CN113145159B - Biodiesel catalyst and preparation method thereof - Google Patents
Biodiesel catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- 239000003225 biodiesel Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 75
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 54
- 239000004917 carbon fiber Substances 0.000 claims abstract description 54
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000002243 precursor Substances 0.000 claims abstract description 36
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 32
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000011261 inert gas Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000000227 grinding Methods 0.000 claims abstract description 16
- 238000002791 soaking Methods 0.000 claims abstract description 15
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000001639 calcium acetate Substances 0.000 claims abstract description 14
- 235000011092 calcium acetate Nutrition 0.000 claims abstract description 14
- 229960005147 calcium acetate Drugs 0.000 claims abstract description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 62
- 238000010438 heat treatment Methods 0.000 claims description 54
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 12
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 12
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 12
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
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- 235000014655 lactic acid Nutrition 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000292 calcium oxide Substances 0.000 abstract description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001569 carbon dioxide Substances 0.000 abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000011068 loading method Methods 0.000 description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
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- 235000012424 soybean oil Nutrition 0.000 description 4
- 239000003549 soybean oil Substances 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000010775 animal oil Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
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- 238000004821 distillation Methods 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
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- 239000000047 product Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- -1 methanol Chemical compound 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 230000008439 repair process Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 238000002336 sorption--desorption measurement Methods 0.000 description 1
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- 239000008117 stearic acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/30—
-
- B01J35/617—
-
- B01J35/643—
-
- B01J35/647—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
A preparation method of a biodiesel catalyst comprises the following steps: soaking the nitrogen-doped porous carbon fiber into titanium dioxide hydrosol to prepare a composite carrier; fully grinding and mixing calcium acetate and calcium carbonate, and then preserving heat for 3-10 hours at 160-260 ℃ in an inert gas atmosphere to obtain a precursor; and (3) fully grinding and mixing the composite carrier and the precursor, placing the mixture in the center of a tubular furnace, introducing inert gas, and roasting to obtain the biodiesel catalyst. The method disclosed by the invention is simple to operate, the steps are relatively few, the prepared catalyst shows good catalytic activity, the inert gas is used for protection in the preparation process, the influence of moisture and carbon dioxide in the air on calcium oxide is avoided in the preparation process of the catalyst, the catalytic activity of the catalyst is improved, the yield is relatively improved and reaches 96.0% -98.5%, the yield of the biodiesel can be up to more than 96%, the catalyst can be repeatedly used for 10 to 12 times, the cost is saved, no corresponding by-product is discharged, and the method is economic and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of biodiesel catalysts, and particularly relates to a biodiesel catalyst and a preparation method thereof.
Background
The biodiesel is a low-price, safe and convenient biomass clean energy source which is obtained by taking renewable resources such as animal and vegetable oil as raw materials and carrying out esterification or ester exchange reaction with short-chain alcohol such as methanol, and the chemical components of the biodiesel are mainly methyl ester or ethyl ester of long-chain saturated and unsaturated fatty acids such as linolenic acid, palmitic acid, stearic acid, oleic acid, linoleic acid and the like, and the properties of the biodiesel are similar to those of diesel oil. Compared with petroleum diesel, the biodiesel not only has very similar combustion performance, but also has incomparable environmental protection and reproducibility of the petroleum diesel, and has very wide application prospect.
At present, the homogeneous catalysis transesterification method is mainly adopted for the industrial production of the biodiesel at home and abroad. The ester exchange method is to carry out ester exchange reaction between animal and vegetable oil and lower alcohol such as methanol or ethanol to generate corresponding fatty acid methyl ester or ethyl ester. However, the catalyst has the problem of strong corrosion to equipment, products after the reaction are difficult to separate, so that the post-treatment process is complicated, and in addition, the output of the treated waste acid and waste water is large, so that the treatment cost is expensive. In order to solve these problems, heterogeneous catalysts have been developed, which have a simpler reaction process, are easy to separate products after reaction, and can be recycled many times, compared to common homogeneous catalysts.
However, the existing solid heterogeneous catalyst has low loading capacity, is easily poisoned by water and carbon dioxide in the air, and influences the catalytic activity of the catalyst, and in addition, the firmness of the combination between the carriers is relatively poor, so that the repeatability is low, and the service life of the catalyst is influenced.
Disclosure of Invention
The technical problems to be solved by the invention are that the existing catalyst is low in loading capacity, easy to be poisoned by water and carbon dioxide in the air, and low in repeatability, and the catalytic activity of the catalyst is influenced.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of a biodiesel catalyst comprises the following steps:
s1, preparation of composite carrier
S1.1 preparation of Nitrogen-doped porous carbon fibers
Placing microcrystalline cellulose in the center of a tube furnace, introducing nitrogen, heating to 300 ℃, preserving heat for 1-5 h, then heating to 500 ℃, and preserving heat for 1-10 h to obtain nitrogen-doped porous carbon fiber; wherein the dosage ratio of the microcrystalline cellulose to the nitrogen is 1g:80-120mL/min;
s1.2 preparation of titanium dioxide hydrosol
Dropwise adding acetic acid and lactic acid with the volume ratio of 1:1 into the ethylenediamine solution, wherein the volume ratio of the lactic acid to the ethylenediamine is 1; slowly dripping tetrabutyl titanate into the solution A, uniformly stirring, and then slowly dripping deionized water, wherein the volume ratio of the tetrabutyl titanate to the solution A to the deionized water is (1-3): 1: (60-100), continuously stirring uniformly after the dripping is finished to obtain a titanium dioxide aqueous solution;
s1.3, soaking the nitrogen-doped porous carbon fiber into titanium dioxide hydrosol, adjusting the pH value to 7.0-8.0, soaking for 6-10h, centrifuging, filtering, drying, and roasting at 500 ℃ for 5-8h in an inert gas atmosphere to obtain a composite carrier;
s2, preparation of precursor
Fully grinding and mixing calcium acetate and calcium carbonate, and then preserving heat for 3-10 hours at 160-260 ℃ in an inert gas atmosphere to obtain a precursor;
s3, preparation of biodiesel catalyst
And (3) fully grinding and mixing the composite carrier obtained in the step (1) and the precursor obtained in the step (2), placing the mixture in the center of a tube furnace, introducing inert gas, gradually heating the tube furnace to 260 ℃, preserving heat for 3-6h, heating to 500-600 ℃, roasting, and preserving heat for 6-12h to obtain the biodiesel catalyst.
S1.1 the heating rate in the preparation step of the nitrogen-doped porous carbon fiber is 5-10 ℃/min.
S1.2 the reaction temperature for preparing the titanium dioxide hydrosol is 20-30 ℃.
S1.3 the mass ratio of the nitrogen-doped porous carbon fiber to the titanium dioxide hydrosol is 1:5-10.
The mass ratio of calcium acetate to calcium carbonate in S2 is 1:1.
S3, the mass ratio of the precursor to the composite carrier is 1:20 to 30.
The heating rate in the roasting process in S1, S2 and S3 is 3-8 ℃/min.
The inert gas in S1.3, S2 and S3 is any one of nitrogen, argon, helium and neon.
The biodiesel catalyst prepared by the preparation method.
Compared with the prior art, the preparation method of the biodiesel catalyst provided by the invention has the following beneficial effects:
1. according to the invention, firstly, the microcrystalline cellulose is subjected to nitrogen doping carbonization to prepare the nitrogen-doped porous carbon fiber, the strength and the carrier activity of the porous carbon fiber are improved by doping nitrogen elements on the porous carbon fiber, so that the porous carbon fiber can be combined with titanium dioxide to form a composite carrier, a relatively stable combined phase is formed, and then the composite carrier is roasted with calcium oxide to form a stable structure, so that the specific surface area and the pore size of the catalyst are increased, and the loading capacity is improved. Meanwhile, in the process of high-temperature roasting of the composite carrier of the nitrogen-doped porous carbon fiber and the precursor, a certain crystalline phase structure is obtained through the synergistic effect of element molecules, and the crystalline phase structure not only can improve the anti-wear and anti-attrition effects of the catalyst, but also can enhance the anti-crushing strength of the catalyst, so that the service life of the catalyst is prolonged.
2. The method disclosed by the invention is simple in operation process and relatively few in steps, the prepared catalyst shows good catalytic activity, the inert gas nitrogen is used for protection in the preparation process, so that the influence of moisture and carbon dioxide in the air on calcium oxide is avoided in the preparation process of the catalyst, the catalytic activity of the catalyst is improved, the yield is relatively improved and reaches 96.0% -98.5%, when the method is applied to the preparation process of biodiesel, the yield of the biodiesel can reach more than 96%, the biodiesel can be recycled for 10-12 times, the cost is saved, no corresponding by-product is discharged, and the method is economical and environment-friendly.
Drawings
FIG. 1 is a plot of the nitrogen adsorption-desorption isotherm of a biodiesel catalyst at-196 ℃.
FIG. 2 is a pore size distribution plot for a biodiesel catalyst.
FIG. 3 is an SEM image of a biodiesel catalyst.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and specific examples, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort belong to the protection scope of the present invention.
A preparation method of a biodiesel catalyst comprises the following steps:
s1, preparation of composite carrier
S1.1 preparation of Nitrogen-doped porous carbon fiber
Placing microcrystalline cellulose in the center of a tube furnace, introducing nitrogen, heating to 300 ℃, preserving heat for 1-5 h, then heating to 500 ℃, and preserving heat for 1-10 h to obtain nitrogen-doped porous carbon fiber; wherein the dosage ratio of the microcrystalline cellulose to the nitrogen is 1g:80-120mL/min;
s1.2 preparation of titanium dioxide hydrosol
Dropwise adding acetic acid and lactic acid with the volume ratio of 1:1 into the ethylenediamine solution, wherein the volume ratio of the lactic acid to the ethylenediamine is 1; slowly dripping tetrabutyl titanate into the solution A, uniformly stirring, and then slowly dripping deionized water, wherein the volume ratio of the tetrabutyl titanate to the solution A to the deionized water is (1-3): 1: (60-100), continuously stirring uniformly after the dripping is finished to obtain a titanium dioxide aqueous solution;
s1.3, soaking the nitrogen-doped porous carbon fiber into titanium dioxide hydrosol, adjusting the pH value to 7.0-8.0, soaking for 6-10h, centrifuging, filtering, drying, and roasting at 500 ℃ for 5-8h in an inert gas atmosphere to obtain a composite carrier;
s2, preparation of precursor
Fully grinding and mixing calcium acetate and calcium carbonate, and then preserving heat for 3-10 hours at 160-260 ℃ in an inert gas atmosphere to obtain a precursor;
s3, preparation of biodiesel catalyst
And (3) fully grinding and mixing the composite carrier obtained in the step (1) and the precursor obtained in the step (2), placing the mixture in the center of a tube furnace, introducing inert gas, gradually heating the tube furnace to 260 ℃, preserving heat for 3-6h, heating to 500-600 ℃, roasting, and preserving heat for 6-12h to obtain the biodiesel catalyst.
S1.1 the heating rate in the preparation step of the nitrogen-doped porous carbon fiber is 5-10 ℃/min.
S1.2 the reaction temperature for preparing the titanium dioxide hydrosol is 20-30 ℃.
S1.3 the mass ratio of the nitrogen-doped porous carbon fiber to the titanium dioxide hydrosol is 1:5-10.
The mass ratio of calcium acetate to calcium carbonate in S2 is 1:1.
S3, the mass ratio of the precursor to the composite carrier is 1:20 to 30.
The heating rates in the roasting processes of S1, S2 and S3 are all 3-8 ℃/min.
The inert gas in S1.3, S2 and S3 is any one of nitrogen, argon, helium and neon.
The biodiesel catalyst prepared by the preparation method.
Compared with the prior art, the preparation method of the biodiesel catalyst provided by the invention has the following beneficial effects:
1. according to the invention, firstly, microcrystalline cellulose is subjected to nitrogen doping carbonization to prepare nitrogen-doped porous carbon fiber, and nitrogen element is doped on the porous carbon fiber to improve the strength and the carrier activity of the porous carbon fiber, so that the porous carbon fiber can be combined with titanium dioxide to form a composite carrier, and a relatively stable combined phase is formed; and S3, after fully grinding and mixing the composite carrier and the precursor, placing the tube furnace in the tube furnace, introducing inert gas, gradually heating the tube furnace to 260 ℃, preserving heat for 3-6h, heating to 500-600 ℃ for roasting, decomposing calcium acetate and calcium carbonate into calcium oxide, and roasting the composite carrier and the calcium oxide to form a stable structure, so that the specific surface area and the pore size of the catalyst are increased, and the loading capacity is improved. Meanwhile, in the process of roasting the composite carrier of the nitrogen-doped porous carbon fiber and the precursor at high temperature, a certain crystalline phase structure is obtained through the synergistic effect of element molecules, and the crystalline phase structure not only can improve the wear-resistant and wear-reducing effects of the catalyst, but also can enhance the crushing strength of the catalyst so as to prolong the service life of the catalyst.
2. The method has simple operation process and relatively few steps, the prepared catalyst shows good catalytic activity, the inert gas nitrogen is used for protection in the preparation process, the influence of moisture and carbon dioxide in the air on calcium oxide is avoided in the preparation process of the catalyst, the catalytic activity of the catalyst is improved, the yield is relatively improved to 96.0-98.5%, when the method is applied to the preparation process of the biodiesel, the yield of the biodiesel can reach more than 96%, the biodiesel can be recycled for 10-12 times, the cost is saved, no corresponding by-product is discharged, and the method is economic and environment-friendly.
Example 1:
a preparation method of a biodiesel catalyst comprises the following steps:
s1, preparation of composite carrier
S1.1 preparation of nitrogen-doped porous carbon fiber
Placing 1g of microcrystalline cellulose at the central hot area of a tubular furnace, introducing nitrogen into the tubular furnace, keeping the temperature for 1h after heating from room temperature to 300 ℃ at the heating rate of 5 ℃/min, continuing heating to 500 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 1h, and obtaining the nitrogen-doped porous carbon fiber after the tubular furnace is naturally cooled to room temperature;
s1.2 preparation of titanium dioxide hydrosol
Slowly dripping 0.5mL of acetic acid and 0.5mL of lactic acid into 0.5mL of ethylenediamine solution at room temperature (20-30 ℃), and continuously stirring for 10min after dripping is finished to obtain a solution A;
slowly dripping 1.5mL of tetrabutyl titanate into the solution A at the dripping speed of 1mL/min, continuously stirring for 60min after finishing dripping, slowly dripping 60mL of deionized water at the dripping speed of 6mL/min, and continuously stirring for 60min after finishing dripping to obtain titanium dioxide hydrosol;
s1.3, soaking 0.5g of nitrogen-doped porous carbon fiber into 2.5g of titanium dioxide hydrosol, adjusting the pH to 7.0 by using a sodium hydroxide solution with a solute mass fraction of 15%, soaking for 6h, centrifuging, filtering, drying, heating to 500 ℃ at a heating speed of 3 ℃/min, roasting for 5h at 500 ℃, introducing nitrogen at a speed of 80ml/min during roasting, and keeping the nitrogen atmosphere to obtain a composite carrier;
s2, preparation of precursor
Fully grinding and mixing calcium acetate and calcium carbonate according to a mass ratio of 1:1, and preserving heat of 1g of mixture for 10 hours at 160 ℃ in a nitrogen atmosphere to obtain a precursor;
s3, preparation of biodiesel catalyst
And (2) fully grinding and mixing 0.033g of the precursor and 0.66g of the composite carrier, placing the mixture at the central hot area of the tubular furnace, introducing nitrogen into the tubular furnace at the flow rate of 80mL/min, heating the temperature of the tubular furnace to 260 ℃ at the heating rate of 3 ℃/min, preserving heat for 3h, heating to 500 ℃ at the heating rate of 3 ℃/min, and preserving heat for 6h to obtain the biodiesel catalyst.
Example 2:
a preparation method of a biodiesel catalyst comprises the following steps:
s1, preparation of composite carrier
S1.1 preparation of nitrogen-doped porous carbon fiber
Placing 1g of microcrystalline cellulose at the central hot area of a tubular furnace, introducing nitrogen into the tubular furnace, wherein the flow rate of the nitrogen is 80mL/min, heating to 300 ℃ from room temperature at the heating rate of 10 ℃/min, keeping the temperature for 5h, then continuously heating to 500 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 10h, and obtaining nitrogen-doped porous carbon fiber after the tubular furnace is naturally cooled to room temperature;
s1.2, preparation of titanium dioxide hydrosol
Slowly dripping 0.5mL of acetic acid and 0.5mL of lactic acid into 0.25mL of ethylenediamine solution at room temperature (20-30 ℃), and continuously stirring for 10min after dripping is finished to obtain a solution A;
slowly dripping 3.75mL of tetrabutyl titanate into the solution A at the dripping speed of 1mL/min, continuously stirring for 60min after finishing dripping, slowly dripping 125mL of deionized water at the dripping speed of 5mL/min, and continuously stirring for 60min after finishing dripping to obtain titanium dioxide hydrosol;
s1.3, soaking 0.5g of nitrogen-doped porous carbon fiber into 5g of titanium dioxide hydrosol, adjusting the pH to 8.0 by using a sodium hydroxide solution with a solute mass fraction of 15%, after soaking for 10h, centrifuging, filtering, drying, heating to 500 ℃ at a heating speed of 8 ℃/min, roasting for 8h at 500 ℃, introducing nitrogen gas at a flow rate of 80ml/min during roasting, and maintaining the nitrogen gas atmosphere to obtain a composite carrier;
s2, preparation of precursor
Fully grinding and mixing calcium acetate and calcium carbonate according to a mass ratio of 1:1, and then preserving heat of 1g of mixture for 3 hours at 260 ℃ in a nitrogen atmosphere to obtain a precursor;
s3, preparation of biodiesel catalyst
And (2) fully grinding and mixing 0.033g of precursor and 0.99g of composite carrier, placing the mixture at the central hot area of a tubular furnace, introducing nitrogen into the tubular furnace at a flow rate of 80mL/min, heating the temperature of the tubular furnace to 260 ℃ at a heating rate of 8 ℃/min, preserving the heat for 6 hours, heating to 600 ℃ at a heating rate of 8 ℃/min, and preserving the heat for 12 hours to obtain the biodiesel catalyst.
Example 3:
a preparation method of a biodiesel catalyst comprises the following steps:
s1, preparation of composite carrier
S1.1 preparation of nitrogen-doped porous carbon fiber
Placing 1g of microcrystalline cellulose at the central hot area of a tubular furnace, introducing nitrogen into the tubular furnace, wherein the flow rate of the nitrogen is 120mL/min, heating to 300 ℃ from room temperature at the heating rate of 8 ℃/min, keeping the temperature for 3h, then continuously heating to 500 ℃ at the heating rate of 8 ℃/min, keeping the temperature for 5h, and obtaining nitrogen-doped porous carbon fiber after the tubular furnace is naturally cooled to room temperature;
s1.2, preparation of titanium dioxide hydrosol
Slowly dripping 0.5mL of acetic acid and 0.5mL of lactic acid into 0.3mL of ethylenediamine solution at room temperature (20-30 ℃), and continuously stirring for 10min after dripping is finished to obtain a solution A;
slowly dripping 2.6mL of tetrabutyl titanate into the solution A at the dripping speed of 1mL/min, continuously stirring for 60min after finishing dripping, slowly dripping 100mL of deionized water at the dripping speed of 5mL/min, and continuously stirring for 60min after finishing dripping to obtain titanium dioxide hydrosol;
s1.3, soaking 0.5g of nitrogen-doped porous carbon fiber into 4g of titanium dioxide hydrosol, adjusting the pH to 7.5 by using a sodium hydroxide solution with a solute mass fraction of 15%, after soaking for 8h, centrifuging, filtering, drying, heating to 500 ℃ at a heating rate of 5 ℃/min, roasting for 6h at 500 ℃, introducing nitrogen gas at a flow rate of 80ml/min during roasting, and keeping an argon atmosphere to obtain a composite carrier;
s2, preparation of precursor
Fully grinding and mixing calcium acetate and calcium carbonate according to a mass ratio of 1:1, and preserving heat of 1g of mixture for 5 hours at 200 ℃ in an argon atmosphere to obtain a precursor;
s3, preparation of biodiesel catalyst
And (2) fully grinding and mixing 0.033g of precursor and 0.83g of composite carrier, placing the mixture at the central hot area of a tubular furnace, introducing argon into the tubular furnace at a flow rate of 80mL/min, heating the temperature of the tubular furnace to 260 ℃ at a heating rate of 5 ℃/min, preserving the temperature for 5 hours, heating to 550 ℃ at a heating rate of 5 ℃/min, and preserving the temperature for 8 hours to obtain the biodiesel catalyst.
Examples 4 to 15
The specific steps of the preparation method of the biodiesel catalyst in the embodiments 4 to 15 are the same as those of the embodiment 1, except that the process parameters of S1.1, preparation of the nitrogen-doped porous carbon fiber and S1.2, and preparation of the titanium dioxide hydrosol are shown in table 1, and the process parameters of S1.3, S2, and preparation of the precursor, and the process parameters of S3 and preparation of the biodiesel catalyst are shown in table 2.
TABLE 1
TABLE 2
Comparative example 1:
a preparation method of a biodiesel catalyst, which is the same as the preparation method of example 3, except that:
s1.1 preparation of nitrogen-doped porous carbon fiber
Placing 1g of microcrystalline cellulose at the central hot area of a tubular furnace, introducing nitrogen into the tubular furnace at a gas flow rate of 80mL/min, heating from room temperature to 500 ℃ at a heating rate of 8 ℃/min, preserving heat for 5h, and naturally cooling the tubular furnace to room temperature to obtain the porous carbon fiber.
Comparative example 2:
a preparation method of a biodiesel catalyst, which is the same as the preparation method of example 3, except that:
s1.3, soaking 0.5g of nitrogen-doped porous carbon fiber into 4g of titanium dioxide hydrosol, adjusting the pH value to 7.5 by using a 15% sodium hydroxide solution, soaking for 8 hours, centrifuging, filtering, drying, heating to 500 ℃ at a heating rate of 5 ℃/min, and roasting at 500 ℃ for 6 hours to obtain the composite carrier.
Comparative example 3:
a method for preparing a biodiesel catalyst, which is the same as the method for preparing the biodiesel catalyst of example 3, except that,
s2, preparation of precursor
Fully grinding and mixing calcium acetate and calcium carbonate according to the mass ratio of 1:1 to obtain a precursor.
Physical Properties of biodiesel catalysts prepared in examples 1 to 3 and comparative examples 1 to 3The performance index is tested, wherein the crushing strength of the catalyst is tested by adopting the existing domestic enterprise standard method, the tester is a DL-II particle strength tester, and the measured crushing strength of the catalyst is the axial crushing strength which can be born by unit area and has the unit of N/cm 2 . The physical property indexes of the biodiesel catalysts prepared in examples 1 to 3 and comparative examples 1 to 3 are shown in Table 3.
TABLE 3
| Item | Specific surface area/m 2 ·g -1 | Pore diameter/mm | Axial pressure/N.cm -2 |
| Example 1 | 630.14 | 11.0 | 970 |
| Example 2 | 627.21 | 10.7 | 950 |
| Example 3 | 632.45 | 10.9 | 980 |
| Comparative example 1 | 518.26 | 6.2 | 530 |
| Comparative example 2 | 564.75 | 7.7 | 610 |
| Comparative example 3 | 571.83 | 8.6 | 570 |
As can be seen from the above Table 3, the biodiesel catalysts prepared in examples 1-3 all have large specific surface areas, and have high crushing strength by high-temperature calcination and multi-component synergistic effect, which is related to the fibrous crystals of the nitrogen-doped porous carbon fibers and the crystalline system after loading titanium dioxide and precursors. The titanium dioxide and the precursor are adsorbed on the surface of the porous carbon fiber doped with nitrogen at the same time, the surface of the porous carbon fiber is modified, the surface structure of fibrous crystals is further adjusted by controlling the mass fraction of the titanium dioxide and the precursor, the specific surface area is further increased, the larger specific surface area is beneficial to loading more active substances, and more precursor substances can be combined on the porous structure of the composite carrier. In addition, due to the introduction of the precursor, the crushing strength of the catalyst is obviously improved in the chemical change process of the composite carrier, the combination is relatively firm, the abrasion-resistant and wear-reducing effects of the catalyst are improved, the service life of the prepared biodiesel catalyst can be prolonged, the prepared catalyst can be reused for 10-12 times, and the cost is further saved.
Comparative example 1 a certain amount of argon gas was introduced during the preparation of porous carbon fibers, and the temperature rise process was continued, so that during the preparation of porous carbon fibers, nitrogen doping and carbonization could not be performed, so that a stable binding phase could not be formed, and the strength was reduced to a certain extent, and the anti-wear effect was reduced.
Comparative example 2 is not protected by nitrogen gas during the preparation of the composite carrier, so that a part of air and a small amount of moisture are doped during the preparation, thereby affecting the catalytic activity of the catalyst and the combination of the precursor.
And in the comparative example 3, the precursor is not roasted in the preparation process, so that when the calcium acetate is combined with the composite carrier, the catalytic activity of the catalyst is influenced by the moisture combined with the calcium acetate, and the service life is shortened.
FIG. 1 is a nitrogen adsorption-desorption isotherm plot at-196 ℃ for a biodiesel catalyst prepared from nitrogen-doped porous carbon fibers prepared in example 3. As can be seen from fig. 1, the isotherm of the catalyst exhibits a typical type iv adsorption-desorption curve and has a relatively significant hysteresis loop of type H1, which indicates the presence of mesopores in the catalyst, which also reflects a broader pore size distribution of the catalyst; when the relative pressure is less than 0.1, the adsorption quantity is rapidly increased, which indicates that the catalyst has a large number of micropores, and when the relative pressure is 0.2-0.8, a hysteresis loop indicates that the catalyst also contains a certain quantity of mesopores. The catalyst has wider pore size distribution, which indicates that the adsorption capacity of the catalyst is stronger, so the activity of the catalyst is higher.
Fig. 2 is a pore size distribution diagram of the biodiesel catalyst prepared from the nitrogen-doped porous carbon fiber prepared in example 3, and it can be seen from fig. 2 that the pore size of the catalyst is mainly distributed between 0.6 nm and 0.8nm, and a large number of micropores are formed, which is beneficial to improving the activity of the catalyst.
Figure 3 gives an SEM topography photograph of a biodiesel catalyst prepared from nitrogen doped porous carbon fibers. As can be seen from FIG. 3, the carbon fiber carrier for preparing the biodiesel catalyst has uniform thickness, and from the appearance, the carbon fiber also maintains the original shape and is uniformly distributed, and the carbon fiber is not obviously damaged in the preparation process of the catalyst. The diameter of the fiber is about 30 μm, active component particles with small particle size are uniformly dispersed on the surface of the fiber, the particle size is uniform, and the active component particles are dispersed and loaded on the carbon fiber. The active ingredient particles can also repair surface portion defects, thereby suppressing the generation of cracks and improving tensile strength. In addition, a small amount of flaky active components are arranged on the periphery of the carbon fibers, and no large particles are agglomerated, so that better contact between the carbon fibers can be promoted, the binding force between fiber matrixes is improved, and the strength of the catalyst is improved.
The biodiesel catalysts prepared in examples 1 to 3 and comparative examples 1 to 3 are applied to the transesterification of soybean oil and methanol, and the specific processes are as follows:
adding soybean oil into a three-neck flask with a condenser pipe, heating to 60 ℃, adding a biodiesel catalyst and methanol under stirring, wherein the mass ratio of the soybean oil to the methanol is 5: 1, the dosage of the biodiesel catalyst accounts for 1.2 percent of the mass of the soybean oil, reacting for 2 hours at 60-80 ℃, distilling under normal pressure after the reaction is finished, recovering the methanol, and separating out a glycerin layer to obtain a biodiesel crude product;
refining the crude product of the biodiesel by adopting a steam distillation method, controlling the liquid phase temperature in a distillation flask to be 200-280 ℃, the gas phase temperature to be 120-220 ℃, the steam temperature to be about 100 ℃, introducing 5L/min of steam, distilling out the biodiesel from the distillation flask, cooling and then carrying out oil-water separation to obtain the biodiesel.
The properties of the biodiesel prepared in examples 1 to 3 and comparative examples 1 to 3 were measured, and the specific results are shown in table 4, and the yields of the biodiesel prepared are shown in table 5.
TABLE 4
Table 4 shows the indexes of the biodiesel produced using the biodiesel catalysts produced in examples 1 to 3 and comparative examples 1 to 3, such as flash point, kinematic viscosity, water content, etc., and it can be seen from table 4 that the biodiesel produced using the biodiesel catalysts produced by the production method disclosed in the present invention all satisfy the requirements of the standard for biodiesel (BD 100) for blending diesel fuel in GB/T20828-2007.
TABLE 5
| Item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Yield of | 96.0％ | 97.2％ | 98.5％ | 92.1％ | 91.4％ | 90.6％ |
From the table 5, it can be seen that when the biodiesel catalyst prepared by the preparation method disclosed by the invention is applied to the preparation process of biodiesel, the yield of the biodiesel is high and can reach more than 96%, the biodiesel can be recycled for 10-12 times, the cost is saved, no corresponding byproduct is discharged, and the method is economical and environment-friendly.
In summary, in the process of preparing the biodiesel catalyst, the porous carbon fibers need to be subjected to nitrogen doping modification, so that the strength of the catalyst is improved, the anti-wear effect of the catalyst is improved, and the service life of the catalyst is prolonged. The preparation process needs protection of nitrogen, and the influence of gases such as moisture in air and carbon dioxide on the catalytic activity of the catalyst is avoided. Therefore, the catalysts prepared in comparative examples 1 to 3 were relatively low in all of loading, catalytic activity and service life, compared to examples 1 to 3 of the present invention.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A preparation method of a biodiesel catalyst is characterized by comprising the following steps:
s1, preparation of composite carrier
S1.1 preparation of nitrogen-doped porous carbon fiber
Placing microcrystalline cellulose in the center of a tube furnace, introducing nitrogen, heating to 300 ℃, preserving heat for 1-5h, then heating to 500 ℃, and preserving heat for 1-10h to obtain nitrogen-doped porous carbon fiber; wherein the dosage ratio of the microcrystalline cellulose to the nitrogen is 1g:80-120mL/min;
s1.2, preparation of titanium dioxide hydrosol
Dropwise adding acetic acid and lactic acid with the volume ratio of 1:1 into an ethylenediamine solution, wherein the volume ratio of the lactic acid to the ethylenediamine is 1: 0.5-1, so as to obtain a solution A; slowly dripping tetrabutyl titanate into the solution A, uniformly stirring, and then slowly dripping deionized water, wherein the volume ratio of the tetrabutyl titanate to the solution A to the deionized water is (1~3): 1: (60 to 100), and continuously stirring uniformly after the dripping is finished to obtain a titanium dioxide aqueous solution;
s1.3, soaking the nitrogen-doped porous carbon fiber into titanium dioxide hydrosol, wherein the mass ratio of the nitrogen-doped porous carbon fiber to the titanium dioxide hydrosol is 1 to 5-10, adjusting the pH value to 7.0 to 8.0, soaking for 6-10h, centrifuging, filtering, drying, and roasting at 500 ℃ for 5-8h under the atmosphere of inert gas to obtain a composite carrier;
s2, preparation of precursor
Fully grinding and mixing calcium acetate and calcium carbonate, and then preserving heat for 3-10 hours at 160-260 ℃ in an inert gas atmosphere to obtain a precursor;
s3, preparation of biodiesel catalyst
Fully grinding and mixing the composite carrier obtained in the step S1 and the precursor obtained in the step S2, placing the mixture in the center of a tube furnace, and introducing inert gas, wherein the mass ratio of the precursor to the composite carrier is 1: and (3) 20-30), gradually heating the tube furnace to 260 ℃, preserving heat for 3-6h, heating to 500-600 ℃, roasting, and preserving heat for 6-12h to obtain the biodiesel catalyst.
2. The method for preparing a biodiesel catalyst according to claim 1, wherein the temperature rise rate in the step of preparing the S1.1 nitrogen-doped porous carbon fiber is 5 to 10 ℃/min.
3. The method for preparing the biodiesel catalyst according to claim 1, wherein the reaction temperature in the preparation of the S1.2 titanium dioxide hydrosol is 20 to 30 ℃.
4. The method for preparing the biodiesel catalyst according to claim 1, wherein the mass ratio of calcium acetate to calcium carbonate in S2 is 1:1.
5. The method for preparing the biodiesel catalyst according to claim 1, wherein the heating rate in the roasting process in S1.3 and S3 is 3~8 ℃/min.
6. The method for preparing a biodiesel catalyst according to claim 1, wherein the inert gas in S1.3, S2, S3 is any one of nitrogen, argon, helium, and neon.
7. A biodiesel catalyst obtained by the production process according to any one of claims 1 to 6.
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