CN102464992A - Hydrogenation method for producing high quality motor fuel by biolipid - Google Patents
Hydrogenation method for producing high quality motor fuel by biolipid Download PDFInfo
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- CN102464992A CN102464992A CN2010105357604A CN201010535760A CN102464992A CN 102464992 A CN102464992 A CN 102464992A CN 2010105357604 A CN2010105357604 A CN 2010105357604A CN 201010535760 A CN201010535760 A CN 201010535760A CN 102464992 A CN102464992 A CN 102464992A
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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
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Abstract
The present invention relates to a hydrogenation method for producing a high quality motor fuel by biolipid. The method comprises that: one or a plurality of materials in the biolipid are adopted as raw material oil; under a hydrogenation operating condition, the raw material oil and hydrogen gas pass through at least two hydrogenation reactors, wherein the raw material oil and the hydrogen gas firstly pass through the low temperature operation hydrogenation reactor, and then pass through the high temperature operation hydrogenation reactor; under the reaction state, the active component of a hydrogenation catalyst is reduced into the reduced-state Pt and/or the reduced-state Pd; the hydrogenated effluent is separated into a gas phase and a liquid phase, wherein the gas phase is recycled, and the liquid phase enters a fractionating tower; the liquid phase is fractionated in the fractionating tower to obtain naphtha, diesel oil and unconverted oil, wherein the partial diesel oil and/or the partial unconverted oil circularly returns to the reaction system. Compared to the prior art, with the method of the present invention, the storage stability of the biolipid can be effectively improved when the biolipid is adopted as the fuel oil, the stability of the hydrogenation device can be effectively prolonged, and the industrial application value of the biolipid hydrogenation technology can be improved.
Description
Technical field
The present invention relates to a kind of method of hydrotreating, particularly a kind of is raw oil with the bio-oil, the method for hydrotreating of direct production high-quality automotive fuel.
Background technology
The energy in the global range is mainly derived from fossil energy at present, and its PetroChina Company Limited. is the main source of automotive fuel.Oil belongs to Nonrenewable energy resources; Not only resource is exhausted day by day; And heaviness and poor qualityization aggravation; And world economy sustainable development, environmental regulation increasingly stringent need be produced a large amount of light clean fuels, and these increase new oil substitutes when all requiring existing oil Refining Technologies improved, and produce satisfactory product with minimum cost.
Bio-oil obtains the extensive attention in the world as renewable resources, and each research unit and enterprise are all making great efforts to carry out its research as clean energy.Utilizing the method production biofuel (being generally fatty acid methyl ester) of transesterify has been proven technique, because the fatty acid methyl ester oxygen level is high, although many countries and regions have been put into effect the standard of biofuel successively, but unsuitable all oil engines.Bio-oil is produced automotive fuel through the method for hydrogenation, and soon oxygen is all removed or partly removed and produce the product that meets the automotive fuel standard, and this method can directly satisfy the requirement of existing market.
Existing animal-plant oil hydrogenation method is produced 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 the vegetables oil hydroconversion process; Adopt coker, diesel oil distillate (straight-run diesel oil, LCO and coker gas oil); Petroleum hydrocarbon cut such as wax oil cut and bio-oil are mixed into the hydrogenation catalyst bed, produce diesel product or preparing ethylene by steam cracking raw material etc.US5705722 discloses vegetables oil such as containing unsaturated fatty acids, fat and animal oil mixing back end hydrogenation is produced the diesel oil blending component of diesel oil distillate scope.
EP1741767 and EP1741768 disclose a kind of method of producing diesel oil distillate with animal-plant oil; Be mainly animal-plant oil and at first pass through hydrotreatment; Through the isomerization catalyst bed layer, obtain the low freezing point diesel fuel component then, but owing to generate water in the hydrotreatment process; Isomerization catalyst is caused very adverse influence, and device can not long-period stable operation.
Comprise that one of subject matter that runs into is the less stable of catalyzer in the bio-oil hydrogenation process of aforesaid method, running period is shorter, the more catalyst changeout of need often stopping work.Particularly be separately raw material or bio-oil blending ratio when higher with the bio-oil, more receive tangible influence the running period of hydrogenation catalyst, can't satisfy industrial application requirements.
Summary of the invention
Deficiency to prior art; The present invention provides a kind of bio-oil to produce the hydroprocessing process of automotive fuel, can be raw oil with the animal-plant oil separately, the method for direct production automotive fuel under the condition of hydrogenation; Can direct production high-quality diesel oil is in harmonious proportion product; Make diesel product that the situation that biofuel that conventional animal-plant oil makes is gone mouldy can not take place, can guarantee that hydrogenation catalyst has long running period, is suitable for industrial application simultaneously.
The method of hydrotreating of bio-oil production high-quality automotive fuel of the present invention comprises following content:
(a) one or more in the bio-oil are raw oil;
(b) under the hydroprocessing condition, raw oil and hydrogen are through at least two hydrogenators, and hydrogenation is anti-
Answer and load hydrogenation catalyst in the device, raw oil and hydrogen is the hydrogenation reaction through cold operation at first
Device, the hydrogenator through high-temperature operation then, under response behaviour, hydrogenation catalyst
Active ingredient is to go back the Pt and/or the Pd of ortho states;
(c) the hydrogenation elute is separated into gas phase and liquid phase, and gas phase recycles, and liquid phase gets into separation column;
(d) fractionation obtains petroleum naphtha, diesel oil and unconverted oil in separation column, optional part diesel oil with/
Or the part unconverted oil can loop back reactive system.
In the inventive method, be prohibited from entering the material of sulfur-bearing, impurity such as nitrogenous in the reactive system.
The bio-oil that the inventive method is used can comprise vegetables oil or animal oil and fat; Vegetables oil comprises one or more in VT 18, peanut oil, Viscotrol C, rapeseed oil, Semen Maydis oil, sweet oil, plam oil, Oleum Cocois, tung oil, oleum lini, til, Oleum Gossypii semen, sunflower seed oil and the rice bran wet goods, and animal oil and fat comprises one or more in butter, lard, sheep oil and the fish oil etc.
The hydroprocessing condition 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, 50 ℃～280 ℃ of average reaction temperature; 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 than the hydrogenator of cold operation high 50 ℃～300 ℃, preferred high 80～220 ℃.Between the hydrogenator of cold operation and the hydrogenator of high-temperature operation process furnace or interchanger are set, with the temperature of reaction of hydrogenator of adjustment high-temperature operation.
At first through in the hydrogenator of cold operation, the active ingredient of the hydrogenation catalyst of use is in the element quality of precious metals pt and/or Pd for reaction mass, and the content of noble metal hydrogenation active ingredient is 0.01%～0.50%.Reaction mass continues the hydrogenator through high-temperature operation, and the active ingredient of the hydrogenation catalyst that uses 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%.The activity of such catalysts component concentration is higher than the catalyzer in the cold operation hydrogenator in the hydrogenator of preferred high-temperature operation, preferred high 0.1～3 percentage point (in the element quality).Reactor drum generally can be provided with 2～5, is preferably 2.A kind of catalyzer can be loaded in each hydrogenator, also multiple catalyzer can be loaded.
The carrier of hydrogenation catalyst is generally aluminum oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc., can contain other auxiliary agent simultaneously, like P, Si, B, Ti, Zr etc.Can adopt the commercial catalyst, also can be by the existing method preparation in this area.Noble metal catalyst such as Fushun Petrochemical Research Institute (FRIPP) develop the HDO-18 catalyzer, also can be by said method preparations such as CN00123141.3.
In the inventive method; The quality that loops back diesel oil and/or the unconverted oil of reactive system is fresh feed oil quality≤50%; Be preferably the fresh feed oil quality≤35%, fresh feed oil is the fresh bio-oil raw material of unmixed circulation diesel oil and/or unconverted oil.
In the inventive method, catalyzer uses hydrogen 200 ℃～500 ℃ temperature before use, reduces under preferred 220 ℃～450 ℃ conditions.Whenever forbid in system, to inject sulfur-bearing, nitrogenous medium, avoid poisoning of catalyst.
The bio-oil hydrogenation is produced the method for automotive fuel in the prior art, generally need with the petroleum fractions hybrid process of larger proportion, otherwise can not guarantee running period.The present invention can be raw material production high-quality automotive fuel with the bio-oil directly through optimize using the grating technology and the operational condition of catalyzer, solved the problem that the bio-oil hydrogenation unit can not the LP steady running, makes this technology have industrial application value.In addition, diesel oil distillate behind the partial reaction and unconverted oil are looped back hydrogenation reaction system, can further improve the stable operation of bio-oil hydrogenation unit.
Description of drawings
Fig. 1 is the method for hydrotreating principle flow chart of bio-oil production high-quality automotive fuel of the present invention.
Embodiment
Method of the present invention is specific as follows: one or more the mixing oil with in the bio-oil is a raw oil; Under the hydroprocessing condition; Raw oil and hydrogen are through the low temperature and the high temperature hydrogenation reactor drum of loading catalyst; The hydrogenated oil that obtains separates the gas circulation that obtains at HP separator (abbreviation high score) to be used, and also can go out system, and the liquid fractionation that obtains obtains following products: one or more in gas, petroleum naphtha, the diesel oil; If further improve the character of diesel product or prolong the cycle of operation, can consider that also a part of diesel oil and unconverted oil loop back reactive system.The bio-oil that embodiment uses is the commercially available prod, filtering solid impurity before using.
Further specify particular case of the present invention through embodiment below.
The main composition and the character of table 1 hydrogenation catalyst
| Catalyzer | Catalyzer 1 | Catalyzer 2 | Catalyzer 3 |
| Catalyzer is formed | |||
| 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 |
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 |
| Raw oil | Oleum Gossypii semen | Oleum Gossypii semen | Oleum Gossypii semen | Oleum Gossypii semen |
| The cold operation reactor drum | ||||
| Catalyzer | Catalyzer 3 | |||
| Reaction pressure, MPa | 10.0 | |||
| The inlet hydrogen to oil volume ratio | 2000∶1 | |||
| Volume space velocity, h -1 | 2.0 | |||
| Average reaction temperature, ℃ | 180 | |||
| The high-temperature operation reactor drum | ||||
| Catalyzer | Catalyzer 2 | Catalyzer 2 | Catalyzer 2 | Catalyzer 23 |
| Reaction pressure, MPa | 10.0 | 10.0 | 10.0 | 10.0 |
| The inlet hydrogen to oil volume ratio | 1000∶1 | 1000∶1 | 1000∶1 | 1000∶1 |
| Volume space velocity, h -1 | 0.67 | 0.5 | 0.5 | 0.5 |
| Average reaction temperature, ℃ | 310 | 310 | 310 | 320 |
| Runtime, h | 1000 | 200 | 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 |
Can find out that by embodiment the method for hydrotreating of bio-oil through present technique can direct production fine-quality diesel oil product, perhaps fine-quality diesel oil blending component, and can long-time steady operation.
Claims (10)
1. the method for hydrotreating of a bio-oil production high-quality automotive fuel is characterized in that comprising following content:
(a) one or more in the bio-oil are raw oil;
(b) under the hydroprocessing condition, raw oil and hydrogen load hydrogenation catalyst through at least two hydrogenators in the hydrogenator; Raw oil and hydrogen is the hydrogenator through cold operation at first; Hydrogenator through high-temperature operation then, under response behaviour, hydrogenation catalyst
Active ingredient is to go back the Pt and/or the Pd of ortho states;
(c) the hydrogenation elute is separated into gas phase and liquid phase, and gas phase recycles, and liquid phase gets into separation column;
(d) fractionation obtains petroleum naphtha, diesel oil and unconverted oil in separation column, and optional part diesel oil and/or part unconverted oil loop back reactive system.
2. according to the described method of claim 1, it is characterized in that: the material that is prohibited from entering sulfur-bearing, impurity such as nitrogenous in the reactive system.
3. according to the described method of claim 1, it is characterized in that: bio-oil comprises vegetables oil or animal oil and fat.
4. according to the described method of claim 3; It is characterized in that: vegetables oil comprises one or more in VT 18, peanut oil, Viscotrol C, rapeseed oil, Semen Maydis oil, sweet oil, plam oil, Oleum Cocois, tung oil, oleum lini, til, Oleum Gossypii semen, sunflower seed oil and the Rice pollard oil, and animal oil and fat comprises one or more in butter, lard, sheep oil and the fish oil.
5. according to the described method of claim 1, it is characterized in that: the hydroprocessing condition 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, 50 ℃～280 ℃ of average reaction temperature; 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 than the hydrogenator of cold operation high 50 ℃～300 ℃, preferred high 80～220 ℃.
6. according to claim 1 or 5 described methods, it is characterized in that: between the hydrogenator of cold operation and the hydrogenator of high-temperature operation process furnace or interchanger are set, with the temperature of reaction of hydrogenator of adjustment high-temperature operation.
7. according to the described method of claim 1; It is characterized in that: reaction mass is at first through in the hydrogenator of cold operation; The active ingredient of the hydrogenation catalyst that uses 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 the hydrogenator through high-temperature operation, and the active ingredient of the hydrogenation catalyst that uses 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%.
8. according to claim 1 or 7 described methods, it is characterized in that: the activity of such catalysts component concentration is higher than the catalyzer in the cold operation hydrogenator in the hydrogenator of high-temperature operation, and is high 0.1～3 percentage point in the element quality.
9. according to the described method of claim 1, it is characterized in that: reactor drum is provided with 2～5.
10. according to the described method of claim 1, it is characterized in that: the quality that loops back diesel oil and/or the unconverted oil of reactive system be the fresh feed oil quality≤50%, be preferably the fresh feed oil quality≤35%.
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| CN2010105357604A CN102464992A (en) | 2010-11-04 | 2010-11-04 | Hydrogenation method for producing high quality motor fuel by biolipid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103725422A (en) * | 2012-10-11 | 2014-04-16 | 台北科技大学 | Method for modifying tung oil methyl esters by utilizing ultrasonic wave |
| 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 |
| CN104845667A (en) * | 2015-05-15 | 2015-08-19 | 河南百优福生物能源有限公司 | Deoxidization bio-oil hydrogenation device with long operation cycle |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the method for paraffinic hydrocarbons |
-
2010
- 2010-11-04 CN CN2010105357604A patent/CN102464992A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the method for paraffinic hydrocarbons |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103725422A (en) * | 2012-10-11 | 2014-04-16 | 台北科技大学 | Method for modifying tung oil methyl esters by utilizing ultrasonic wave |
| 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 |
| CN104845667A (en) * | 2015-05-15 | 2015-08-19 | 河南百优福生物能源有限公司 | Deoxidization bio-oil hydrogenation device with long operation cycle |
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Application publication date: 20120523 |