CN103614155A - Preparation method for hydrocarbon fuels from algae oil - Google Patents
Preparation method for hydrocarbon fuels from algae oil Download PDFInfo
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- CN103614155A CN103614155A CN201310413871.1A CN201310413871A CN103614155A CN 103614155 A CN103614155 A CN 103614155A CN 201310413871 A CN201310413871 A CN 201310413871A CN 103614155 A CN103614155 A CN 103614155A
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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 invention discloses a preparation method for hydrocarbon fuels from algae oil. The method comprises the following steps: in a nitrogen atmosphere, grease compounds are transported to a tubular reactor loaded with supported molybdenum catalysts for catalytic decarboxylation reaction through a pump, and hydrocarbon fuels are obtained. In the decarboxylation and deoxidation reaction, the reaction atmosphere is nitrogen, the reaction pressure is normal pressure, the reaction temperature is 300-360 DEG C, the reaction time is 1.5-3.0h, and the material charging rate is 0.03-0.30g/(cm<2>*min). The supported molybdenum catalysts take molybdenum as active metal, and take active carbon as a catalyst carrier. Compared with the prior art, the supported molybdenum catalysts take active carbon as a catalyst carrier, the catalytic activity is high, the reaction conditions are mild ( no hydrogen is needed and the reaction can be carried out under normal pressure), and the conversion rate and deoxidation rate of the raw materials and the yield of liquid hydrocarbon are high.
Description
Technical field
The present invention relates to biomass energy preparing technical field, especially a kind of preparation method of algae oil production hydrocarbon fuel.
Background technology
Along with industry and economic fast development, energy shortage and environmental problem are day by day serious, and seeking a kind of clean, new forms of energy reproducible, alternative fossil energy is the problem that the mankind need solution badly.In the various new forms of energy such as sun power, wind energy, underground heat, biomass energy, biomass energy is unique a kind of new forms of energy that can produce liquid fuel.
The production ways of biomass energy mainly contains three: animals and plants, microbial oil are by ester-exchange technology production biofuel, and starch, Mierocrystalline cellulose are by producing fuel ethyl alcohol by ferment, and wood chip, stalk etc. are by heat/catalytic pyrolysis production bio oil.The main component of biofuel is fatty acid methyl ester, also contains a large amount of ester classes, organic acid and aldehyde compound in biomass cracked oil by using, and therefore, their oxygen level is high.High oxygen level can cause the poor storage stability of oil product, viscosity is high, calorific value is low, ignition characteristic is poor, thereby has limited its application.
At present, the method for grease deoxidation mainly contains two kinds of hydrogenation and decarboxylations.Oil hydrogenation is mainly under catalyst action, and grease and hydrogen react, and the oxygen in grease removes with the form of water.Grease decarboxylic reaction is mainly under the effect of catalyzer, and the oxygen in grease is with CO
2form remove.The hydrogenation deoxidation of grease needs the atmosphere of hydrogen, and reaction process need to consume hydrogen, and needs higher hydrogen pressure (3Mpa-10Mpa) and temperature (200 ℃-600 ℃), and the noble metal catalyst such as Pd/Pt.The decarboxylation of grease does not consume hydrogen, and the environment of an anaerobic only need be provided, and reaction pressure is relevant with the activity of used catalyst, generally at 0.5Mpa, far below the pressure of hydrogenation deoxidation.The present invention adopts the method for catalytic decarboxylation to remove the oxygen in grease, a kind of high reactivity, non-noble metal decarboxylation catalyst are provided, grease decarboxylation procedure is carried out under normal pressure, both catalyzer and equipment investment cost had been reduced, the security that has improved operation, has again high grease deoxidation rate and liquid hydrocarbon productivity.In addition, it is raw material that the present invention not only can be take common animal-plant oil and their methyl esters compound, and also can take algae oil and methyl esters compound thereof is raw material, changes oxygen level and the correlated performance of grease, makes it meet the requirement of fuel applications.
Summary of the invention
The present invention will solve the shortcoming of above-mentioned prior art, a kind of preparation method of algae oil production hydrocarbon fuel is provided, a kind of preparation method of low liquid hydrocarbon fuel, the problem solving is to prepare a kind of high reactivity, non-precious metal catalyst, this catalyzer can make grease in normal pressure nitrogen atmosphere, there is decarboxylic reaction at lower temperature, the method has higher grease deoxidation rate and liquid hydrocarbon productivity, and to take the various animals and plants of algae wet goods, microbial oil be raw material, the strong adaptability of raw material.
The present invention solves the technical scheme that its technical problem adopts: the preparation method of this algae oil production hydrocarbon fuel, the method comprises the following steps: in nitrogen atmosphere, oil compounds is carried out to catalytic decarboxylation reaction by pump delivery to being equipped with in the tubular reactor of loading type molybdenum catalyst, obtain hydrocarbon fuel; The reaction atmosphere of described decarboxylation deoxidation reaction is nitrogen, and reaction pressure is normal pressure, and temperature of reaction is 300-360 ℃, and the reaction times is 1.5-3.0h, and feeding rate is 0.03-0.30g/(cm
2﹒ min); Wherein said loading type molybdenum catalyst be take molybdenum as active metal, take gac as support of the catalyst.
Described oil compounds is the mixed methyl aliphatic ester of algae oil and the preparation of algae oil.
Described loading type molybdenum catalyst is prepared as follows: the absorbent charcoal carrier of handling well is impregnated in the aqueous solution of molybdenum catalyst presoma, and dry rear calcining, after calcining, logical hydrogen activates, and obtains molybdenum C catalyst; Wherein molybdenum catalyst precursor is Ammonium Molybdate Tetrahydrate, and calcining temperature is 400 ℃, and calcination time is 2 hours; Activation temperature is 400 ℃, and soak time is 3 hours, and the load factor of Mo on gac is 15-50%.
The effect that the present invention is useful is: compared with prior art, due to the present invention adopt to take the catalytic activity of the loading type molybdenum catalyst that gac is carrier high, reaction conditions is gentle, the ester conversion rate obtaining, deoxidation rate and liquid hydrocarbon productivity are higher.Experimental result shows, preparation method provided by the invention is at normal pressure, nitrogen atmosphere, and the load factor of Mo on gac is 15%-50%, and temperature of reaction is 300-360 ℃, and feeding rate is 0.03-0.30g/(min ﹒ cm
2), under the condition of residence time 1.5h – 3.0h, the transformation efficiency of stock oil is 34.8%-99.3%, and deoxidation rate is 34.3%-99.1%, and liquid hydrocarbon productivity is 46.1%-78.6% left and right.
Accompanying drawing explanation
Fig. 1 is reaction unit figure;
Fig. 2 is the GC-MS figure of algae oil methyl esters (reaction raw materials);
Fig. 3 is the GC-MS figure of the liquid product prepared of the embodiment of the present invention;
Embodiment
Below the technical scheme in embodiment of the present invention is clearly and completely described, described embodiment is only the present invention's part example, rather than whole embodiment.Embodiment based in the present invention, the every other embodiment that those of ordinary skills obtain under the prerequisite of not making creative work, belongs to the scope of protection of the invention.
The invention discloses a kind of preparation method of algae oil production hydrocarbon fuel, the method comprises the following steps: in nitrogen atmosphere, oil compounds is carried out to catalytic decarboxylation reaction by pump delivery to being equipped with in the tubular reactor of loading type molybdenum catalyst, obtain hydrocarbon fuel; The reaction atmosphere of described decarboxylation deoxidation reaction is nitrogen, and reaction pressure is normal pressure, and temperature of reaction is 300-360 ℃, and the reaction times is 1.5-3.0h, and feeding rate is 0.03-0.30g/(cm
2﹒ min); Wherein said loading type molybdenum catalyst be take molybdenum as active metal, take gac as support of the catalyst.
In the present invention, described grease is from the grease extracting in micro-algae.
This loading type molybdenum catalyst be take metal molybdenum as active ingredient, and meanwhile, support of the catalyst is selected the gac that specific surface area is large, between metal molybdenum and absorbent charcoal carrier, acts synergistically, and has greatly improved the activity of catalysis.Specifically principle is, complexing formation reaction intermediate occurs between the ester group in grease and transition metal molybdenum, and at a certain temperature, ester bond and parent molecule depart from, and discharges with the form of carbonic acid gas; When ester bond departs from parent molecule, parent molecule generates hydrocarbon, and molybdate compound is reduced to metal molybdenum.
Compared with prior art, because adopting, the present invention usings the loading type molybdenum catalyst of gac as support of the catalyst, catalyst activity is higher, under the synergy of molybdenum and carrier, reduced the reaction conditions of grease decarboxylation deoxidation reaction, reaction nitrogen buffer gas carries out under normal pressure, greatly reduce production cost, increased the security of producing.
In order to further illustrate technical scheme of the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
1) preparation of catalyzer
The loading type molybdenum catalyst that the present invention adopts is preferably prepared according to pickling process, more preferably be prepared as follows: dry absorbent charcoal carrier is impregnated in the aqueous solution of molybdenum catalyst precursor, calcining after dry, after calcining, logical hydrogen reducing, obtains loading type molybdenum catalyst.Described molybdenum catalyst precursor is preferably Ammonium Molybdate Tetrahydrate; Described drying temperature is 70 ℃, and be 5h time of drying; Described calcining temperature is 400 ℃, and calcination time is 2h; Described reduction pressure is normal pressure, and hydrogen flowing quantity is 100ml/min, and reduction temperature is 400 ℃, and the recovery time is 3h.The preparation method of above-mentioned loading type molybdenum catalyst is easy and simple to handle, simple to equipment requirements, and catalyzer preparation is repeatable high, is easy to suitability for industrialized production.
Embodiment 1
30g Ammonium Molybdate Tetrahydrate is joined in 100mL distilled water, and stirring and dissolving, obtains ammonium molybdate aqueous solution.
The dried absorbent charcoal carrier of 20g is joined in described ammonium molybdate solution, at 25 ℃, stir dipping 2h, standing over night, suction filtration is removed supernatant liquid, and gained filter cake is dried to constant weight at 70 ℃, and it is packed in tubular reactor by the method shown in Fig. 1.Logical nitrogen is calcined 2h at 400 ℃, more logical hydrogen reduces 3h at 400 ℃, obtains load factor and be 40% Mo-C catalyzer.
20g Ammonium Molybdate Tetrahydrate is joined in 100mL distilled water, and stirring and dissolving, obtains ammonium molybdate aqueous solution.
The dried absorbent charcoal carrier of 20g is joined in described ammonium molybdate solution, and other operates with embodiment 1, obtains load factor and be 27% Mo-C catalyzer.
Embodiment 3
15g Ammonium Molybdate Tetrahydrate is joined in 100mL distilled water, and stirring and dissolving, obtains ammonium molybdate aqueous solution.
The dried absorbent charcoal carrier of 20g is joined in described ammonium molybdate solution, and other operates with embodiment 1, obtains load factor and be 18% Mo-C catalyzer.
30g Ammonium Molybdate Tetrahydrate is joined in 100mL distilled water, and stirring and dissolving, obtains ammonium molybdate aqueous solution.
The dried silica supports of 20g is joined in described ammonium molybdate solution, and other operates with embodiment 1, obtains load factor and be 34.8% Mo-SiO
2catalyzer.
Embodiment 5
20g Ammonium Molybdate Tetrahydrate is joined in 100mL distilled water, and stirring and dissolving, obtains ammonium molybdate aqueous solution.
By the dried Al of 20g
2o
3carrier joins in described ammonium molybdate solution, and other operates with embodiment 1, obtains load factor and be 23.7% Mo-Al
2o
3catalyzer.
By 50g Mg(NO
3)
2﹒ 6H
2o joins in 100mL distilled water, and stirring and dissolving, obtains magnesium nitrate aqueous solution.
By the dried Al of 20g
2o
3carrier joins in described magnesium nitrate solution, stirs dipping 2h at 25 ℃, standing over night, and suction filtration is removed supernatant liquid, and gained filter cake is dried to constant weight at 70 ℃; Put into retort furnace, at 450 ℃, calcine 12h.Obtain load factor and be 20.0% MgO-Al
2o
3catalyzer.
2) decarboxylic reaction is prepared liquid hydrocarbon fuels
Embodiment 1
Press method shown in Fig. 1, first long to 60cm, external diameter 20mm, in the tubular reactor of internal diameter 16mm, load 10g quartz sand, then on quartz sand, load 20g load factor and be 40% Mo-C catalyzer, be highly about 12cm, finally at catalyzer top remaining space, load quartz sand; Open heating and temperature-control device, the quartz sand in tubular reactor and catalyzer are heated and maintain 340 ℃ (temperature of reaction); By fuel oil preheating to 70 ℃, by pump with 0.08g/(cm
2﹒ min) feeding rate is transported to tubular reactor from top; The material flowing out from tubular reactor lower end is through the cooling liquid product that obtains of prolong (condensing temperature is 25 ℃); The liquid product of collecting, weighs, with the gas chromatographic analysis content of unreacted fatty acid methyl ester wherein, and composition and the content of the liquid hydrocarbon generating, according to formula (1), calculate the transformation efficiency of raw material, according to formula (2), calculate deoxidation rate, according to formula (3), calculate liquid hydrocarbon productivity.
Under operational condition described in embodiment 1, transformation efficiency is 91.2%, and deoxidation rate is 91.1%, and liquid hydrocarbon productivity is about 79.6%.
Embodiment 1 is prepared to product liquid and carry out GC-MS analysis, as shown in Figure 3, as can be seen from the figure, this product is mainly C15 to result, the hydrocarbon compound of C17, and raw fatty acid methyl esters transforms substantially completely.
Other embodiment
The operating parameters of other embodiment and result are different from embodiment 1, but working method and process are with embodiment 1.Table 1 has been listed the result under different operating parameter.
The operating parameters of each embodiment of table 1 and result
Comparative example
Catalyzer used in comparative example is different from embodiment, respectively with 34.8% Mo-SiO
2, 23.7% Mo-Al
2o
3with 20.0% MgO-Al
2o
3for catalyzer, the operating process of reaction and working method are identical with embodiment 1.Table 2 has compared the liquid hydrocarbon condition of production in each catalyzer situation.
The comparison of table 2 different catalysts effect
In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of requirement of the present invention.
Claims (3)
1. the preparation method of algae oil production hydrocarbon fuel, it is characterized in that: the method comprises the following steps: in nitrogen atmosphere, oil compounds is carried out to catalytic decarboxylation reaction by pump delivery to being equipped with in the tubular reactor of loading type molybdenum catalyst, obtain hydrocarbon fuel; The reaction atmosphere of described decarboxylation deoxidation reaction is nitrogen, and reaction pressure is normal pressure, and temperature of reaction is 300-360 ℃, and the reaction times is 1.5-3.0h, and feeding rate is 0.03-0.30g/(cm
2﹒ min); Wherein said loading type molybdenum catalyst be take molybdenum as active metal, take gac as support of the catalyst.
2. the preparation method of algae oil production hydrocarbon fuel according to claim 1, is characterized in that: described oil compounds is the mixed methyl aliphatic ester of algae oil and the preparation of algae oil.
3. the preparation method of algae according to claim 1 oil production hydrocarbon fuel, it is characterized in that, described loading type molybdenum catalyst is prepared as follows: the absorbent charcoal carrier of handling well is impregnated in the aqueous solution of molybdenum catalyst presoma, calcining after dry, after calcining, logical hydrogen activation, obtains molybdenum C catalyst; Wherein molybdenum catalyst precursor is Ammonium Molybdate Tetrahydrate, and calcining temperature is 400 ℃, and calcination time is 2 hours; Activation temperature is 400 ℃, and soak time is 3 hours, and the load factor of Mo on gac is 15-50%.
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| CN105567285A (en) * | 2016-03-04 | 2016-05-11 | 浙江大学 | Method for simultaneously preparing long-chain alkane and arene by taking gutter oil as raw material |
| CN105567284A (en) * | 2016-03-04 | 2016-05-11 | 浙江大学 | Method for simultaneously preparing long-chain alkane and arene by taking microalgae oil as raw material |
| CN105670679A (en) * | 2016-03-04 | 2016-06-15 | 浙江大学 | Method for simultaneously preparing long-chain alkanes and aromatics from oleic acid |
| CN108586181A (en) * | 2018-05-21 | 2018-09-28 | 华东师范大学 | Grease decarbonylation is the method for long chain alkane under a kind of hydrogen-free condition |
| CN109052320A (en) * | 2018-08-24 | 2018-12-21 | 上海理工大学 | A kind of method that microalgae alkali extraction heat oil prepares hydrogen |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108586181A (en) * | 2018-05-21 | 2018-09-28 | 华东师范大学 | Grease decarbonylation is the method for long chain alkane under a kind of hydrogen-free condition |
| CN108586181B (en) * | 2018-05-21 | 2021-09-21 | 华东师范大学 | Method for decarbonylating grease into long-chain alkane under hydrogen-free condition |
| CN109052320A (en) * | 2018-08-24 | 2018-12-21 | 上海理工大学 | A kind of method that microalgae alkali extraction heat oil prepares hydrogen |
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