CN102464997B - Hydrogenation method for producing motor fuel from biological grease - Google Patents
Hydrogenation method for producing motor fuel from biological grease Download PDFInfo
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- CN102464997B CN102464997B CN201010536293.7A CN201010536293A CN102464997B CN 102464997 B CN102464997 B CN 102464997B CN 201010536293 A CN201010536293 A CN 201010536293A CN 102464997 B CN102464997 B CN 102464997B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The invention relates to a hydrogenation method for producing a motor fuel from biological grease. The method comprises the following steps: 1, allowing hydrogen and raw oil which comprises one or more of biological grease to go through at least two hydrogenation reactors under hydrogenation operation conditions: allowing the raw oil and hydrogen to firstly go through a low temperature operation hydrogenation reactor and then go through a high temperature operation hydrogenation reactor, wherein the active component of a hydrogenation catalyst in a reaction state comprises one or several of W, Mo, Ni and Co; 2, separating a hydrogenation effluent into a gas phase which is circularly used and a liquid phase which enters a fractionating tower; and 3, supplying a sulfur-containing substance to reaction materials to maintain the content of hydrogen sulfide in the circulation gas. Compared with the prior art, the method of the invention can effectively improve the storage stability of the biological grease as fuel oil and also can effectively prolong the stability of a hydrogenation device.
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 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 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, the petroleum fractions hybrid process of general needs and larger proportion, otherwise can not ensure running period.The present invention uses the grating technology of catalyzer and operational condition by optimizing, and can take directly bio-oil as raw material production high-quality automotive fuel, and 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 the method for hydrotreating that a kind of bio-oil produces automotive fuel, can be separately stock oil with bio-oil, the method of direct production automotive fuel under the condition of hydrogenation, 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 that bio-oil of the present invention produces automotive fuel 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, 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 () hydrogenation effluent 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, diesel oil and unconverted oil, wherein part diesel oil and/or portion of non-converted oil can loop back reactive system;
E () supplements S-contained substance in reaction mass, to maintain hydrogen sulfide content in circulation gas.
The bio-oil that the inventive method uses 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.Also can other raw material of mixing portion in bio-oil, as petroleum fractions, liquefied coal coil, coal tar, shale wet goods, blending ratio is determined on demand, is generally less than 50% (weight).
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 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 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.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.
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 the catalyzer in cold operation hydrogenator.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.
In the inventive method, the quality of the diesel oil and/or unconverted oil that loop back reactive system be fresh feed oil quality≤50%, be preferably fresh feed oil quality≤35%, the fresh feed of fresh feed oil and unmixed circulation diesel oil and/or unconverted oil is oily.
The sulfur-containing medium supplemented in reaction mass 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, makes the hydrogen sulfide content in circulation gas be not less than 0.005v%, preferred 0.01v% ~ 2.0v%, ensures that hydrogenation catalyst is in active higher sulphided state.
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 and hydrogen pass through low temperature and the high temperature hydrogenation reactor of loading catalyst, the hydrogenated oil obtained is separated in high-pressure separator (abbreviation high score) gas circulation obtained and uses, also system can be gone out, the liquid fractionation obtained obtains following products: gas, petroleum naphtha, one or more in diesel oil, if improve the character of diesel product further or extend the cycle of operation, also consider that a part of diesel oil and unconverted oil loop back 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 |
| Catalyzer forms | |||
| MoO 3，wt％ | 7.0 | 15.7 | 24.5 |
| NiO，wt％ | 2.0 | 3.8 | |
| CoO，wt％ | 2.4 | ||
| 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 2 embodiment processing condition and test-results
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 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 | Catalyzer 3 | Catalyzer 3 |
| 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 | 0.67 | 0.5 | 0.5 | 0.5 |
| Average reaction temperature, DEG C | 330 | 330 | 330 | 340 |
| Sulfur-containing medium | CS2 | CS2 | CS2 | CS2 |
| Hydrogen sulfide content in circulation gas, | 500 | 500 | 500 | 500 |
| μL/L | ||||
| Runtime, h | 1000 | 200 | 300 | 500 |
| Per pass conversion, quality % | About 80 | About 70 | About 60 | About 40 |
| Diesel product | ||||
| Density, g/cm 3 | 0.787 | 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 diesel product by the method for hydrotreating of this technology, or fine-quality diesel oil blending component, and can long-time steady operation.
Claims (10)
1. bio-oil produces a method of hydrotreating for 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 are by 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, and the carrier of hydrogenation catalyst is aluminum oxide;
C () hydrogenation effluent 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, diesel oil and unconverted oil;
E () supplements S-contained substance in reaction mass, to maintain hydrogen sulfide content in circulation gas;
Wherein: 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 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 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 130 DEG C ~ 300 DEG C.
2. in accordance with the method for claim 1, it is characterized in that: bio-oil comprises 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 pollard oil, and animal grease comprises one or more in butter, lard, sheep oil and fish oil.
3. according to the method described in claim 1 or 2, it is characterized in that: other raw material of mixing portion in bio-oil, other raw material is selected from petroleum fractions, liquefied coal coil, coal tar or shale oil, and other raw material mixed weight ratio is less than 50%.
4. in accordance with the method for claim 1, it is characterized in that: process furnace or interchanger are set between the hydrogenator of cold operation and the hydrogenator of high-temperature operation.
5. in accordance with the method for claim 1, it is characterized in that: 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%.
6. according to the method described in claim 1 or 5, it is characterized in that: the active ingredient of the hydrogenation catalyst used in the hydrogenator of high-temperature operation counts 15% ~ 40% with oxide weight.
7. in accordance with the method for claim 1, it is characterized in that: the part diesel oil that fractionation obtains and/or portion of non-converted oil circulation time reactive system, the quality of the diesel oil and/or unconverted oil that loop back reactive system be fresh feed oil quality≤50%.
8. in accordance with the method for claim 7, it is characterized in that: the part diesel oil that fractionation obtains and/or portion of non-converted oil circulation time reactive system, the quality of the diesel oil and/or unconverted oil that loop back reactive system be fresh feed oil quality≤35%.
9. in accordance with the method for claim 1, it is characterized in that: the sulfur-containing medium supplemented in reaction mass, makes the hydrogen sulfide content in circulation gas be not less than 0.005v%.
10. in accordance with the method for claim 9, it is characterized in that: the sulfur-containing medium supplemented in reaction mass, makes the hydrogen sulfide content in circulation gas be 0.01v% ~ 2.0v%.
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| CN104845668A (en) * | 2015-05-15 | 2015-08-19 | 河南百优福生物能源有限公司 | Method for prolonging operation cycle of deoxidized biomass oil hydrogenation device |
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| CN101463263A (en) * | 2007-12-18 | 2009-06-24 | 中国石油化工股份有限公司 | Preparation of diesel component |
| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the method for paraffinic hydrocarbons |
| CN101842465A (en) * | 2007-06-15 | 2010-09-22 | 纳幕尔杜邦公司 | Catalytic process for converting renewable resources into paraffins for use as diesel blending stocks |
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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 |
| CN101842465A (en) * | 2007-06-15 | 2010-09-22 | 纳幕尔杜邦公司 | Catalytic process for converting renewable resources into paraffins for use as diesel blending stocks |
| CN101463263A (en) * | 2007-12-18 | 2009-06-24 | 中国石油化工股份有限公司 | Preparation of diesel component |
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