | 2500 | 1000 | 400 | 600 |
| Per pass conversion, quality % | About 80 | About 80 | About 65 | About 45 |
| Diesel product | ||||
| Density, g/cm 3 | 0.785 | 0.786 | 0.809 | 0.862 |
| Sulphur content, μ g/g | <5 | <5 | <5 | <5 |
| Cetane value | >80 | >80 | 78 | 70 |
Table 6 embodiment processing condition and test-results.
| Processing condition | Embodiment 10 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| Stock oil | Oleum Gossypii semen | Oleum Gossypii semen | Oleum Gossypii semen | Oleum Gossypii semen |
| Cold operation reactor operating condition | ||||
| Catalyzer | Catalyzer 4 | |||
| Reaction pressure, MPa | 10.0 | |||
| Entrance hydrogen to oil volume ratio | 2000:1 | |||
| Volume space velocity, h -1 | 2.0 | |||
| Average reaction temperature, DEG C | 170 | |||
| High-temperature operation reactor operating condition | ||||
| Catalyzer | Catalyzer 6 | Catalyzer 6 | Catalyzer 6 | Catalyzer 6 |
| 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 | 0.67 | 0.5 | 0.5 |
| Average reaction temperature, DEG C | 330 | 330 | 330 | 340 |
| Runtime, h | 2500 | 1000 | 300 | 500 |
| Per pass conversion, quality % | About 80 | About 80 | About 60 | About 40 |
| Diesel product | ||||
| Density, g/cm 3 | 0.785 | 0.791 | 0.812 | 0.865 |
| Sulphur content, μ g/g | <5 | <5 | <5 | <5 |
| Cetane value | >80 | >80 | 78 | 70 |
As can be seen from embodiment, bio-oil can direct production fine-quality diesel oil 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. a method of hydrotreating for bio-oil production high-quality automotive fuel, 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 are by least two hydrogenators, hydrogenation catalyst is loaded in hydrogenator, stock oil and hydrogen are first by the hydrogenator of cold operation, the upper reaches operating method that the hydrogenator of cold operation adopts gas and liquid flowing upwards to flow, the reaction effluent of the hydrogenator of cold operation enters the hydrogenator of high-temperature operation, under response behaviour, the active ingredient of hydrogenation catalyst is the precious metal of reduction-state or the base metal of reduction-state;
C the hydrogenation reaction effluent of the hydrogenator of () high-temperature operation is separated into gas phase and liquid phase, gas phase recycles, and liquid phase enters separation column;
D () fractionation in separation column obtains petroleum naphtha and diesel oil;
In the hydrotreating reactor of described high-temperature operation, the active component content of catalyzer is higher than the catalyzer in cold operation hydrotreating reactor, when adopting non-noble metal hydrogenation catalyst, high 5 ~ 25 percentage points with oxide basis with active ingredient; When adopting noble metal catalyst, high 0.1 ~ 3 percentage point in element quality.
2. in accordance with the method for claim 1, it is characterized in that: in reactive system, be prohibited from entering sulfur-bearing, nitrogenous material.
3. in accordance with the method for claim 1, it is characterized in that: the hydrogenator of high-temperature operation adopts upper reaches operating method, or the operating method adopting gas and liquid flowing to flow downward.
4. in accordance with the method for claim 1, it is characterized in that: bio-oil comprises vegetables oil and/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 pollard oil, and animal grease comprises one or more in butter, lard, sheep oil and fish oil.
5. according to the method described in claim 1 or 3, it is characterized in that: the Hydroprocessing conditions of the hydrogenator of cold operation is 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 50 DEG C ~ 280 DEG C; The operational condition of the hydrogenator 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 hydrogenator of cold operation 50 DEG C ~ 300 DEG C.
6. in accordance with the method for claim 5, it is characterized in that: the average reaction temperature of the hydrogenator of high-temperature operation is higher than the hydrogenator of cold operation 80 ~ 220 DEG C.
7. in accordance with the method for claim 1, it is characterized in that: hydrogenation catalyst adopts non-noble metal hydrogenation catalyst, reaction mass is first by the hydrotreating reactor of cold operation, the active ingredient of hydrotreating catalyst used 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.
8. in accordance with the method for claim 1, it is characterized in that: hydrogenation catalyst adopts noble metal catalyst, reaction mass is first by 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, 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%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110217557.7A CN102911698B (en) | 2011-08-01 | 2011-08-01 | Hydrogenation method for producing high-quality motor fuels with biological oil and fat |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110217557.7A CN102911698B (en) | 2011-08-01 | 2011-08-01 | Hydrogenation method for producing high-quality motor fuels with biological oil and fat |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102911698A CN102911698A (en) | 2013-02-06 |
| CN102911698B true CN102911698B (en) | 2015-04-01 |
Family
ID=47610282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110217557.7A Active CN102911698B (en) | 2011-08-01 | 2011-08-01 | Hydrogenation method for producing high-quality motor fuels with biological oil and fat |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102911698B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5705722A (en) * | 1994-06-30 | 1998-01-06 | Natural Resources Canada | Conversion of biomass feedstock to diesel fuel additive |
| CN101103093A (en) * | 2005-01-14 | 2008-01-09 | 耐思特石油公司 | Method for the manufacture of hydrocarbons |
| CN101448918A (en) * | 2006-05-17 | 2009-06-03 | 新日本石油株式会社 | Hydrorefining process |
| CN101463263A (en) * | 2007-12-18 | 2009-06-24 | 中国石油化工股份有限公司 | Preparation of diesel component |
Family Cites Families (1)
| 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 |
-
2011
- 2011-08-01 CN CN201110217557.7A patent/CN102911698B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5705722A (en) * | 1994-06-30 | 1998-01-06 | Natural Resources Canada | Conversion of biomass feedstock to diesel fuel additive |
| CN101103093A (en) * | 2005-01-14 | 2008-01-09 | 耐思特石油公司 | Method for the manufacture of hydrocarbons |
| CN101448918A (en) * | 2006-05-17 | 2009-06-03 | 新日本石油株式会社 | Hydrorefining process |
| CN101463263A (en) * | 2007-12-18 | 2009-06-24 | 中国石油化工股份有限公司 | Preparation of diesel component |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102911698A (en) | 2013-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102464996A (en) | Hydrogenation method for producing biological grease by motor fuel | |
| CN102911696B (en) | Hydrotreating method for producing motor fuels with biological oil and fat | |
| CN102464994B (en) | Hydrogenation method for producing motor fuel from biological oil | |
| CN102464992A (en) | Hydrogenation method for producing high quality motor fuel by biolipid | |
| CN102464997B (en) | Hydrogenation method for producing motor fuel from biological grease | |
| CN102911698B (en) | Hydrogenation method for producing high-quality motor fuels with biological oil and fat | |
| CN102911697A (en) | Method for producing clean fuels by hydrogenation of biological oil and fat | |
| CN103102917B (en) | Produce the two-stage method method of hydrotreating of low condensation point automotive fuel | |
| CN103102920B (en) | The two-stage method method of hydrotreating of production high-quality solvent oil | |
| CN103102900B (en) | Hydrogenation method for producing high quality solvent oil from biological oil | |
| CN102911725B (en) | Hydrogenation process for biological oil and fat blended with diesel oil | |
| CN103102902B (en) | Hydrocracking method for producing low aromatic hydrocarbon solvent oil from biological oil | |
| CN103102897A (en) | Hydrogenation method for production of low-condensation point motor fuel from biolipid | |
| CN103102912B (en) | Two-stage hydrogenation method for producing high quality low freezing point motor fuel | |
| CN102464993B (en) | Hydrogenation method for producing high-quality motor fuel with biological grease | |
| CN102464995B (en) | Hydroprocessing method for producing motor fuel from biological oil | |
| CN103102925B (en) | Hydrogenation method for producing high quality low freezing point motor fuel from biological oil | |
| CN103102905B (en) | Bio-oil produces the two-stage method method of hydrotreating of high-grade low-freezing point automotive fuel | |
| CN103102921B (en) | Two-stage hydrogenation method for producing high quality low freezing point motor fuel | |
| CN103102909B (en) | Two-stage hydrogenation method for producing low freezing point motor fuel from biological oil | |
| CN103102895B (en) | Hydro-upgrading method for production of low-condensation point motor fuel from biolipid | |
| CN103102922B (en) | Two-stage hydrogenation method for producing solvent oil | |
| CN103102908B (en) | Two-stage hydrogenation method for producing low aromatic hydrocarbon solvent oil from biological oil | |
| CN103374410B (en) | Hydrogenation method for producing high-quality kerosene | |
| CN103102904A (en) | Two-stage hydrogenation method for producing high quality low freezing point motor fuel from biological oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |