CN103666519B - Non-edible animals and plants oil hydrogenation deoxidation prepares the method for alkane - Google Patents
Non-edible animals and plants oil hydrogenation deoxidation prepares the method for alkane Download PDFInfo
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- CN103666519B CN103666519B CN201210322774.7A CN201210322774A CN103666519B CN 103666519 B CN103666519 B CN 103666519B CN 201210322774 A CN201210322774 A CN 201210322774A CN 103666519 B CN103666519 B CN 103666519B
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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
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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
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The present invention relates to a kind of method that non-edible animals and plants oil hydrogenation deoxidation prepares alkane, the nickel molybdenum catalyst of 3 ~ 5wt% cerium oxide and silicon oxide is contained at reactor constant temperature zone loading 5 ~ 10mL, reactor upper-lower section is all filled in inert material, nitrogen replacement 3 times, with non-edible animals and plants oil for raw material, exist at varsol, temperature of reaction is 200 ~ 500 DEG C, pressure is 1.0 ~ 6.0MPa, and air speed is 0.5 ~ 10h
-1hydrogen to oil volume ratio be occur under 200 ~ 2000 conditions hydrogenation deoxidation reaction preparation main component be the alkane of C15 ~ C18; Non-edible animals and plants oil forms primarily of the glycerin fatty acid ester of C9 ~ C24; Catalyzer is that the anharmonic ratioes such as conventional nickel molybdenum hydrogenation deoxidation catalyst add 3 ~ 5wt% cerium oxide and silicon oxide; Present method raw material is inedible oil, and cost is low; Technique is simple, no coupling product; Fatty acid carbon chain keeps former carbon chain lengths; Product stable, calorific value are high and green, renewable.
Description
Technical field
The present invention relates to the method that non-edible animals and plants oil hydrogenation deoxidation prepares alkane, adopt the non-edible animals and plants oil not striving grain with people to be raw material, under the effect of high-performance non-noble metal hydrogenation dehydrogenation catalyst, prepare the method for renewable alkane through hydrogenation deoxidation.
Background technology
Along with the development of world economy, increasing progressively with day of petroleum resources consumption, energy shortage has become the significant problem affecting human society sustainable development.Bioenergy is due to rich reserves, and there is environmental friendliness and reproducible feature, while meeting Future Society energy demand, also the theory of sustainable scientific development and recycling economy is met, European Union points out in its " European Union's energy development strategy Green Book " issued, by 2015, current for biomass energy consumption is accounted for total energy consumption about 2% and brings up to 15%, to the fossil oil that the year two thousand twenty biomass fuel will substitute 20%.Therefore how to develop and use bioenergy to become the integral part of world energy strategy.
From early 1980s, American scientist Craham Quick there has been biofuel after the methyl esters of the linseed oil of preparation is used successfully to motor spirit.Lipid acid methyl/ethyl ester prepared by transesterify belongs to first-generation biofuel to utilize the low-carbon alcohol such as methyl alcohol, ethanol to carry out, although also can motor spirit be used as, but its chemical constitution, structure, character etc. are obviously different from fossil fuels, oxygen level is higher, poor stability, calorific value are lower, corrosion engine, also can produce a large amount of trade effluent containing acid, alkali, grease aborning.Therefore, carry out novel method to prepare green, recyclable fuel is significant.
With non-edible animals and plants oil for raw material, adopt the renewable alkane of hydrogenation deoxidation explained hereafter, i.e. so-called biofuel of new generation, it is similar to fossil fuels with properties at composition, do not need more to reengine and prime the fuel system, directly can join in fossil oil or separately and use as fuel, and the quantity discharged of greenhouse gases is lower than fossil fuels by about 50% in life cycle.At present, adopt this kind of technique to prepare renewable alkane, become the focus of various countries' research and extension.
With renewable material for raw material, prepare green alkane through hydrogenation deoxidation and be used as the attention that automotive fuel has been subject to scholars, patent EP1728844A1 (taking edible soybean oil as raw material), CN101842465A (take edible soybean oil as raw material, reaction pressure is higher), CN101326267A (take edible soybean oil as raw material, reaction pressure is higher, precious metals pd catalyzer) etc. the hydrogenation deoxidation of report prepare the biomass material mainly food grade vegetables oil of alkane, 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 also utilized preferably, this all limits the application of mass-producing in the industry.
Summary of the invention
The object of this invention is to provide a kind of method that non-edible animals and plants oil hydrogenation deoxidation prepares alkane, adopt cheap non-edible animals and plants oil to be raw material, adopt high-performance non-precious metal catalyst, prepare method that is green, renewable alkane through hydrogenation deoxidation.
Non-edible animals and plants oil hydrogenation deoxidation of the present invention prepares the method for alkane, is that the nickel molybdenum non-precious metal catalyst catalytic hydrodeoxygenation preparation of 3 ~ 5wt% cerium oxide and the silicon oxide obtained through conventional method by non-edible animals and plants oil is green, renewable alkane.Preparation process is, contain the nickel molybdenum catalyst of the anharmonic ratio cerium oxide such as 3 ~ 5wt% and silicon oxide at reactor constant temperature zone loading 5 ~ 10mL, reactor upper-lower section all uses 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, n-nonane, n-decane, n-undecane, under n-dodecane and their mixture or fossil fuel equal solvent exist, temperature of reaction 200 ~ 500 DEG C, preferable reaction temperature is 290 ~ 400 DEG C, most preferably temperature of reaction is 320 ~ 380 DEG C, 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, raw material generation hydrogenation deoxidation reaction preparation composition, character is similar to fossil fuel, comparatively stablizes, calorific value is high and be reproduciblely rich in C15 ~ C18 alkane.Liquid hydrocarbon yield is at 82 (mass) more than %.
The non-food grade vegetable and animals oils adopting main component to be made up of the glycerin fatty acid ester of C9 ~ C24 is raw material, with the nickel molybdenum base metal containing 3 ~ 5wt% cerium oxide and silicon oxide for hydrogenation deoxidation catalyst, under the processing condition comparatively relaxed, there is the flow process that hydrogenation deoxidation reaction prepares alkane be simply easy to large-scale promotion application, object product is easy to be separated, the fatty acid carbon chain of composition tri-glyceride does not rupture, still former carbon chain lengths is kept, 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 produced can regenerate, in life cycle, the greenhouse gases of discharge are lower, today of increasingly stringent is required in current energy-saving and emission-reduction call and environmental regulation, the method that non-edible animals and plants oil hydrogenation deoxidation prepares alkane is significant.
Preparation method of the present invention, prepare green to the oily hydrogenation deoxidation of non-edible animals and plants, renewable alkane yield is higher, compared with other prepare biofuel technology, feature of the present invention is, the raw material of use is inedible oil, and cost is low; Preparation technology's flow process is simple, without difficult by product; Fatty acid carbon chain not cracking, keeps former carbon chain lengths; Catalyzer adopts ordinary method preparation, adds 3 ~ 5wt% cerium oxide and silicon oxide, makes the nickel molybdenum catalyst hydrogenation deoxidation activity of 3 ~ 5%wt cerium oxide and silicon oxide, selectivity and hydrothermal energy better; Product stable, calorific value are high and green, renewable, are conducive to large-scale promotion application.
Embodiment
Embodiment 1
Jatropha curcas oil hydrogenation deoxidation prepares alkane
Nickel molybdenum catalyst 10mL being contained 3 ~ 5wt% cerium oxide and silicon oxide loads constant temperature zone in reactor, reactor upper-lower section is all filled in absorbent cotton, quartz sand, nitrogen replacement 3 times, take Jatropha curcas oil as raw material, under octane solvent exists, 380 DEG C, 4.0MPa, 5.0h
-1, hydrogen/Jatropha curcas oil 1000, reaction 10h, by GC-MS, qualitative and quantitative analysis is carried out to product, liquid hydrocarbon yield 82.23%, wherein C15 ~ C18 alkane yield 80.21%.
Embodiment 2
Non-food grade plam oil hydrogenation deoxidation prepares alkane
Nickel molybdenum catalyst 10mL being contained 3 ~ 5wt% cerium oxide and silicon oxide loads constant temperature zone in reactor, reactor upper-lower section is all filled in absorbent cotton, quartz sand, nitrogen replacement 3 times, with non-food grade plam oil for raw material, under octane solvent exists, 360 DEG C, 3.5MPa, 5.0h
-1, hydrogen/non-food grade plam oil 1000, reaction 10h, by GC-MS, qualitative and quantitative analysis is carried out to product, liquid hydrocarbon yield 82.56%, wherein C15 ~ C18 alkane yield 79.56%.
Embodiment 3
Sewer oil hydrogenation deoxidation prepares alkane
Nickel molybdenum catalyst 10mL being contained 3 ~ 5wt% cerium oxide and silicon oxide loads constant temperature zone in reactor, and reactor upper-lower section is all filled in absorbent cotton, quartz sand, nitrogen replacement 3 times, take sewer oil as raw material, under octane solvent exists, and 380 DEG C, 4.0MPa, 4.5h
-1, hydrogen/sewer oil 900, reaction 10h, by GC-MS, qualitative and quantitative analysis is carried out to product, liquid hydrocarbon yield 82.17%, wherein C15 ~ C18 alkane yield 78.69%.
Embodiment 4
Viscotrol C hydrogenation deoxidation prepares alkane
Nickel molybdenum catalyst 10mL being contained 3 ~ 5wt% cerium oxide and silicon oxide loads constant temperature zone in reactor, and reactor upper-lower section is all filled in absorbent cotton, quartz sand, nitrogen replacement 3 times, take Viscotrol C as raw material, under solvent benzol exists, and 380 DEG C, 4.0MPa, 5.0h
-1, hydrogen/Viscotrol C 1000, reaction 10h, by GC-MS, qualitative and quantitative analysis is carried out to product, liquid hydrocarbon yield 82.06%, wherein C15 ~ C18 alkane yield 75.17%.
Claims (7)
1. a non-edible animals and plants oil hydrogenation deoxidation prepares the method for alkane, it is characterized in that: the nickel molybdenum catalyst containing 3 ~ 5wt% cerium oxide and silicon oxide at reactor constant temperature zone loading 5 ~ 10mL, reactor upper-lower section is all filled in inert material, nitrogen replacement 3 times, with non-edible animals and plants oil for raw material, exist at varsol, temperature of reaction is 200 ~ 500 DEG C, pressure is 1.0 ~ 6.0MPa, and air speed is 0.5 ~ 10h
-1hydrogen to oil volume ratio be occur under 200 ~ 2000 conditions hydrogenation deoxidation reaction preparation main component be the alkane of C15 ~ C18;
Described non-edible animals and plants oil forms primarily of the glycerin fatty acid ester of C9 ~ C24;
The described nickel molybdenum catalyst containing 3 ~ 5wt% cerium oxide and silicon oxide for add 3 ~ 5wt% cerium oxide and silicon oxide in conventional nickel molybdenum hydrogenation deoxidation catalyst, and in 3 ~ 5wt% cerium oxide and silicon oxide, cerium oxide, silicon oxide weight ratio are 1:1.
2. non-edible animals and plants oil hydrogenation deoxidation according to claim 1 prepares 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 and algae oil.
3. non-edible animals and plants oil hydrogenation deoxidation according to claim 1 prepares the method for alkane, it is characterized in that: it is normal hexane, benzene,toluene,xylene, normal heptane, octane, n-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 prepares the method for alkane, it is characterized in that: temperature of reaction is 320 ~ 380 DEG C.
5. non-edible animals and plants oil hydrogenation deoxidation according to claim 1 prepares 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 prepares 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 prepares the method for alkane, it is characterized in that: reaction hydrogen to oil volume ratio is 800 ~ 1000.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN107573968B (en) * | 2017-09-18 | 2020-01-03 | 肖连朝 | Method for preparing high-purity bio-alkane by using waste oil |
| CN114672337B (en) * | 2022-03-18 | 2023-05-12 | 大连理工大学 | Method for catalyzing biological grease hydrodeoxygenation by using bimetallic nitride |
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| US8053615B2 (en) * | 2007-03-08 | 2011-11-08 | Virent Energy Systems, Inc. | Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons |
| CN102399567A (en) * | 2010-09-08 | 2012-04-04 | Ifp新能源公司 | Process for the continuous hydrogenation of triglyceride containing raw materials using a nickel and molybdenum-based catalyst |
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| CN101321847A (en) * | 2005-11-30 | 2008-12-10 | 新日本石油株式会社 | Hydrorefining process and hydrorefined oil |
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