CN103772100A - Method for preparation of n-eicosane by natural acid-peanut acid - Google Patents
Method for preparation of n-eicosane by natural acid-peanut acid Download PDFInfo
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- CN103772100A CN103772100A CN201210408516.0A CN201210408516A CN103772100A CN 103772100 A CN103772100 A CN 103772100A CN 201210408516 A CN201210408516 A CN 201210408516A CN 103772100 A CN103772100 A CN 103772100A
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Abstract
The invention relates to a method for preparation of n-eicosane by natural acid-peanut acid, the peanut acid is mixed with a solvent for hydrogenation reaction in the presence of a catalyst and hydrogen, the catalyst is a palladium / carbon nanotube catalyst, the hydrogen contas 5-50 mu L / L of NH3, the hydrogenation pressure is 1-10MPa, the reaction temperature 220-320 DEG C, and the reaction time is 3-10h. The catalyst uses multi-wall carbon nanotube as a carrier, and 2%-10% by mass of palladium as an active component; the solvent is one of n-hexane, n-heptane, n-octane or dodecane. Compared with the prior art, the method has the advantages of simple preparation process, low reaction temperature, less solvent consumption, high reaction activity and higher yield of an objective product.
Description
Technical field
The present invention relates to a kind of eicosanoic acid generates NSC 62789 hydrocarbon method through liquid phase catalytic hydrogenation deoxidation, belong to catalysis technical field.
Background technology
Normal paraffin is as one of key ingredient of diesel oil at low-temperature improving agent and environmental protection liquid fuel composition, obtained application widely, normal paraffin monomer is also being brought into play extremely important effect at analysis fields such as geology, crude oil, Atmospheric particulates and organism simultaneously.
The preparation method of existing normal paraffin mainly contains following several: one, take molecular sieve or urea dewaxing to prepare the mixture of normal paraffin, and then carry out that segmentation is freezing, the method for separating normal alkane monomer, wherein typical technique has the independently developed IVDW technique of China; Two, take the symmetrical normal paraffin of Woertz reaction preparation; Three, adopt alkane iodide method of reducing; Four, use sherwood oil and normal hexane, normal heptane to make solvent link haloalkane method.Although above method can obtain corresponding normal paraffin monomer, all there is certain problem in each method: as first method processing condition more complicated, require very high to some equipment, material; Second method is only applicable to symmetry even number alkane, and generating article needs ether solvent repeatedly to extract; Third and fourth kind of method operational danger is large, and sherwood oil is very easily eruption in sodium Metal 99.5 and haloalkane vigorous reaction, and safety coefficient is low, and cost is higher.
CN200810151995.6 discloses a kind of synthetic and New Method of Purification of NSC 62789, and the step of its preparation method comprises: mix positive structure butyl bromide (1) with bromo n-hexadecane; (2) after sherwood oil is mixed with mixed solution, add sodium, back flow reaction 1～2 hour; (3) drip after dehydrated alcohol, water, separate organic phase and be washed to neutrality; (4) cut of 320～360 ℃ is collected in distillation, through wash colourless to organic phase or be faint yellow after, be washed to neutrality; (5) by after dry organic phase rear filtration, absorption, in the middle of underpressure distillation collection, just cut obtains NSC 62789 product.
Can prepare corresponding alkane with higher fatty acid ester through hydrogenation, but in hydrogenation process, can there is a large amount of decarboxylic reaction and decarbonylation reaction, make reaction product composition complicated, can produce the alkane that more carbon number reduces, the productive rate that is unfavorable for improving on the one hand object product, decarboxylic reaction and decarbonylation reaction can produce carbon monoxide or carbonic acid gas on the other hand, can produce adverse influence to hydrogenation reaction.
CN200910100260.5 discloses a kind of method of preparing alkane by high fatty acid ester, take the fatty acid methyl ester that contains 8～22 carbon atoms or the fatty-acid ethyl ester that contains 8～22 carbon atoms as raw material, carry out hydrogenation reaction and produce alkane, but can find out, in the alkane product obtaining, carbon in lipid acid still has major part to be removed, as take stearic acid methyl ester (stearic acid is as 18 carbon carboxylic acids) as raw material, the heptadecane hydrocarbon obtaining and the total recovery of octodecane hydrocarbon only have 75%, therefore, the yield of the product of decarburization direct hydrogenation (octodecane hydrocarbon) can be not lower.Meanwhile, the boiling point of heptadecane hydrocarbon and octodecane hydrocarbon differs very little, further obtains octodecane hydrocarbon by isolation technique very difficult.And adopt method of hydrotreating production NSC 62789 technology to yet there are no report.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method that natural acid-eicosanoic acid is prepared NSC 62789 hydrocarbon, the inventive method, under the higher condition of eicosanoic acid feed stock conversion, can obtain higher NSC 62789 yield.
The method that eicosanoic acid of the present invention is prepared NSC 62789 hydrocarbon comprises following content: eicosanoic acid raw material and solvent, under catalyzer and hydrogen existence, carry out hydrogenation reaction, and in hydrogen, contain the NH of 5～50 μ L/L
3, catalyzer is palladium/carbon nano-tube catalyst, and the reaction pressure of hydrogenation reaction is 1～10MPa, is preferably 2～8MPa, and temperature of reaction is 220～320 ℃, is preferably 260～300 ℃, and the reaction times is 3～10h, is preferably 4～7h.
In the inventive method, hydrogenation process can adopt intermittent reaction, also can adopt continuous reaction.While adopting intermittent reaction, be preferably under agitation condition and carry out, the volume ratio of eicosanoic acid and catalyzer is l.0～2.5:0.2～0.5.While adopting continuous reaction, hydrogen and liquid phase (eicosanoic acid and the solvent) volume ratio under standard state is 100:1～1200:1, is preferably 300:1～800:1.
In the inventive method, in the hydrogen that hydrogenation reaction is used, preferably contain the NH of 5～50 μ L/L
3, be preferably 10～20 μ L/L, to improve the selectivity of object product NSC 62789.
In the inventive method, natural acid raw material refers to and from peanut oil, is hydrolyzed isolated eicosanoic acid.
In the inventive method, solvent is one or more in normal hexane, normal heptane, octane or dodecane, and the volume ratio of eicosanoic acid and solvent is: l.0～2.5:7～20.
In the inventive method, catalyzer is take multi-walled carbon nano-tubes as carrier, take the palladium of quality percentage composition 2%～10% as active ingredient.Multi-walled carbon nano-tubes is common commercial goods.
The preparation method of used catalyst of the present invention is as follows: under 50～100 ℃ of conditions, with the HNO of 2～8Mol/L
3multi-walled carbon nano-tubes is carried out to oxide treatment 1～5h, then filter, be washed to neutrality, 100～150 ℃ of oven dry; Then be added to the water, ultrasonic dispersion, adds H by the quality percentage composition 2%～10% of palladium in catalyzer
2pdC1
4solution, adds formaldehyde solution after stirring, and with NaOH solution adjusting pH value to 8～11, stirs, filters, washes, dries, and obtains Pd/MWCNTs catalyzer.
Find through large quantity research, method of the present invention, the hydrogenation deoxidation of eicosanoic acid is had to very high catalytic activity and object product (NSC 62789) selectivity, decarboxylic reaction and decarbonylation reaction that carbon number is reduced are little, while particularly containing a small amount of ammonia in hydrogen, the selectivity of object product is higher.Compared with prior art, the feature that the present invention has is: 1, catalyst preparation process is simple, can be recycled.2, temperature of reaction significantly reduces, and is the production process of less energy-consumption.3, solvent load is few, cheap and easy to get, and boiling point is low, is easy to recycle.4, this process operation is flexible.
5, object product selectivity is high, is conducive to subsequent separation process.
Embodiment
Embodiment 1
Catalyzer preparation
In 80 ℃ of oil baths, use 6M HNO
3multi-walled carbon nano-tubes (diameter 40～60nm, length 5～15 μ m, nanometer port, Shenzhen company limited provides for commercial goods, purity >95%) is carried out to oxide treatment 2h, then filter, be washed to neutrality, 120 ℃ of oven dry; Get the carbon nanotube that above-mentioned oxide treatment is crossed, add 70mL water, ultrasonic dispersion; Be that active ingredient adds H by the palladium of quality percentage composition 2%～10%
2pdC1
4solution, after stirring, add formaldehyde solution, by 1M NaOH solution adjusting pH value to 9, stir 25min, filter, massive laundering, dries, obtain Pd/ multi-walled carbon nano-tubes catalyzer (Pd/MwCNTs), preparing two kinds of catalyzer is that catalyzer 1(palladium mass content is 4%) and catalyzer 2(palladium mass content be 7%).
Embodiment 2
2.5 parts of (parts by volume, lower same) eicosanoic acids, 1 and 20 parts of normal hexanes of 0.3 part of Pd/MwCNTs catalyzer are added in 100mL reactor, be filled with hydrogen, initial hydrogen pressure 2.5MPa, opens and stirs and heating, stopped reaction after 280 ℃ of reaction 6h, to be cooled to room temperature, filter to isolate catalyzer.By gas-chromatography, product is carried out to detection by quantitative, the transformation efficiency of known raw material eicosanoic acid is 85%, and the total recovery of product NSC 62789 is 80%(molar yield, and product NSC 62789 accounts for the per-cent of raw material eicosanoic acid, lower same).
Embodiment 3
1.5 parts of eicosanoic acids, 2 and 16 parts of normal hexanes of 0.4 part of Pd/MwCNTs catalyzer are added in 100mL reactor, be filled with the hydrogen (NH that contains 5 μ L/L
3), initial hydrogen pressure 5.0MPa, opens and stirs and heating, and stopped reaction after 260 ℃ of reaction 7h is to be cooled to room temperature, filters to isolate catalyzer.By gas-chromatography, product is carried out to detection by quantitative, the transformation efficiency of known raw material eicosanoic acid is 89%, and the yield of product NSC 62789 is 85%.
Embodiment 4
2.0 parts of eicosanoic acids, 2 and 18 parts of normal hexanes of 0.5 part of Pd/MwCNTs catalyzer are added in 100mL reactor, be filled with the hydrogen (NH that contains 20 μ L/L
3), initial hydrogen pressure 6.0MPa, opens and stirs and heating, and stopped reaction after 300 ℃ of reaction 7h is to be cooled to room temperature, filters to isolate catalyzer.Product is carried out to detection by quantitative by gas-chromatography, known raw material eicosanoic acid transformation efficiency be 94%, the yield of product NSC 62789 is 88%.
Claims (10)
1. natural acid-eicosanoic acid is prepared a method for NSC 62789 hydrocarbon, it is characterized in that comprising following content: eicosanoic acid raw material and solvent, under catalyzer and hydrogen existence, carry out hydrogenation reaction, and in hydrogen, contain the NH of 5～50 μ L/L
3, catalyzer is palladium/carbon nano-tube catalyst, and the reaction pressure of hydrogenation reaction is 1～10MPa, and temperature of reaction is 220～320 ℃, and the reaction times is 3～10h.
2. in accordance with the method for claim 1, it is characterized in that: the reaction pressure of hydrogenation reaction is 2～8MPa, temperature of reaction is 280～330 ℃, and the reaction times is 4～7h.
3. in accordance with the method for claim 1, it is characterized in that: hydrogenation process adopts intermittent reaction, reaction is carried out under agitation condition, and the volume ratio of eicosanoic acid and catalyzer is l.0～2.5:0.2～0.5.
4. in accordance with the method for claim 1, it is characterized in that: hydrogenation process adopts continuous reaction, and hydrogen and the liquid phase volume ratio under standard state is 100:1～1200:1.
5. according to the method described in claim 1,3 or 4, it is characterized in that: the NH that preferably contains 5～50 μ L/L in the hydrogen that hydrogenation reaction is used
3.
6. it is characterized in that in accordance with the method for claim 5: the NH that preferably contains 10～20 μ L/L in the hydrogen that hydrogenation reaction is used
3.
7. it is characterized in that in accordance with the method for claim 1: natural acid is 20 acid of making a comment or criticism.
8. in accordance with the method for claim 1, it is characterized in that: solvent is one or more in normal hexane, normal heptane, octane or dodecane, and the volume ratio of eicosanoic acid and solvent is: l.0～2.5:7～20.
9. in accordance with the method for claim 1, it is characterized in that: catalyzer is take multi-walled carbon nano-tubes as carrier, in catalyst quality containing active component palladium 2%～10%.
10. in accordance with the method for claim 9, it is characterized in that: the preparation method of catalyzer is as follows, under 50～100 ℃ of conditions, with the HNO of 2～8Mol/L
3multi-walled carbon nano-tubes is carried out to oxide treatment 1～5h, then filter, be washed to neutrality, 100～150 ℃ of oven dry; Then be added to the water, ultrasonic dispersion, adds H by the quality percentage composition 2%～10% of palladium in catalyzer
2pdC1
4solution, adds formaldehyde solution after stirring, and with NaOH solution adjusting PH value to 8～11, stirs, filters, washes, dries, and obtains Pd/MWCNTs catalyzer.
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| CN201210408516.0A CN103772100B (en) | 2012-10-24 | 2012-10-24 | Method for preparation of n-eicosane by natural acid-peanut acid |
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| CN201210408516.0A CN103772100B (en) | 2012-10-24 | 2012-10-24 | Method for preparation of n-eicosane by natural acid-peanut acid |
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| CN103772100B CN103772100B (en) | 2015-05-13 |
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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 |
| CN101597508A (en) * | 2009-07-02 | 2009-12-09 | 浙江大学 | A kind of method of preparing alkane by high fatty acid ester |
| US20120029250A1 (en) * | 2010-08-02 | 2012-02-02 | Battelle Memorial Institute | Deoxygenation of fatty acids for preparation of hydrocarbons |
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- 2012-10-24 CN CN201210408516.0A patent/CN103772100B/en active Active
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 |
| CN101597508A (en) * | 2009-07-02 | 2009-12-09 | 浙江大学 | A kind of method of preparing alkane by high fatty acid ester |
| US20120029250A1 (en) * | 2010-08-02 | 2012-02-02 | Battelle Memorial Institute | Deoxygenation of fatty acids for preparation of hydrocarbons |
Non-Patent Citations (2)
| Title |
|---|
| JUNXING HAN ET AL.: "Nanostructured molybdenum carbides supported on carbon nanotubes as efficient catalysts for one-step hydrodeoxygenation and isomerization of vegetable oils", 《GREEN CHEMISTRY》, vol. 13, 29 July 2011 (2011-07-29), pages 2561 - 2568 * |
| 赵阳等: "棕榈油加氢制备高十六烷值柴油组分", 《石油学报（石油化工）》, vol. 27, no. 4, 31 August 2011 (2011-08-31), pages 501 - 507 * |
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