CN103666519A - Method for preparing alkanes by hydrodeoxygenation of non-edible animal and vegetable oil - Google Patents
Method for preparing alkanes by hydrodeoxygenation of non-edible animal and vegetable oil Download PDFInfo
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- CN103666519A CN103666519A CN201210322774.7A CN201210322774A CN103666519A CN 103666519 A CN103666519 A CN 103666519A CN 201210322774 A CN201210322774 A CN 201210322774A CN 103666519 A CN103666519 A CN 103666519A
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
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Abstract
The invention relates to a method for preparing alkanes by hydrodeoxygenation of non-edible animal and vegetable oil. The method comprises the following steps: loading 5-10mL of nickel-molybdenum catalyst containing 3-5wt% of cerium oxide and silicon oxide into a constant-temperature section of a reactor, well filling an upper section and a lower section of the reactor by using an inert material, replacing air with nitrogen three times, and performing hydrodeoxygenation reaction on the non-edible animal and vegetable oil as raw materials in the presence of a hydrocarbon type solvent under the conditions that the reaction temperature is 200-500 DEG C, the pressure is 1.0-6.0MPa, the air speed is 0.5-10h<-1> and the hydrogen-oil volume ratio is 200-2000 to prepare the alkanes taking C15-C18 as main components, wherein the non-edible animal and vegetable oil mainly comprises fatty acid glycerides of C9-C24, and the catalyst is a conventional nickel-molybdenum hydrodeoxygenation catalyst added with 3-5wt% of cerium oxide and silicon oxide in equal weight ratio. The raw materials used in the method are non-edible oil, and the cost is low; the process is simple, and no byproducts are produced; fatty acid carbon chains keep lengths of the original carbon chains; the products are stable, high in calorific value, green and renewable.
Description
Technical field
The present invention relates to non-edible animals and plants oil hydrogenation deoxidation and prepare the method for alkane, adopting not the non-edible animals and plants oil of striving grain with people is raw material, under the effect of high-performance non-noble metal hydrogenation dehydrogenation catalyst, prepares the method for renewable alkane through hydrogenation deoxidation.
Background technology
Along with the development of world economy, what petroleum resources were consumed increased progressively with day, and energy shortage has become the significant problem that affects human society sustainable development.Bioenergy is because reserves are abundant, and there is environmental friendliness and reproducible feature, when meeting Future Society energy demand, also the theory that meets sustainable scientific development and recycling economy, European Union points out in " European Union's energy development strategy Green Book " of its issue, by 2015, the current consumption of biomass energy is accounted for to total energy consumption 2% left and right and bring up to 15%, arrive the year two thousand twenty biomass fuel by the fossil oil that substitutes 20%.Therefore how to develop and to use bioenergy to become the integral part of world energy strategy.
From early 1980s, American scientist Craham Quick successfully for after motor spirit, has just had biofuel by the methyl esters of the linseed oil of preparation.Utilize the low-carbon alcohol such as methyl alcohol, ethanol to carry out lipid acid methyl/ethyl ester prepared by transesterify and belong to first-generation biofuel, although also can be used as motor spirit, but its chemical constitution, structure, character etc. are obviously different from fossil base fuel, oxygen level is higher, poor stability, calorific value are lower, corrosion engine, also can produce aborning a large amount of trade effluents containing acid, alkali, grease.Therefore, carry out that novel method is prepared green, recyclable fuel is significant.
The non-edible animals and plants oil of take is raw material, adopt the renewable alkane of hydrogenation deoxidation explained hereafter, it is so-called biofuel of new generation, it is similar to fossil base fuel with properties at composition, do not need more to reengine and prime the fuel system, can directly join in fossil oil or separately and use as fuel, and in life cycle the quantity discharged of greenhouse gases than low 50% left and right of fossil base fuel.At present, adopt this kind of technique to prepare renewable alkane, become the focus of various countries' research and extension.
Take renewable material as raw material, through hydrogenation deoxidation, prepare green alkane and as automotive fuel, be subject to various countries scholar's attention, patent EP1728844A1 (take edible soybean oil as raw material), CN101842465A (be take edible soybean oil as raw material, reaction pressure is higher), CN101326267A (be take edible soybean oil as raw material, reaction pressure is higher, precious metals pd catalyzer) etc. to prepare the biomass material of alkane be mainly food grade vegetables oil to the hydrogenation deoxidation of report, and reaction pressure is higher, use precious metal as the active ingredient of hydrogenation deoxidation catalyst, this makes production cost higher, and discarded non-edible animals and plants oil is not utilized preferably yet, this has all limited mass-producing application in industry.
Summary of the invention
The object of this invention is to provide a kind of non-edible animals and plants oil hydrogenation deoxidation and prepare the method for alkane, adopting cheap non-edible animals and plants oil is raw material, adopts high-performance non-precious metal catalyst, through hydrogenation deoxidation, prepares method green, renewable alkane.
Non-edible animals and plants oil hydrogenation deoxidation of the present invention is prepared the method for alkane, is that the nickel molybdenum non-precious metal catalyst catalytic hydrodeoxygenation preparation of 3 ~ 5wt% cerium oxide that non-edible animals and plants oil is obtained through conventional method and silicon oxide is green, renewable alkane.Preparation process is, at reactor constant temperature zone, packs 5 ~ 10mL into containing the nickel molybdenum catalyst of the anharmonic ratio cerium oxide such as 3 ~ 5wt% and silicon oxide, and reactor upper-lower section is all used absorbent cotton, the inert materials such as quartz sand are filled in, and nitrogen replacement 3 times, with Thistle oil, tori seed oil, non-food grade plam oil, Yatall MA, Viscotrol C, oleum gossypii seminis, hempseed oil, Jatropha curcas oil, Toenol 1140, sewer oil, yellow and brown grease and the non-edible animals and plants oil of algae wet goods are raw material, and more preferably raw material is Jatropha curcas oil, non-food grade plam oil, sewer oil, castor-oil plant wet goods, at normal hexane, benzene, toluene, dimethylbenzene, normal heptane, octane, positive nonane, n-decane, n-undecane, under n-dodecane and their mixture or fossil fuel equal solvent exist, 200 ~ 500 ℃ of temperature of reaction, preferable reaction temperature is 290 ~ 400 ℃, most preferably temperature of reaction is 320 ~ 380 ℃, reaction pressure 1.0 ~ 6.0MPa, preferred reaction pressure is 2.0 ~ 5.0MPa, and most preferably reaction pressure is 3.0 ~ 4.0MPa, reaction velocity 0.5 ~ 10h
-1, preferred reaction air speed is 2.0 ~ 7.0h
-1, most preferably reaction velocity is 4.0 ~ 6.0h
-1reaction hydrogen to oil volume ratio is 200 ~ 2000, preferred reaction hydrogen to oil volume ratio is 500 ~ 1500, most preferably reacting hydrogen to oil volume ratio is under 800 ~ 1000 conditions, composition is prepared in raw material generation hydrogenation deoxidation reaction, character is similar to fossil fuel, stablizes, calorific value is high and reproducible C15 ~ C18 alkane that is rich in.Liquid hydrocarbon yield is at 82 (mass) more than %.
The non-food grade vegetable and animals oils that adopts main component to be comprised of the glycerin fatty acid ester of C9 ~ C24 is raw material, the nickel molybdenum base metal of take containing 3 ~ 5wt% cerium oxide and silicon oxide is hydrogenation deoxidation catalyst, hydrogenation deoxidation reaction occurs under the processing condition that relax to be prepared the flow process of alkane and is simply easy to large-scale promotion application, object product is easy to separation, the fatty acid carbon chain that forms tri-glyceride does not rupture, still keep former carbon chain lengths, nickel molybdenum non-noble metal hydrogenation dehydrogenation catalyst containing 3 ~ 5%wt cerium oxide and silicon oxide is active in hydro-thermal situation, selectivity is better, object product is due to oxygen-free rear structure, performance is more stable, combustion heat value is higher, the alkane producing can be regenerated, in life cycle, the greenhouse gases of discharge are lower, in today of energy-saving and emission-reduction call at present and environmental regulation requirement increasingly stringent, the method that non-edible animals and plants oil hydrogenation deoxidation is prepared alkane is significant.
Preparation method of the present invention, green to the preparation of non-edible animals and plants oil hydrogenation deoxidation, renewable alkane yield is higher, to prepare biofuel technology with other and compare, feature of the present invention is, and the raw material of use is inedible oil, and cost is low; Preparation technology's flow process is simple, without difficult by product; Not cracking of fatty acid carbon chain, keeps former carbon chain lengths; Catalyzer adopts ordinary method preparation, has added 3 ~ 5wt% cerium oxide and silicon oxide, makes nickel molybdenum catalyst hydrogenation deoxidation activity, selectivity and the hydrothermal energy of 3 ~ 5%wt cerium oxide and silicon oxide better; Product is stable, calorific value is high and green, renewable, is conducive to large-scale promotion application.
Embodiment
Embodiment 1
Jatropha curcas oil hydrogenation deoxidation is prepared alkane
The nickel molybdenum catalyst that 10mL is contained to 3 ~ 5wt% cerium oxide and silicon oxide packs constant temperature zone in reactor into, reactor upper-lower section is all filled in absorbent cotton, quartz sand, and nitrogen replacement 3 times be take Jatropha curcas oil as raw material, under octane solvent exists, 380 ℃, 4.0MPa, 5.0h
-1, hydrogen/Jatropha curcas oil 1000, reaction 10h, by GC-MS, product is carried out to qualitative and quantitative analysis, liquid hydrocarbon yield 82.23%, wherein C15 ~ C18 alkane yield 80.21%.
Embodiment 2
Non-food grade plam oil hydrogenation deoxidation is prepared alkane
The nickel molybdenum catalyst that 10mL is contained to 3 ~ 5wt% cerium oxide and silicon oxide packs constant temperature zone in reactor into, reactor upper-lower section is all filled in absorbent cotton, quartz sand, nitrogen replacement 3 times, and the non-food grade plam oil of take is raw material, under octane solvent exists, 360 ℃, 3.5MPa, 5.0h
-1, hydrogen/non-food grade plam oil 1000, reaction 10h, by GC-MS, product is carried out to qualitative and quantitative analysis, liquid hydrocarbon yield 82.56%, wherein C15 ~ C18 alkane yield 79.56%.
Embodiment 3
Sewer oil hydrogenation deoxidation is prepared alkane
The nickel molybdenum catalyst that 10mL is contained to 3 ~ 5wt% cerium oxide and silicon oxide packs constant temperature zone in reactor into, and reactor upper-lower section is all filled in absorbent cotton, quartz sand, and nitrogen replacement 3 times be take sewer oil as raw material, under octane solvent exists, and 380 ℃, 4.0MPa, 4.5h
-1, hydrogen/sewer oil 900, reaction 10h, by GC-MS, product is carried out to qualitative and quantitative analysis, liquid hydrocarbon yield 82.17%, wherein C15 ~ C18 alkane yield 78.69%.
Embodiment 4
Viscotrol C hydrogenation deoxidation is prepared alkane
The nickel molybdenum catalyst that 10mL is contained to 3 ~ 5wt% cerium oxide and silicon oxide packs constant temperature zone in reactor into, and reactor upper-lower section is all filled in absorbent cotton, quartz sand, and nitrogen replacement 3 times be take Viscotrol C as raw material, under solvent benzol exists, and 380 ℃, 4.0MPa, 5.0h
-1, hydrogen/Viscotrol C 1000, reaction 10h, by GC-MS, product is carried out to qualitative and quantitative analysis, liquid hydrocarbon yield 82.06%, wherein C15 ~ C18 alkane yield 75.17%.
Claims (7)
1. a non-edible animals and plants oil hydrogenation deoxidation is prepared the method for alkane, it is characterized in that: at reactor constant temperature zone, pack 5 ~ 10mL into containing the nickel molybdenum catalyst of 3 ~ 5wt% cerium oxide and silicon oxide, reactor upper-lower section is all filled in inert material, nitrogen replacement 3 times, the non-edible animals and plants oil of take is raw material, at varsol, exists, and temperature of reaction is 200 ~ 500 ℃, pressure is 1.0 ~ 6.0MPa, and air speed is 0.5 ~ 10h
-1hydrogen to oil volume ratio is that the alkane that hydrogenation deoxidation reaction preparation main component is C15 ~ C18 occurs under 200 ~ 2000 conditions;
Described non-edible animals and plants oil is mainly comprised of the glycerin fatty acid ester of C9 ~ C24;
The described nickel molybdenum catalyst containing 3 ~ 5wt% cerium oxide and silicon oxide is that the anharmonic ratioes such as conventional nickel molybdenum hydrogenation deoxidation catalyst add 3 ~ 5wt% cerium oxide and silicon oxide.
2. non-edible animals and plants oil hydrogenation deoxidation according to claim 1 is prepared the method for alkane, it is characterized in that: non-edible animals and plants grease separation is from Thistle oil, tori seed oil, non-food grade plam oil, Yatall MA, Viscotrol C, oleum gossypii seminis, hempseed oil, Jatropha curcas oil, Toenol 1140, sewer oil, yellow and brown grease and algae oil.
3. non-edible animals and plants oil hydrogenation deoxidation according to claim 1 is prepared the method for alkane, it is characterized in that: it is normal hexane, benzene,toluene,xylene, normal heptane, octane, positive nonane, n-decane, n-undecane, n-dodecane and composition thereof or fossil fuel that varsol is selected.
4. non-edible animals and plants oil hydrogenation deoxidation according to claim 1 is prepared the method for alkane, it is characterized in that: temperature of reaction is 320 ~ 380 ℃.
5. non-edible animals and plants oil hydrogenation deoxidation according to claim 1 is prepared the method for alkane, it is characterized in that: reaction pressure is 3.0 ~ 4.0MPa.
6. non-edible animals and plants oil hydrogenation deoxidation according to claim 1 is prepared the method for alkane, it is characterized in that: reaction velocity is 4.0 ~ 6.0h
-1.
7. non-edible animals and plants oil hydrogenation deoxidation according to claim 1 is prepared the method for alkane, it is characterized in that: reaction hydrogen to oil volume ratio is 800 ~ 1000.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327878A (en) * | 2014-10-11 | 2015-02-04 | 肖连朝 | N-alkane and preparation method thereof |
| CN105176698A (en) * | 2015-08-12 | 2015-12-23 | 中国科学技术大学先进技术研究院 | Method for preparing aviation biofuel by catalytic hydrogenation of Jatropha carcas L. oil |
| CN105295997A (en) * | 2015-11-03 | 2016-02-03 | 何巨堂 | Arrangement method of downward-flowing type high oxygen and hydrocarbon hydrogenation reactor layered catalyst bed |
| CN107573968A (en) * | 2017-09-18 | 2018-01-12 | 肖连朝 | A kind of method that high-purity biology alkane is prepared using waste grease |
| CN114672337A (en) * | 2022-03-18 | 2022-06-28 | 大连理工大学 | Method for catalyzing biological oil hydrodeoxygenation by using bimetal nitride |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327878A (en) * | 2014-10-11 | 2015-02-04 | 肖连朝 | N-alkane and preparation method thereof |
| CN105176698A (en) * | 2015-08-12 | 2015-12-23 | 中国科学技术大学先进技术研究院 | Method for preparing aviation biofuel by catalytic hydrogenation of Jatropha carcas L. oil |
| CN105295997A (en) * | 2015-11-03 | 2016-02-03 | 何巨堂 | Arrangement method of downward-flowing type high oxygen and hydrocarbon hydrogenation reactor layered catalyst bed |
| CN107573968A (en) * | 2017-09-18 | 2018-01-12 | 肖连朝 | A kind of method that high-purity biology alkane is prepared using waste grease |
| CN107573968B (en) * | 2017-09-18 | 2020-01-03 | 肖连朝 | Method for preparing high-purity bio-alkane by using waste oil |
| CN114672337A (en) * | 2022-03-18 | 2022-06-28 | 大连理工大学 | Method for catalyzing biological oil hydrodeoxygenation by using bimetal nitride |
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| CN103666519B (en) | 2015-09-23 |
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