CN105670679B - A kind of method for preparing long chain alkane and aromatic hydrocarbons simultaneously by raw material of oleic acid - Google Patents
A kind of method for preparing long chain alkane and aromatic hydrocarbons simultaneously by raw material of oleic acid Download PDFInfo
- Publication number
- CN105670679B CN105670679B CN201610123819.6A CN201610123819A CN105670679B CN 105670679 B CN105670679 B CN 105670679B CN 201610123819 A CN201610123819 A CN 201610123819A CN 105670679 B CN105670679 B CN 105670679B
- Authority
- CN
- China
- Prior art keywords
- oleic acid
- aromatic hydrocarbons
- long chain
- catalyst
- raw material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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 present invention relates to a kind of method for preparing long chain alkane and aromatic hydrocarbons simultaneously by raw material of oleic acid, comprise the following steps：1) oleic acid and catalyst, heat temperature raising reaction are added in high-temperature high-pressure reaction kettle；Described catalyst is Pt/C；2) reaction product is cooled down, organic solvent dissolving, and liquid product and solid-phase catalyst are obtained after filtering.Not additional any hydrogen, hydrogen supply agent or solvent in above-mentioned preparation method, using oleic acid and Pt/C catalytic action one-step synthesis long chain alkane and aromatic hydrocarbons, yield can be respectively up to 72% and more than 19%.
Description
Technical field
The present invention relates to the preparation method of long chain alkane and aromatic hydrocarbons, and in particular to one kind prepares length simultaneously by raw material of oleic acid
The method of alkane and aromatic hydrocarbons.
Background technology
With developing rapidly for aircraft industry, it will be got on the car to the amount of carbon dioxide produced by the year two thousand fifty aircraft more than ground row
The summation put, and with the atrophy of petroleum resources, crude oil price will when the river rises the boat goes up, airline is faced huge existence
Pressure.Under the pressure of pressure, people are hardy seeking the substitute of traditional fossil energy, biology boat coal be using renewable resource as
The aviation kerosine of raw material production, compared with conventional petroleum base aviation kerosine, not only has drop well in whole life cycle
The effect of low carbon dioxide emission, but also be regenerative resource, the research and development application of bio-aviation fuel turns into international airline
One of main trend of industry future development.Aviation Fuel basic composition is alkane of the carbon chain lengths between 8-17, cycloalkane,
Aromatic hydrocarbons and a small amount of additive.Although alkane has more preferable combustibility, the expansion function of the whole elastic system of fuel oil is also
It is that must obtain to be realized by aromatic hydrocarbons, so aromatic hydrocarbons is also essential composition.Grease is the high-energy-density of C, H, O formation
Compound, main component is triglyceride and free fatty.Grease is efficiently converted into catalysis technique biological aviation fuel into
It is most popular and most have one of technology of industrial prospect for biomass energy source domain.
It is with H by the O in grease at present using mainstream technology that grease is the biological aviation fuel of raw material production as hydrogenation deoxidation2O's
Form is sloughed and obtains long chain alkane, and then long chain alkane prepares biological aviation fuel by isomerization.Cheng Jun et al. (CN
103897753A) in H2A kind of biological Aviation Fuel is obtained using HZSM-5 catalysis under atmosphere, however, the H of hydrogenation deoxidation method2
Consumption is larger.
And hydrolysis-decarboxylation method is the new technology being developed in recent years, the complicated low-grade grease of energy processes composition is first hydrolyzed
Aliphatic acid is obtained, then the oxygen in fatty acid molecule is removed by non-hydrogen decarboxylation, hydrocarbon compound is converted into.O during decarboxylation
It is with CO2Form slough, hydrogen is not consumed in terms of deoxidation, thus reduce in biological aviation fuel production process hydrogen consumption.But, oil
(40~60%) containing a large amount of oleic acid in the aliphatic acid that fat hydrolysis is obtained, still suffer from suitable hydrogen consumption.
As being sayed above, aromatic hydrocarbons is very important component in Aviation Fuel, but be difficult from technology it is very ripe plus
Obtain, both typically be from virgin kerosene in hydrogen deoxy technology or F- T synthesis.It is considerably less from biomass production aromatic hydrocarbons, only
The method of some cracking can produce a small amount of aromatic hydrocarbons, and can produce the biology of usually these low energy density of lignin of aromatic hydrocarbons
Matter, and the aromatic hydrocarbons produced is polycyclic mostly, and do not meet requirement (Fuel, 2015.160 of Aviation Fuel:p.375-
385).For preparing aromatic hydrocarbons from grease cracking, although aromatics yield can reach 24%, but condition is very harsh, temperature
Spend for 800 DEG C, the quality requirement of catalyst is 20 times of biomass, and there remains 24% unknown residue.Go out for oleic acid
Hair prepares aromatic hydrocarbons, Rabaev (Fuel, 2015.161:P.287-294 research) shows Pt/Al2O3Under/SAPO-11 catalysis,
Oleic acid is unable to aromatisation, even the yield of the palm oil aromatisation containing 52.8% single unsaturated bond and 12.2% how unsaturated key
Also there was only 1.7%.
《Aliphatic acid (ester) non-hydrogen catalytic decarboxylation repercussion study》(Yang Cuiyue, Chinese excellent MA theses full text number
According to II volume of storehouse engineering science and technology) disclose microalgae grease in a kind of high temperature liquid water and carry out non-hydrogen catalytic decarboxylation and prepare long chain alkane
Method, but the reaction does not have aromatic hydrocarbons generation, and this method needs aqueous solvent, and the presence just because of reaction reclaimed water causes not
The dehydrogenation of saturated acid and its intermediate product is suppressed, so as to can not proceed intramolecular D-A reaction aromatisation, is caused final
Product does not have aromatic hydrocarbons.
The content of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide one kind by raw material of oleic acid while preparing long alkane
The method of hydrocarbon and aromatic hydrocarbons, solves from oleic acid and prepares the technical deficiency of biological Aviation Fuel, while solving biological boat
The problem of hydrogen consumption is big in air-fuel oil, hydrogen supply dosage hardly possible is controlled, aromatic hydrocarbons hardly possible is obtained and alkane yield is not high.
The present invention solves the technical scheme that is provided of above-mentioned technical problem：
A kind of method for preparing long chain alkane and aromatic hydrocarbons simultaneously by raw material of oleic acid, comprises the following steps：
1) oleic acid and catalyst, heat temperature raising reaction are added in high-temperature high-pressure reaction kettle；Described catalyst is Pt/C；
2) reaction product is cooled down, organic solvent dissolving, and liquid product and solid-phase catalyst are obtained after filtering.
Step 1 in above-mentioned technical proposal) in only add oleic acid and Pt/C, not additional any hydrogen, hydrogen supply agent or molten
Agent, exactly because without external hydrogen source in system of the present invention, Pt/C can just make a part of oleic acid and its decarboxylate 17
Alkene dehydrogenation and further intramolecular D-A reactions aromatisation hydrogen supply, the hydrogen of generation are rapidly saturated remaining oleic acid into stearic acid, stearic
Acid decarboxylation couples dehydrogenation, decarboxylation, hydrogenation, four steps of technical process one of aromatisation, it is length to make oleic acid Efficient Conversion into heptadecane
Alkane and aromatic hydrocarbons.
Preferably, described oleic acid and the mass ratio of catalyst are 5:1~15:1.
Preferably, described step 1) in be heated to 290~370 DEG C.In the range of reaction temperature, temperature is improved
The activity of catalyst and reaction substrate can be increased, accelerate reaction speed, reaction yield is improved
Preferably, described step 1) in the reaction time be 1~10h.
Preferably, described organic solvent can be acetone, n-hexane or dichloromethane etc..
As an improvement, described step 2) in solid-phase catalyst proceed to clean and be dried in vacuo.Solid-phase catalyst is passed through
It can be used, increased economic efficiency with circulating repetition after over cleaning and drying.
It is 5 as the mass ratio of further preferred, described oleic acid and catalyst:1~10:1.
Be used as further preferred, described step 1) in be heated to 330~370 DEG C.It is long in the heating temperature range
The yield of alkane be more than 50% and aromatic hydrocarbons yield be more than 14%.
It is 5 as the mass ratio of further preferred, described oleic acid and catalyst:1~6:1；Described step 1) in plus
Heat is warming up to 350~370 DEG C, and the reaction time is 1~2h.Under the optimum condition, the yield of long chain alkane is more than 72% and virtue
The yield of hydrocarbon is more than 19%.
Compared with the existing technology, beneficial effects of the present invention are embodied in：
(1) the not additional any hydrogen of the present invention, hydrogen supply agent or solvent, make a part of oleic acid using Pt/C catalytic action
And simultaneously further intramolecular D-A reacts aromatisation hydrogen supply for its alkene dehydrogenation of decarboxylate 17, the hydrogen of generation is rapidly saturated being left
Oleic acid into stearic acid, stearic acid decarboxylation is into heptadecane, by dehydrogenation, decarboxylation, hydrogenation, the step coupling of four technical process of aromatisation one
Close, make oleic acid Efficient Conversion for long chain alkane and aromatic hydrocarbons, the yield of long chain alkane and aromatic hydrocarbons can be respectively up to 72% and more than 19%.
(2) present invention only needs to add appropriate oleic acid and catalyst in high-temperature high-pressure reaction kettle, it is not necessary to add hydrogen
Gas, hydrogen supply agent, solvent and any other hydrogen source, realize zero hydrogen consumption, but also directly obtained hydrogenation deoxidation and Fischer-Tropsch conjunction
Into the aromatic hydrocarbons for being difficult to obtain.Solid-liquid two-phase can be to realize separation through filtering after the completion of reaction, and product separation process is simple, solid
Catalyst is easy to be recycled, and production process green, zero hydrogen consumption, energy consumption is low, simply preferably go, safe and reliable.
Brief description of the drawings
Fig. 1 is that the present invention consumes one-step method by raw material zero hydrogen of oleic acid while preparing the technique of the method for long chain alkane and aromatic hydrocarbons
General flow chart.
Embodiment
The gas chromatograph-mass spectrometer (GC-MS) (Agilent 5977A MSD) provided with three shuntings is used in the present invention while right
Long chain alkane and aromatic hydrocarbons carry out qualitative and quantitative analysis, and concrete analysis condition is as follows：Chromatographic column is Agilent HP-5MS capillarys
Tubing string (30m × 0.25mm × 0.25 μm), injector temperature：300℃；Sample introduction flow：11.383mL/min；Sample size：1μL；Three
Individual detector FID, TCD, MS detection temperature are 300 DEG C；Temperature programming：50 DEG C are kept for 4 minutes, afterwards with 25 DEG C/min's
Speed is warming up to 190 DEG C, and 200 DEG C are warming up to 5 DEG C/min speed, 250 DEG C is warming up to 15 DEG C/min speed, with 25
DEG C/min speed is warming up to 300 DEG C, last 300 DEG C are kept for 2.5 minutes.
Embodiment 1
240g oleic acid and 16g Pt/C catalyst are added in 500mL intermittent high temperatures autoclaves, 350 DEG C are warming up to instead
Answer 90min；After the completion of reaction, reaction product cooling, with acetone solution, filtering；Liquid product after acetone constant volume with using GC-MS-
FID is analyzed, and it is respectively 54% and 14%, specific technological process that calculating, which obtains C8-17 long chain alkanes and the molar yield of aromatic hydrocarbons,
As shown in Figure 1.
Embodiment 2
240g oleic acid and 24g Pt/C sieve catalysts are added in 500mL intermittent high temperatures autoclaves, 350 DEG C are warming up to
React 90min；After the completion of reaction, reaction product cooling, with acetone solution, filtering；Liquid product after acetone constant volume with using GC-
MS-FID is analyzed, and it is respectively 58% and 14% that calculating, which obtains C8-17 long chain alkanes and the molar yield of aromatic hydrocarbons,.
Embodiment 3
240g oleic acid and 32g Pt/C catalyst are added in 500mL intermittent high temperatures autoclaves, 350 DEG C are warming up to instead
Answer 90min；After the completion of reaction, reaction product cooling, with acetone solution, filtering；Liquid product after acetone constant volume with using GC-MS-
FID is analyzed, and it is respectively 61% and 14% that calculating, which obtains C8-17 long chain alkanes and the molar yield of aromatic hydrocarbons,.
Embodiment 4
240g oleic acid and 40g Pt/C catalyst are added in 500mL intermittent high temperatures autoclaves, 350 DEG C are warming up to instead
Answer 90min；After the completion of reaction, reaction product cooling, with acetone solution, filtering；Liquid product after acetone constant volume with using GC-MS-
FID is analyzed, and it is respectively 71% and 17% that calculating, which obtains C8-17 long chain alkanes and the molar yield of aromatic hydrocarbons,.
Embodiment 5
240g oleic acid and 48g Pt/C catalyst are added in 500mL intermittent high temperatures autoclaves, 350 DEG C are warming up to instead
Answer 90min；After the completion of reaction, reaction product cooling, with acetone solution, filtering；Liquid product after acetone constant volume with using GC-MS-
FID is analyzed, and it is respectively 68% and 18% that calculating, which obtains C8-17 long chain alkanes and the molar yield of aromatic hydrocarbons,.
Embodiment 6
240g oleic acid and 48g Pt/C catalyst are added in 500mL intermittent high temperatures autoclaves, 290 DEG C are warming up to instead
Answer 200min；After the completion of reaction, reaction product cooling, with acetone solution, filtering；Liquid product after acetone constant volume with using GC-MS-
FID is analyzed, and it is respectively 14% and 5% that calculating, which obtains C8-17 long chain alkanes and the molar yield of aromatic hydrocarbons,.
Embodiment 7
240g oleic acid and 48g Pt/C catalyst are added in 500mL intermittent high temperatures autoclaves, 290 DEG C are warming up to instead
Answer 560min；After the completion of reaction, reaction product cooling, with acetone solution, filtering；Liquid product after acetone constant volume with using GC-MS-
FID is analyzed, and it is respectively 32% and 9% that calculating, which obtains C8-17 long chain alkanes and the molar yield of aromatic hydrocarbons,.
Embodiment 8
240g oleic acid and 48g Pt/C catalyst are added in 500mL intermittent high temperatures autoclaves, 330 DEG C are warming up to instead
Answer 110min；After the completion of reaction, reaction product cooling, with acetone solution, filtering；Liquid product after acetone constant volume with using GC-MS-
FID is analyzed, and it is respectively 50% and 17% that calculating, which obtains C8-17 long chain alkanes and the molar yield of aromatic hydrocarbons,.
Embodiment 9
240g oleic acid and 48g Pt/C catalyst are added in 500mL intermittent high temperatures autoclaves, 330 DEG C are warming up to instead
Answer 150min；After the completion of reaction, reaction product cooling, with acetone solution, filtering；Liquid product after acetone constant volume with using GC-MS-
FID is analyzed, and it is respectively 56% and 17% that calculating, which obtains C8-17 long chain alkanes and the molar yield of aromatic hydrocarbons,.
Embodiment 10
240g oleic acid and 48g Pt/C catalyst are added in 500mL intermittent high temperatures autoclaves, 330 DEG C are warming up to instead
Answer 200min；After the completion of reaction, reaction product cooling, with acetone solution, filtering；Liquid product after acetone constant volume with using GC-MS-
FID is analyzed, and it is respectively 63% and 19% that calculating, which obtains C8-17 long chain alkanes and the molar yield of aromatic hydrocarbons,.
Embodiment 11
240g oleic acid and 48g Pt/C catalyst are added in 500mL intermittent high temperatures autoclaves, 370 DEG C are warming up to instead
Answer 80min；After the completion of reaction, reaction product cooling, with acetone solution, filtering；Liquid product after acetone constant volume with using GC-MS-
FID is analyzed, and it is respectively 72% and 19% that calculating, which obtains C8-17 long chain alkanes and the molar yield of aromatic hydrocarbons,.
Claims (5)
1. a kind of method for preparing long chain alkane and aromatic hydrocarbons simultaneously by raw material of oleic acid, it is characterised in that comprise the following steps：
1) oleic acid and catalyst, heat temperature raising reaction are added in high-temperature high-pressure reaction kettle；Described catalyst is Pt/C；It is described
Oleic acid and catalyst mass ratio be 5:1~15:1；Described is heated to 290~370 DEG C；The described reaction time is
1~10h；
2) reaction product is cooled down, organic solvent dissolving, and liquid product and solid-phase catalyst are obtained after filtering.
2. the method according to claim 1 for preparing long chain alkane and aromatic hydrocarbons simultaneously by raw material of oleic acid, it is characterised in that
Described step 2) in solid-phase catalyst proceed to clean and be dried in vacuo.
3. the method according to claim 1 for preparing long chain alkane and aromatic hydrocarbons simultaneously by raw material of oleic acid, it is characterised in that
Described oleic acid and the mass ratio of catalyst are 5:1~10:1.
4. the method according to claim 1 for preparing long chain alkane and aromatic hydrocarbons simultaneously by raw material of oleic acid, it is characterised in that
Described step 1) in be heated to 330~370 DEG C.
5. the method according to claim 1 for preparing long chain alkane and aromatic hydrocarbons simultaneously by raw material of oleic acid, it is characterised in that
Described oleic acid and the mass ratio of catalyst are 5:1~6:1；Described step 1) in be heated to 350~370 DEG C, reaction
Time is 1~2h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610123819.6A CN105670679B (en) | 2016-03-04 | 2016-03-04 | A kind of method for preparing long chain alkane and aromatic hydrocarbons simultaneously by raw material of oleic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610123819.6A CN105670679B (en) | 2016-03-04 | 2016-03-04 | A kind of method for preparing long chain alkane and aromatic hydrocarbons simultaneously by raw material of oleic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105670679A CN105670679A (en) | 2016-06-15 |
| CN105670679B true CN105670679B (en) | 2017-08-01 |
Family
ID=56307852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610123819.6A Active CN105670679B (en) | 2016-03-04 | 2016-03-04 | A kind of method for preparing long chain alkane and aromatic hydrocarbons simultaneously by raw material of oleic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105670679B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106423203B (en) * | 2016-09-26 | 2019-04-02 | 浙江大学 | A kind of method of fatty acid non-hydrogen decarboxylation |
| CN111346660B (en) * | 2020-03-06 | 2021-09-21 | 浙江大学 | Preparation method and product application of nano-alloy M-Zn/NC catalyst |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8389782B2 (en) * | 2010-08-31 | 2013-03-05 | Chevron U.S.A. Inc. | Biofuel production through catalytic deoxygenation |
| CN103614155B (en) * | 2013-09-11 | 2016-08-10 | 浙江工业大学 | A kind of algae oil produces the preparation method of HC fuel |
| WO2015042253A1 (en) * | 2013-09-18 | 2015-03-26 | University Of Louisville Research Foundation, Inc. | Single-step process for production of branched, cyclic, aromatic, and cracked hydrocarbons from fatty acids |
| CN104673352B (en) * | 2015-01-30 | 2016-09-14 | 浙江大学 | A kind of method preparing long chain alkane for raw material low hydrogen consumption with waste oil |
-
2016
- 2016-03-04 CN CN201610123819.6A patent/CN105670679B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105670679A (en) | 2016-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bravo et al. | Bio-crude oil production using catalytic hydrothermal liquefaction (HTL) from native microalgae harvested by ozone-flotation | |
| Huang et al. | Hydrothermal liquefaction of pretreated low-lipid microalgae for the production of bio-oil with low heteroatom content | |
| Tian et al. | Effect of operating conditions on hydrothermal liquefaction of Spirulina over Ni/TiO2 catalyst | |
| CN105237319B (en) | Method for preparation of long-chain alkane from unsaturated fatty acid at zero hydrogen consumption | |
| Huang et al. | Homogeneous Catalytic Hydrogenation of Bio‐Oil and Related Model Aldehydes with RuCl2 (PPh3) 3 | |
| CN104403683A (en) | Method for using non-noble metal catalyst to catalyze decarboxylation of saturated fatty acid to prepare long-chain alkane | |
| Hu et al. | The catalytic pyrolysis of microalgae to produce syngas | |
| CN107460005B (en) | The method and device of aromatic hydrocarbon and alkene is prepared using bio oil catalytic hydrogenation coupling and catalyzing cracking | |
| TWI551548B (en) | Method for preparing fuel from bio-oil | |
| Xu et al. | Catalytic supercritical water gasification of aqueous phase directly derived from microalgae hydrothermal liquefaction | |
| Jiang et al. | Behavior, kinetic and product characteristics of the pyrolysis of oil shale catalyzed by cobalt-montmorillonite catalyst | |
| CN102154023A (en) | Method for preparing hydrocarbon fuel by using microwave-assisted catalytic soap decarboxylation method | |
| CN105670679B (en) | A kind of method for preparing long chain alkane and aromatic hydrocarbons simultaneously by raw material of oleic acid | |
| CN105175205B (en) | A kind of bio-oil prepares the method that carboxylate methyl ester catalytic aromatization prepares aromatic hydrocarbons | |
| CN101831328B (en) | Green fuel oil and preparation method thereof | |
| CN103464179A (en) | Catalyst used for extracting shale oil from oil shale and application method of catalyst | |
| Wang et al. | Creating values from wastes: Producing biofuels from waste cooking oil via a tandem vapor-phase hydrotreating process | |
| CN106540743A (en) | A kind of catalyst that biological Aviation Fuel is prepared for jatropha oil and preparation method thereof | |
| Tong et al. | Two-stage liquefaction of sewage sludge in methanol-water mixed solvents with low-medium temperature | |
| Dong et al. | The production of light olefins by catalytic cracking of the microalga Isochrysis zhanjiangensis over a modified ZSM-5 catalyst | |
| Wang et al. | Effect of unsaturation degree on microwave-assisted pyrolysis of fatty acid salts | |
| Ding et al. | Ketonization of xylose over CeO2 to produce mono-functional ketones | |
| CN103897753A (en) | Method for preparing biological aircraft fuel by using mesoporous molecular sieve | |
| Yu et al. | Biofuel potential of liquid products from protein-and lipid-rich biomass hydrothermal liquefaction | |
| CN103254923B (en) | Biomass hydrogen-donating pyrolysis technique of naphthenic base oil in presence of hydrogen-donating distillate oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |