CN102464993A - Hydrogenation method for producing high-quality motor fuel with biological grease - Google Patents
Hydrogenation method for producing high-quality motor fuel with biological grease Download PDFInfo
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- CN102464993A CN102464993A CN2010105357680A CN201010535768A CN102464993A CN 102464993 A CN102464993 A CN 102464993A CN 2010105357680 A CN2010105357680 A CN 2010105357680A CN 201010535768 A CN201010535768 A CN 201010535768A CN 102464993 A CN102464993 A CN 102464993A
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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 invention relates to a hydrogenation method for producing a high-quality motor fuel with biological grease. The method comprises: taking one or several kinds of biological grease as raw oil; passing the raw oil and hydrogen through at least two precious metal hydrogenation catalyst beds, the hydrogenation active component contents of which increase in order, leaving the raw oil and hydrogen first to pass through a catalyst bed with low hydrogenation active component content and then to pass through a catalyst bed with high hydrogenation active component content, with reduced Pt and/or Pd adopted as the hydrogenation active component under a reaction state; separating a hydrogenation effluent into a gas phase and a liquid phase, recycling the gas phase and leaving the liquid phase to enter a fractionating tower; conducting fractionation in the fractionating tower so as to obtain naphtha, diesel oil and unconverted oil, circulating part of the diesel oil and/or part of the unconverted oil back to a reaction system. Compared with prior art, the method of the invention not only can effectively improve the storage stability of biological grease taken as fuel oil, and simultaneously can realize long-period stable operation of a device.
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 method of hydrotreating of bio-oil production high-quality automotive fuel, is raw oil with bio oil, fat separately, the method for direct production automotive fuel under the condition of hydrogenation; The high-quality diesel oil mediation of direct production product; Make diesel product that the situation that biofuel that conventional animal-plant oil makes is gone mouldy can not take place, the hydrogenation technique process stabilization, running period is long.
The method of hydrotreating of a kind of bio-oil production of the present invention high-quality automotive fuel comprises following content:
(a) one or more in the bio-oil are raw oil;
(b) the noble metal hydrogenation catalyst bed that raises successively through comprising at least two hydrogenation activity component concentrations of raw oil and hydrogen; Raw oil and hydrogen are at first through the low beds of hydrogenation activity component concentration; Then through the high beds of hydrogenation activity component concentration; Under response behaviour, the hydrogenation activity component 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 wherein part diesel oil and/or part unconverted oil can loop back reactive system.
(e) 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.
In the inventive method, in the low beds of the hydrogenation activity component concentration that reaction mass at first passes through, in the element of precious metals pt and/or Pd, the content of noble metal hydrogenation active ingredient is 0.01%～0.50%.The hydrogenation activity component of the downstream catalyst that reaction mass passes through increases by 0.5～3.0 percentage point in precious metal element than adjacent upstream catalyzer.2～5 beds generally can be set, can be seated in the reactor drum, also can be seated in two or more reactor drums by the scale of reactor drum.
In the inventive method, the catalyzer that the low activity hydrogenation catalyst bed that reaction mass at first passes through uses accounts for 10%～80% of all hydrogenation catalyst volumes, preferred 20%～70%, best 30%～60%.
In the inventive method, 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, 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.
In the inventive method, the hydroprocessing condition is generally reaction pressure 2.0MPa～20.0MPa, and hydrogen to oil volume ratio is 200: 1～3000: 1, and volume space velocity is 0.1h
-1～6.0h
-1, 50 ℃～465 ℃ of average reaction temperature; Preferred hydroprocessing condition is reaction pressure 3.0MPa～18.0MPa, hydrogen to oil volume ratio 300: 1～2500: 1, volume space velocity 0.3h
-1～6.0h
-1, 80 ℃～445 ℃ of average reaction temperature.
In the inventive method, the quality that loops back diesel oil and/or the unconverted oil of reactive system be fresh feed oil≤50%, be preferably fresh feed oil≤35%, fresh feed oil is the fresh feed oil of unmixed circulation diesel oil and/or unconverted oil.
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.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 that bio-oil of the present invention is produced automotive fuel.
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 comprising the hydroconversion reaction zone of at least two kinds of hydrogenation catalysts; The hydrotreatment that obtains generates oil and separates the gas circulation use that obtains at HP separator (abbreviation high score), 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, 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 hydrotreating 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
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) the noble metal hydrogenation catalyst bed that raises successively through comprising at least two hydrogenation activity component concentrations of raw oil and hydrogen; Raw oil and hydrogen are at first through the low beds of hydrogenation activity component concentration; Then through the high beds of hydrogenation activity component concentration; Under response behaviour, the hydrogenation activity component 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 wherein part diesel oil and/or part unconverted oil can loop back reactive system.
(e) be prohibited from entering the material of sulfur-bearing, impurity such as nitrogenous in the reactive system.
2. according to the described method of claim 1, it is characterized in that: bio-oil comprises vegetables oil or animal oil and fat.
3. according to the described method of claim 2, 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; Animal oil and fat comprises one or more in butter, lard, sheep oil and the fish oil.
4. according to the described method of claim 1, it is characterized in that: in the low beds of the hydrogenation activity component concentration that reaction mass at first passes through, in the element of precious metals pt and/or Pd, the content of noble metal hydrogenation active ingredient is 0.01%～0.50%.
5. according to claim 1 or 4 described methods, it is characterized in that: the hydrogenation activity component of the downstream catalyst that reaction mass passes through increases by 0.5～3.0 percentage point in precious metal element than adjacent upstream catalyzer.
6. according to the described method of claim 5, it is characterized in that: hydrotreatment is provided with 2～5 beds.
7. according to the described method of claim 1, it is characterized in that: the catalyzer that the low activity hydrogenation catalyst bed that reaction mass at first passes through uses accounts for 10%～80% of all hydrogenation catalyst volumes, preferred 20%～70%, best 30%～60%.
8. according to the described method of claim 1, it is characterized in that: catalyzer uses hydrogen 200 ℃～500 ℃ temperature before use, reduces under preferred 220 ℃～450 ℃ conditions.
9. according to the described method of claim 1, it is characterized in that: the hydroprocessing condition is reaction pressure 2.0MPa～20.0MPa, and hydrogen to oil volume ratio is 200: 1～3000: 1, and volume space velocity is 0.1h
-1～6.0h
-1, 50 ℃～465 ℃ of average reaction temperature; Preferred hydroprocessing condition is reaction pressure 3.0MPa～18.0MPa, hydrogen to oil volume ratio 300: 1～2500: 1, volume space velocity 0.3h
-1～6.0h
-1, 80 ℃～445 ℃ of average reaction temperature.
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 fresh feed oil≤50%, be preferably fresh feed oil≤35%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010535768.0A CN102464993B (en) | 2010-11-04 | 2010-11-04 | Hydrogenation method for producing high-quality motor fuel with biological grease |
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| CN201010535768.0A CN102464993B (en) | 2010-11-04 | 2010-11-04 | Hydrogenation method for producing high-quality motor fuel with biological grease |
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| CN102464993A true CN102464993A (en) | 2012-05-23 |
| CN102464993B CN102464993B (en) | 2014-10-15 |
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Citations (2)
| 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 |
| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the method for paraffinic hydrocarbons |
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2010
- 2010-11-04 CN CN201010535768.0A patent/CN102464993B/en active Active
Patent Citations (2)
| 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 |
| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the method for paraffinic hydrocarbons |
Non-Patent Citations (1)
| Title |
|---|
| 徐春明等主编: "《石油炼制工程（第四版）》", 30 September 2009, article ""异构化催化剂"", pages: 516-518 * |
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