CN104099120A - Method for preparing aviation liquid fuel by using biodiesel - Google Patents
Method for preparing aviation liquid fuel by using biodiesel Download PDFInfo
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- CN104099120A CN104099120A CN201310125497.5A CN201310125497A CN104099120A CN 104099120 A CN104099120 A CN 104099120A CN 201310125497 A CN201310125497 A CN 201310125497A CN 104099120 A CN104099120 A CN 104099120A
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- biofuel
- catalytic cracking
- liquid fuel
- biodiesel
- aviation
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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
-
- 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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- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
- Y02T50/678—Aviation using fuels of non-fossil origin
Abstract
The invention relates to a method for preparing an aviation liquid fuel by using biodiesel (fatty acid methyl ester). The method comprises the following steps: adding a water-methanol mixed liquid having a volume 2-3 times the volume of biodiesel to a raw material biodiesel, adding an alkali accounting for 1-5% of the weight of the biodiesel, hydrolyzing at 30-100DEG C, and carrying out electrolytic synthesis in an electrolytic tank to obtain long carbon chain alkanes; carrying out catalytic cracking on the long carbon chain alkanes under normal pressure at 300-450DEG C under a space velocity of 0.2-2.0h<-1> under the action of a catalyst; carrying out an isomerization reaction under normal pressure at 220-350DEG C under a space velocity of 0.5-2.5h<-1> with mordenite as a catalyst; and distilling a product obtained after the isomerization reaction, and collecting a fraction at a cutting temperature of 105-240DEG C to obtain a refined aviation fuel blend component. The method has the advantages of simple and stable process, mild reaction conditions, low energy consumption and high product yield.
Description
Technical field
The present invention relates to clean energy production field, specifically a kind of method of utilizing biofuel to prepare aviation liquid fuel.
Background technology
At present, air-transport industry role in economic globalization process is more and more important, and the quantity of personnel's air transport and airfreight is with annual 4.9% and 5.3% rate increase, and the use of Aviation Fuel also accounts for 8% of whole petroleum products output.According to statistics, the carbonic acid gas of global air-transport industry discharge in 2008 is up to 6.77 hundred million tons, although the CO2 emissions of air-transport industry only accounts for 2% of global total release, as trans-regional global air system, its impact is still and can not be ignored.In order to reduce the be rivals in a contest impact of environment of aviation platoon, International Air Transport Assoiciation (IATA) promises to undertake that clean quantity discharged that the year two thousand fifty realizes carbon was than minimizing 50% in 2005.From 2012, European Union reduced discharging target in order to reach aviation, will arrive at and leave the domestic commercial airliners of European Union and impose carbon emission tax all.2000 Duo Jia airlines will be included into European Union's discharge trade system, comprising 35 Chinese companies.When the time comes, the annual cost of World Airways, Inc. will increase by 3,500,000,000 Euros, and the countries in the world airline including China all deals with the dual-pressure of the rapid fluctuation of aviation fuel price and aviation carbon emission reduction at positive seeking solution.Although can play a role by improving aircraft efficiency of combustion and airline's operation efficiency, cannot fundamentally realize carbon emission and reduce.Therefore, the renewable aviation biological substitution of exploitation s-generation fuel is the large outlet that air system reduced discharging and reduced fuel cost.International Air Transport Assoiciation's report title, s-generation biofuel is expected to 2012 to start, in formally commercialization of air-transport industry, can reduce the greenhouse gas emission that is up to 96%.
European Union's biofuel 2005 yearly capacities, at 6,070,000 t, are promoted and are reached 8,300,000 t to biofuel in 2010.Since 1993 Japan the research trial to biofuel, and to have set up in 1999 with frying oil be the industrial experiment device of raw material production biofuel, throughput is 259L/d.Current Japanese biofuel annual production can reach 400,000 t.China's biofuel industry formally started to walk in calendar year 2001, had set up at present Duo Jia manufacturing enterprise, and biofuel annual production can reach 1,000,000 t left and right.But, biofuel due to oxygen level high (10% left and right) and condensation point too high, cannot be directly use as aviation fuel.Current is mainly catalytic decarboxylation technique and hydrogenation deoxidation technique for biofuel etc. containing the technique of oxygen raw material production Aviation Fuel, catalytic decarboxylation technique is mainly to pass through taking sewer oil as raw material, after filter residue, desalination, dehydration, decolouring processing, to add decarboxylation catalyst reaction to obtain biological aviation kerosene.And hydrogenation deoxidation method temperature of reaction is high, working pressure is large, and yield is low, higher to catalyzer service requirements.Typical technique comprises the exploitation Bio-Synfining of Syntroleum company
tMprocess technology, and the exploitation Ecofining of Honeywell Uop Inc.
tMsPK process technology.The research that adopts electrolysis deoxidation technology that biofuel (fatty acid methyl ester) is changed into aviation liquid fuel has no report.
Summary of the invention
The object of the invention is to provide a kind of method of utilizing biofuel to prepare aviation liquid fuel.
The technical solution used in the present invention is for achieving the above object:
Utilize biofuel to prepare a method for aviation liquid fuel, biofuel, through electrolytic synthesis, catalytic cracking/isomerization reaction, air distillation, be specially:
Electrolytic synthesis: to raw material biofuel (fatty acid methyl ester, C
14-C
20) in add the water-methanol mixture of its 2～3 times of volumes, and add the alkali of raw materials quality per-cent 1～5%, in 30～100 ° of C hydrolysis, after hydrolysis, in electrolyzer, electrolytic synthesis obtains the alkane of long carbochain;
Catalytic cracking/isomerization reaction: by the alkane of long carbochain after above-mentioned electrolysis under normal pressure in 300 ° of C～450 ° C, through catalyzer, with 0.2～2.0h
-1volume space velocity under effect carry out catalytic cracking; Then be the lower 220 ° of C～350 ° C of normal pressure, using mordenite as catalyzer, volume space velocity is controlled at 0.5～2.5h
-1isomerization reaction;
Air distillation: the product after isomerization reaction is processed through distillation, collects the cut of cutting temperature between 105～240 ° of C and can obtain refining aviation fuel blend component.
Cut catalytic cracking reaction again by above-mentioned cutting temperature higher than 240 ° of C.
Described oxygen level is remained on to 10～15% biofuel, by electrolytic synthesis, the oxygen in raw material biofuel is removed completely.
The catalyzer of described catalytic cracking is zeolite molecular sieve, ZSM-5, ZSM-11, ZSM-22, ZSM-23, HY molecular sieve or NaY molecular sieve.
In described electrolytic synthesis process, current density is higher than 50mA/cm
2; Anode material is platinum, glass carbon or stainless steel.
The hydrolysis of described biofuel and the process of electrolysis are carried out in same reaction unit simultaneously; Catalytic cracking and isomerization reaction can be carried out in same reactor simultaneously.
The present invention has advantages of: compare with existing hydrocracking technology, technique of the present invention is simple, stable, reaction conditions gentleness, energy consumption is low, product yield is high, has good safety and stability performance and combustionproperty, can significantly solve freezing point of biodiesel high simultaneously, oxygen level is high, easily an oxidized difficult problem.The Aviation Fuel product sulphur content making is low, and condensation point can reach-40 ° below C, and viscosity meets the requirements, sufficient combustion, pollute little, can be as the blend component of current commercial aviation fuel.Adopt art production process of the present invention there is no dirty useless outer row, meet current Environmental Protection in China requirement.The hydrogen of by-product high-quality, paraffin, propylene etc. in production process, be suitable for large-scale industrial production simultaneously.
Brief description of the drawings
The process flow sheet that Fig. 1 provides for the embodiment of the present invention.
Embodiment
Embodiment 1
Electrolytic synthesis: to raw material biofuel (fatty acid methyl ester, C
14-C
20) in add the water-methanol mixture of its 2 times of volumes, and add the sodium hydroxide holding temperature of raw material weight per-cent 3% at 45 ° of C, make fatty acid methyl ester in biofuel be hydrolyzed into lipid acid/soap.Then the mixing solutions after hydrolysis is carried out to electrolysis, anode adopts platinum electrode, and control current density is 150mA/cm
2, the alkane of long carbochain will be separated out in platinum electrode surface, and the oxygen in raw material can be overflowed with the form of carbonic acid gas.Meanwhile, the hydrogen that electrode surface is separated out high added value can be widely used in relevant chemical industry.Wherein, in water-methanol mixture, water is identical with methyl alcohol volume.
Fatty acid methyl ester composition list in biodiesel raw material in the present embodiment
| Methyl esters component | Percentage composition wt.% |
| C 14:0 | 6.37 |
| C 16:0 | -- |
| C 16:1 | 5.26 |
| C 18:0 | 3.92 |
| C 18:1 | 55.73 |
| C 18:2 | 26.98 |
| C 20:0 | 1.74 |
Catalytic cracking/isomerization reaction: by the alkane of long carbochain after above-mentioned electrolysis under normal pressure in 350 ° of C, using ZSM-5 molecular sieve as catalytic cracking catalyst, with 0.5h
-1volume space velocity under effect carry out catalytic cracking, reacted product liquid mainly comprises carbon number at 5～20 hydrocarbon polymer, gaseous product is mainly propylene and butylene; The product liquid of collecting from catalytic cracking reaction reduces the condensation point of product again through isomerization reaction, adopt mordenite as isomerization catalyst, controls temperature of reaction at 350 ° of C, and volume space velocity is controlled at 1.5h
-1.Reacted product liquid comprises carbon number and still remains between 5～20, and gaseous product is few.
Air distillation: the product after isomerization reaction is through rectifying, the cut of collection cutting temperature between 105～240 ° of C be that the blend component of aviation fuel (is hydrocarbon compound, C5-C16), cutting temperature is carried out to catalytic cracking reaction again higher than the cut of 240 ° of C, the reaction conditions of this recycle stock is identical with the condition that starting material carry out catalytic cracking, and recycle stock and biodiesel raw material parallel feeding charging.This aviation fuel product is 60% from the transformation efficiency of biodiesel raw material.
Embodiment 2
Electrolytic synthesis: add the water-methanol mixture of its 3 times of volumes in raw material biofuel, and add the sodium hydroxide holding temperature of raw material weight per-cent 5% at 60 ° of C, make fatty acid methyl ester in biofuel be hydrolyzed into lipid acid/soap.Then the mixing solutions after hydrolysis is carried out to electrolysis, anode adopts platinum electrode, and control current density is 200mA/cm
2, the alkane of long carbochain will be separated out in platinum electrode surface, and the oxygen in raw material is overflowed with the form of carbonic acid gas.Wherein, in water-methanol mixture, water and methyl alcohol volume ratio are 2:1.
Fatty acid methyl ester composition list in biodiesel raw material in the present embodiment
| Methyl esters component | Percentage composition wt.% |
| C 14:0 | 0.71 |
| C 16:0 | 0.66 |
| C 16:1 | 1.00 |
| C 18:0 | 1.43 |
| C 18:1 | 34.23 |
| C 18:2 | 61.31 |
| C 20:0 | 0.59 |
Catalytic cracking/isomerization reaction: by the alkane of long carbochain after above-mentioned electrolysis under normal pressure in 410 ° of C, using HY molecular sieve as catalytic cracking catalyst, with 0.8h
-1volume space velocity under effect carry out catalytic cracking, reacted product liquid mainly comprises carbon number at 5～20 hydrocarbon polymer, gaseous product is mainly propylene and butylene; The product liquid of collecting from catalytic cracking reaction reduces the condensation point of product again through isomerization reaction, adopt mordenite as isomerization catalyst, controls temperature of reaction at 320 ° of C, and volume space velocity is controlled at 1.0h
-1.Reacted product liquid comprises carbon number and still remains between 5～20.
Air distillation: the product after isomerization reaction is through rectifying, and collecting the cut of cutting temperature between 105～240 ° of C is the blend component of aviation fuel.Cutting temperature is carried out to catalytic cracking reaction again higher than the cut of 240 ° of C, and the reaction conditions of this recycle stock is identical with the condition that starting material carry out catalytic cracking, and recycle stock is independent charging.This aviation fuel product is 55% from the transformation efficiency of biodiesel raw material.
Embodiment 3
Electrolytic synthesis: add the water-methanol mixture of its 2 times of volumes in raw material biofuel, and add the sodium hydroxide holding temperature of raw material weight per-cent 2.5% at 70 ° of C, make fatty acid methyl ester in biofuel be hydrolyzed into lipid acid/soap.Then the mixing solutions after hydrolysis is carried out to electrolysis, anode adopts glass-carbon electrode, and control current density is 180mA/cm
2, the alkane of long carbochain will be separated out in platinum electrode surface, and the oxygen in raw material is overflowed with the form of carbonic acid gas.Wherein, in water-methanol mixture, water and methyl alcohol volume ratio are 1.5:1.
Fatty acid methyl ester composition list in biodiesel raw material in the present embodiment
| Methyl esters component | Percentage composition wt.% |
| C 14:0 | -- |
| C 16:0 | -- |
| C 16:1 | 0.92 |
| C 18:0 | 3.56 |
| C 18:1 | 82.60 |
| C 18:2 | 12.62 |
| C 20:0 | 0.30 |
Catalytic cracking/isomerization reaction: by the alkane of long carbochain after above-mentioned electrolysis under normal pressure in 450 ° of C, using ZSM-11 molecular sieve as catalytic cracking catalyst, with 1.2h
-1volume space velocity under effect carry out catalytic cracking, reacted product liquid mainly comprises carbon number at 5～20 hydrocarbon polymer, gaseous product is mainly propylene and butylene; The product liquid of collecting from catalytic cracking reaction reduces the condensation point of product again through isomerization reaction, adopt mordenite as isomerization catalyst, controls temperature of reaction at 300 ° of C, and volume space velocity is controlled at 0.8h
-1.Reacted product liquid comprises carbon number and still remains between 5～20.
Air distillation: the product after isomerization reaction is through rectifying, and collecting the cut of cutting temperature between 105～240 ° of C is the blend component of aviation fuel.Cutting temperature is carried out to catalytic cracking reaction again higher than the cut of 240 ° of C, and the reaction conditions of this recycle stock is identical with the condition that starting material carry out catalytic cracking, and recycle stock is independent charging.This aviation fuel product is 55% from the transformation efficiency of biodiesel raw material.
After testing: the aviation liquid fuel overall conversion that above-mentioned each embodiment makes is all more than 55%, and its physical properties is: density (15 ° of C) 794.9kg/m
3, freezing point-52 ° C, 46 ° of C of flash-point, acid number 0.086mg KOH/g, viscosity (20 ° of C) is 1.30mm
2/ s, net thermal value 49.1MJ/kg, gum level 6.5mg/100ml, has good low temperature flowability and combustionproperty.
Within technical scheme of the present invention is not restricted to the scope of embodiment of the present invention.The present invention not technology contents of detailed description is known technology.
Claims (6)
1. utilize biofuel to prepare a method for aviation liquid fuel, biofuel, through electrolytic synthesis, catalytic cracking/isomerization reaction, air distillation, be is characterized in that:
Electrolytic synthesis: to raw material biofuel (fatty acid methyl ester, C
14-C
20) in add the water-methanol mixture of its 2～3 times of volumes, and add the alkali of raw materials quality per-cent 1～5%, in 30～100 ° of C hydrolysis, after hydrolysis, in electrolyzer, electrolytic synthesis obtains the alkane of long carbochain;
Catalytic cracking/isomerization reaction: by the alkane of long carbochain after above-mentioned electrolysis under normal pressure in 300 ° of C～450 ° C, through catalyzer, with 0.2～2.0h
-1volume space velocity under effect carry out catalytic cracking; Then be the lower 220 ° of C～350 ° C of normal pressure, using mordenite as catalyzer, volume space velocity is controlled at 0.5～2.5h
-1isomerization reaction;
Air distillation: the product after isomerization reaction is processed through distillation, collects the cut of cutting temperature between 105～240 ° of C and can obtain refining aviation fuel blend component.
2. by the method for utilizing biofuel to prepare aviation liquid fuel claimed in claim 1, it is characterized in that: the cut catalytic cracking reaction again by cutting temperature higher than 240 ° of C.
3. by the method for utilizing biofuel to prepare aviation liquid fuel claimed in claim 1, it is characterized in that: described oxygen level is remained on to 10～15% biofuel, by electrolytic synthesis, the oxygen in raw material biofuel is removed completely.
4. by the method for utilizing biofuel to prepare aviation liquid fuel claimed in claim 1, it is characterized in that: the catalyzer of described catalytic cracking is zeolite molecular sieve, ZSM-5 ZSM-11, ZSM-22, ZSM-23, HY molecular sieve or NaY molecular sieve.
5. by the method for utilizing biofuel to prepare aviation liquid fuel claimed in claim 1, it is characterized in that: in described electrolytic synthesis process, current density is higher than 50mA/cm
2; Anode material is platinum, glass carbon, graphite or stainless steel.
6. by the method for utilizing biofuel to prepare aviation liquid fuel claimed in claim 1, it is characterized in that: the hydrolysis of described biofuel and the process of electrolysis are carried out in same reaction unit simultaneously; Catalytic cracking and isomerization reaction can be carried out in same reactor simultaneously.
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Citations (7)
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| US20120197050A1 (en) * | 2011-02-01 | 2012-08-02 | Joshi Chandrashekhar H | Production of hydrocarbon fuels from plant oil and animal fat |
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2013
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| WO2007027669A1 (en) * | 2005-08-29 | 2007-03-08 | Cps Biofuels, Inc. | Improved biodiesel fuel, additives, and lubbricants |
| CN101952392A (en) * | 2007-12-21 | 2011-01-19 | 环球油品公司 | Prepare aviation fuel from biological renewable raw materials |
| CN101597508A (en) * | 2009-07-02 | 2009-12-09 | 浙江大学 | A kind of method of preparing alkane by high fatty acid ester |
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