CN102464993B - 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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- CN102464993B CN102464993B CN201010535768.0A CN201010535768A CN102464993B CN 102464993 B CN102464993 B CN 102464993B CN 201010535768 A CN201010535768 A CN 201010535768A CN 102464993 B CN102464993 B CN 102464993B
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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 taking bio-oil as stock oil, the method for hydrotreating of direct production high-quality automotive fuel.
Background technology
The energy in 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 day by day exhausted, and heaviness and in poor quality aggravation, and world economy sustainable development, environmental regulation increasingly stringent need to be produced a large amount of light clean fuels, these all require to increase new oil substitutes when existing oil Refining Technologies is improved, 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.Utilizing the method production biofuel (being generally fatty acid methyl ester) of transesterify has been proven technique, but because fatty acid methyl ester oxygen level is high, although many countries and regions have been put into effect the standard of biofuel successively, and be not suitable for all oil engines.Bio-oil is produced automotive fuel by the method for hydrogenation, all removes or partly remove and produce the product that meets automotive fuel standard by oxygen, and this method can directly meet 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 vegetables oil hydroconversion process, adopt coker gasoline cut, 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 containing the vegetables oil such as unsaturated fatty acids, fat and animal oil mixing back end hydrogenation and has 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 first pass through hydrotreatment, then by isomerization catalyst bed layer, obtain low freezing point diesel fuel component, but owing to generating water in hydrotreatment process, isomerization catalyst is caused to very adverse influence, and device can not long-period stable operation.
Comprise that in the bio-oil hydrogenation process of aforesaid method, one of subject matter running into is the less stable of catalyzer, running period is shorter, the more catalyst changeout of need to often stopping work.Particularly, separately taking bio-oil as raw material or when bio-oil blending ratio is higher, be more subject to obvious impact the running period of hydrogenation catalyst, cannot meet the requirement of industrial application.
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 taking bio oil, fat as stock oil, the method of 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 occur, hydrogenation process is stable, and 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 bio-oil are stock oil;
(b) the noble metal hydrogenation catalyst bed that stock oil and hydrogen raise successively by comprising at least two hydrogenation activity component concentrations, stock oil and hydrogen are first by the low beds of hydrogenation activity component concentration, then by the high beds of hydrogenation activity component concentration, under response behaviour, the Pt that hydrogenation activity component is reduction-state and/or Pd;
(c) hydrogenation effluent is separated into gas phase and liquid phase, and gas phase recycles, and liquid phase enters separation column;
(d) in separation column, fractionation obtains petroleum naphtha, diesel oil and unconverted oil, and wherein part diesel oil and/or part unconverted oil can loop back reactive system.
(e) in reactive system, be prohibited from entering the material of sulfur-bearing, the impurity such as nitrogenous.
The bio-oil that the inventive method is used can comprise vegetables oil or animal grease, vegetables oil comprises one or more in soybean oil, peanut oil, Viscotrol C, rapeseed oil, Semen Maydis oil, sweet oil, plam oil, Oleum Cocois, tung oil, oleum lini, sesame oil, Oleum Gossypii semen, sunflower seed oil and rice bran wet goods, and animal grease comprises one or more in butter, lard, sheep oil and fish oil etc.
In the inventive method, in the low beds of hydrogenation activity component concentration that first reaction mass 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 a reactor by the scale of reactor, also can be seated in two or more reactors.
In the inventive method, the catalyzer that low activity hydrogenation catalyst bed that first reaction mass passes through uses accounts for 10%～80% of all hydrogenation catalyst volumes, and preferably 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, as P, Si, B, Ti, Zr etc. simultaneously.Can adopt commercial catalyst, also can be by the existing method preparation in this area.Noble metal catalyst, also can be by described method preparations such as CN00123141.3 as the development HDO-18 of Fushun Petrochemical Research Institute (FRIPP) catalyzer.
In the inventive method, catalyzer uses hydrogen 200 DEG C～500 DEG C temperature before use, under preferably 220 DEG C～450 DEG C conditions, reduces.Whenever forbid to inject sulfur-bearing, nitrogenous medium in system, avoid poisoning of catalyst.
In the inventive method, 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 DEG C～465 DEG C 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 DEG C～445 DEG C of average reaction temperature.
In the inventive method, loop back the diesel oil of reactive system and/or the quality of unconverted oil and 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.
In prior art, bio-oil hydrogenation is produced the method for automotive fuel, generally need to the petroleum fractions hybrid process of larger proportion, otherwise can not ensure running period.The present invention uses grating technology and the operational condition of catalyzer by optimization, can be directly taking bio-oil as raw material production high-quality automotive fuel, solve the problem that bio-oil hydrogenation unit can not long period steady running.In addition, diesel oil distillate after partial reaction and unconverted oil are looped back to hydrogenation reaction system, can further improve the stable operation of bio-oil hydrogenation unit.
Brief description of the 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: taking one or more the mixing oil in bio-oil as stock oil, under hydroprocessing condition, stock oil and hydrogen are by comprising the hydroconversion reaction zone of at least two kinds of hydrogenation catalysts, the hydrotreatment obtaining generates oil and separates the gas circulation use obtaining in high-pressure separator (abbreviation high score), also can go out system, the liquid fractionation obtaining obtains following products: gas, petroleum naphtha, one or more in diesel oil, if further improve the character of diesel product 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, filtering solid impurity before using.
Further illustrate particular case of the present invention below by embodiment.
The chief component of table 1 hydrotreating catalyst and character
| Catalyzer | Catalyzer 1 | Catalyzer 2 | Catalyzer 3 |
| Catalyzer composition | |||
| 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 be found out by embodiment, the method for hydrotreating of bio-oil by this technology can direct production fine-quality diesel oil product, or fine-quality diesel oil blending component, and can long-time steady operation.
Claims (13)
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) the noble metal hydrogenation catalyst bed that stock oil and hydrogen raise successively by comprising at least two hydrogenation activity component concentrations, stock oil and hydrogen are first by the low beds of hydrogenation activity component concentration, then by the high beds of hydrogenation activity component concentration, under response behaviour, the Pt that hydrogenation activity component is reduction-state and/or Pd; The carrier of hydrogenation catalyst is aluminum oxide;
(c) hydrogenation effluent is separated into gas phase and liquid phase, and gas phase recycles, and liquid phase enters separation column;
(d) in separation column, fractionation obtains petroleum naphtha, diesel oil and unconverted oil, and wherein part diesel oil and/or part unconverted oil can loop back reactive system;
(e) in reactive system, be prohibited from entering the material of sulfur-bearing, the impurity such as nitrogenous;
Wherein, in the low beds of hydrogenation activity component concentration that first reaction mass 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, 50 DEG C～465 DEG C of average reaction temperature.
2. it is characterized in that in accordance with the method for claim 1: bio-oil comprises vegetables oil or animal grease.
3. it is characterized in that in accordance with the method for claim 2: 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; Animal grease comprises one or more in butter, lard, sheep oil and fish oil.
4. it is characterized in that in accordance with the method for claim 1: hydrotreatment arranges 2～5 beds.
5. it is characterized in that in accordance with the method for claim 1: the catalyzer that the low activity hydrogenation catalyst bed that first reaction mass passes through uses accounts for 10%～80% of all hydrogenation catalyst volumes.
6. it is characterized in that in accordance with the method for claim 5: the catalyzer that the low activity hydrogenation catalyst bed that first reaction mass passes through uses accounts for 20%～70% of all hydrogenation catalyst volumes.
7. it is characterized in that in accordance with the method for claim 5: the catalyzer that the low activity hydrogenation catalyst bed that first reaction mass passes through uses accounts for 30%～60% of all hydrogenation catalyst volumes.
8. it is characterized in that in accordance with the method for claim 1: catalyzer reduces under 200 DEG C～500 DEG C temperature condition with hydrogen before use.
9. in accordance with the method for claim 1, it is characterized in that: hydroprocessing condition is reaction pressure 2.0MPa～20.0MPa, hydrogen to oil volume ratio is 200: 1～3000: 1, and volume space velocity is 0.1h
-1～6.0h
-1.
10. it is characterized in that in accordance with the method for claim 1: loop back the diesel oil of reactive system and/or the quality of unconverted oil and be fresh feed oil≤50%.
11. in accordance with the method for claim 8, it is characterized in that: catalyzer reduces under 220 DEG C～450 DEG C temperature condition with hydrogen before use.
12. in accordance with the method for claim 9, it is characterized in that: 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 DEG C～445 DEG C of average reaction temperature.
13. in accordance with the method for claim 10, it is characterized in that: loop back the diesel oil of reactive system and/or the quality of unconverted oil and be fresh feed oil≤35%.
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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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| 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 CN102464993A (en) | 2012-05-23 |
| CN102464993B true 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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| 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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