CN117884109A - Preparation method and application of biomass acid-base dual-function heterogeneous catalyst - Google Patents
Preparation method and application of biomass acid-base dual-function heterogeneous catalyst Download PDFInfo
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- CN117884109A CN117884109A CN202410136293.XA CN202410136293A CN117884109A CN 117884109 A CN117884109 A CN 117884109A CN 202410136293 A CN202410136293 A CN 202410136293A CN 117884109 A CN117884109 A CN 117884109A
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- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002028 Biomass Substances 0.000 title abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 60
- 239000003225 biodiesel Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 21
- 210000003278 egg shell Anatomy 0.000 claims abstract description 20
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 241000219000 Populus Species 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 238000001354 calcination Methods 0.000 claims description 36
- 239000000292 calcium oxide Substances 0.000 claims description 32
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 32
- 239000003921 oil Substances 0.000 claims description 28
- 235000019198 oils Nutrition 0.000 claims description 28
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 11
- 230000001588 bifunctional effect Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 7
- 239000010775 animal oil Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 102000002322 Egg Proteins Human genes 0.000 claims description 2
- 108010000912 Egg Proteins Proteins 0.000 claims description 2
- 238000006277 sulfonation reaction Methods 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims 2
- 238000004140 cleaning Methods 0.000 claims 2
- 235000019482 Palm oil Nutrition 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 239000007791 liquid phase Substances 0.000 claims 1
- 239000002540 palm oil Substances 0.000 claims 1
- 239000002585 base Substances 0.000 abstract description 23
- 241001494479 Pecora Species 0.000 abstract description 20
- 239000002253 acid Substances 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052791 calcium Inorganic materials 0.000 abstract description 5
- 239000011575 calcium Substances 0.000 abstract description 5
- 238000002386 leaching Methods 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 33
- 239000000047 product Substances 0.000 description 13
- 239000011949 solid catalyst Substances 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 11
- 238000004817 gas chromatography Methods 0.000 description 11
- 238000002390 rotary evaporation Methods 0.000 description 11
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 7
- 239000005642 Oleic acid Substances 0.000 description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 235000015278 beef Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
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- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
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- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
Classifications
-
- 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
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Abstract
The invention relates to a biomass acid-base dual-functional heterogeneous catalyst for synthesizing biodiesel and a preparation method thereof, and the biomass acid-base dual-functional heterogeneous catalyst has wide raw material sources and low cost. The poplar leaves and eggshells are used as catalyst raw materials, so that waste is changed into valuable. The catalyst has high reaction yield in the process of catalyzing the transesterification of the sheep oil to synthesize the biodiesel. The sulfuric acid sulfonated biochar is compounded with eggshells, so that the catalyst has acid-base double sites, and therefore, has good acid resistance. The biochar is used as a carrier, so that the loaded active components are not easy to fall off, the specific surface area is increased, and the activity and the reaction stability of the catalyst are enhanced. The method can relieve the problems of easy leaching of active sites, poor reusability, weak acid resistance and the like in the process of catalyzing transesterification by calcium-based heterogeneous alkali, and has important practical significance for practical industrial production.
Description
Technical Field
The invention relates to the technical field of preparing biodiesel by catalyzing a heterogeneous catalyst, in particular to a preparation method and application of an acid-base bifunctional heterogeneous catalyst. The invention belongs to the field of catalyst preparation, and in particular relates to a preparation method of an acid-base dual-function heterogeneous catalyst which takes sulfonated biochar (poplar leaves) as a carrier and calcium oxide in eggshells as an active site and application of the catalyst in catalyzing transesterification to produce biodiesel.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Biodiesel is a long-chain fatty acid monoalkyl ester synthesized from renewable raw materials such as vegetable oil, animal oil and the like through esterification reaction. Has the advantages of biodegradability, low pollutant emission and the like. Because of its various physicochemical properties very similar to fossil diesel, it can be used directly or in combination with petroleum-based diesel without adversely affecting the engine. Therefore, it is widely considered as a typical clean energy source, and the problem of energy shortage can be alleviated to some extent. In the process of producing biodiesel by a catalytic transesterification method, the effect of a catalyst is important. The research on the catalyst with high efficiency and low price for the biodiesel preparation process becomes a research hotspot. Compared with the homogeneous catalysts (KOH, naOH, etc.) which are put into industrial production, the heterogeneous catalysts have the advantages of recycling, reuse, environmental protection, small corrosion to equipment, and the like. The use of waste as a catalyst feedstock is an important way to reduce catalyst costs. Efficient, cost-effective heterogeneous catalysts are found from biomass materials (leaves, walnut shells, eggshells, shells, beef bones, etc.), which help to reduce the cost of biodiesel production and promote the long-term growth and development of the biofuel industry. Since eggshells have rich calcium-based components. CaO is the most commonly used base catalyst for preparing biodiesel by catalysis because of the advantages of high cost benefit, high catalytic activity, strong alkalinity, easily available raw materials and the like. But has the problems of small specific surface area, easy leaching of active sites, weak acid resistance and the like. Research has shown that supported alkali/alkaline earth heterogeneous alkali catalysts can improve the problems, but still have the problems of easy leaching of active sites, poor reusability and weak acid resistance.
Disclosure of Invention
The invention aims to solve the problems of easy leaching of active sites, poor reusability, weak acid resistance and the like in the process of calcium-based heterogeneous base catalytic transesterification, and provides a preparation method of a heterogeneous catalyst which takes sulfonated biochar as a carrier and has acid-base dual functions and application of the heterogeneous catalyst in biodiesel production. The catalyst has the advantages of simple preparation method, low cost, higher transesterification catalytic efficiency under mild conditions, stronger acid resistance, low requirements on the quality of raw oil products and capability of meeting the requirements of industrial production to a certain extent.
In order to achieve the above object, the present invention provides the following technical solutions:
in one aspect, an acid-base dual function heterogeneous catalyst comprises:
A carrier;
Calcium oxide supported on a carrier;
wherein the carrier raw material is poplar leaf, and the calcium oxide raw material is eggshell.
The research of the application finds that: the calcium oxide is loaded on the sulfonated biochar, so that the mass transfer resistance of the catalyst in the transesterification process can be reduced, the acid-base dual-function characteristics of the catalyst are fully exerted, the acid resistance of the calcium-based catalyst is enhanced, namely, under the synergistic effect of sulfonic acid groups, the acid resistance of the catalyst is ensured on the premise that the catalytic performance is high; particularly, the sensitivity to the oleic acid component of the raw material is greatly reduced, and the application range of the raw material oil is effectively widened.
On the other hand, the invention also provides a preparation method of the acid-base bifunctional heterogeneous catalyst, which comprises the following steps:
Calcining eggshells in an N2 atmosphere at the temperature of not lower than 800 ℃ to obtain porous CaO; calcining poplar leaves in an N2 atmosphere at 600 ℃ to obtain biochar; sulfonating the obtained biochar with sulfuric acid (W: V1: 10) to obtain sulfonated biochar; dissolving CaO in deionized water, stirring for 30min, adding sulfonated biochar, heating, stirring until the water is evaporated to dryness, and drying, and calcining the dried sample for the second time in N2 atmosphere at the temperature of not lower than 800 ℃ for 2h to obtain an acid-base dual-function heterogeneous catalyst; the research of the application finds that: the acid-base dual-function heterogeneous catalyst can obtain better catalytic performance and acid-resistant capability only through simple aging and calcination, and the preparation method is simple and easy to industrially popularize.
In a third aspect, an acid-base bifunctional heterogeneous catalyst is obtained by the preparation method.
In a fourth aspect, the application of the acid-base bifunctional heterogeneous catalyst in catalytic synthesis of biodiesel is provided.
In a fifth aspect, a method for synthesizing biodiesel, which adopts the acid-base dual-function heterogeneous catalyst to catalyze the transesterification of the sheep oil and methanol.
The invention has the beneficial effects that:
(1) The catalyst prepared by the invention has wide sources of raw materials and low cost. The biomass resources in China are rich, and the biochar and eggshells are used as catalyst raw materials, so that waste materials can be changed into things of value, and the purpose of reducing the catalyst cost is achieved.
(2) The catalyst prepared by the invention has high catalytic reaction yield, and the sulfuric acid sulfonated biochar is compounded with eggshells, so that the catalyst has acid-base double-function sites, thus having good acid resistance and low requirements on the quality of raw oil products. The biochar is used as a carrier, so that the loaded active components are not easy to fall off, the specific surface area is increased, and the activity and the reaction stability of the catalyst are enhanced;
(3) The method has the advantages of simplicity, low cost, universality and easiness in large-scale production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application.
FIG. 1 is an XRD pattern of the catalysts obtained in examples 1-6;
FIG. 2 is an SEM image of porous CaO obtained in example 1;
FIG. 3 is an SEM image of the catalyst obtained in example 4;
FIG. 4 is a graph showing the transesterification yields of sheep oil catalyzed by the catalysts obtained in examples 1-7.
FIG. 5 is a graph showing transesterification yields of sheep oil catalyzed by the catalyst of example 4 and containing oleic acid in different proportions.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present application. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
As introduced in the background art, aiming at the problems of easy leaching of active sites, poor reusability and weak acid resistance in the transesterification process of the calcium-based heterogeneous base catalyst, the invention provides a method for preparing an acid-base bifunctional heterogeneous catalyst, wherein the catalyst is CaO/C-s, and the method comprises the steps of taking poplar leaves and eggshells as raw materials.
Preferably, the method for preparing the acid-base bifunctional solid catalyst comprises the following steps:
(1) Calcining eggshells for the first time in an N2 atmosphere to obtain porous CaO;
(2) Calcining poplar leaves for the first time in N2 atmosphere to obtain biochar;
(3) Sulfonating the biochar in the step (2) with sulfuric acid to obtain sulfonated biochar;
(4) Mixing the sulfonated biochar in the step (3) and the porous CaO in the step (1) in different proportions in deionized water, carrying out hydrothermal stirring until moisture is evaporated to dryness, and carrying out secondary calcination after drying to obtain the acid-base bifunctional heterogeneous catalyst;
Preferably, in the step (1), the temperature of the first calcination of the eggshells is 800-950 ℃, the temperature rising rate is 10 ℃/min, and the time is 1-4 h. Preferably at a calcination temperature of 900℃for a calcination time of 3 hours.
Preferably, in the step (2), the first calcination temperature of the poplar leaves is fixed at 600 ℃, the heating rate is 10 ℃/min, and the calcination time is 4 hours.
Preferably, in the step (3), the mixing ratio of the biochar and the concentrated sulfuric acid is 1:10 (w: v) sulfonation temperature was 98℃and time was 4 hours.
Preferably, in the step (4), the mass ratio of the calcium oxide to the sulfonated biochar is 1: (0.3-3). Preferably, the mass ratio of the calcium oxide to the sulfonated biochar is 1:1.
Preferably, in the step (4), the temperature of the second calcination is 800-900 ℃, the temperature rising rate is 10 ℃/min, and the time is 2h. The calcination temperature is preferably 850 ℃.
In some embodiments, the method of preparing biodiesel comprises: and uniformly mixing the raw oil, methanol and the mixture of the acid-base dual-function heterogeneous catalyst with different proportions, and performing transesterification reaction to prepare the biodiesel.
Preferably, the raw oil is mutton fat and mutton fat containing a certain amount of oleic acid.
Preferably, the raw oil is animal oil or vegetable oil, preferably animal oil; the animal oil is preferably sheep oil.
Preferably, the alcohol is an alcohol capable of undergoing transesterification, preferably methanol.
Preferably, the molar ratio of the raw oil to the alcohol is 1:6-14, preferably 1:8.
Preferably, the catalyst is added in an amount of 4 to 10wt%, preferably 6% of the feed oil.
Preferably, the transesterification temperature is 50-75deg.C, preferably 65deg.C.
Preferably, the transesterification reaction time is 1 to 3 hours, preferably 2.5 hours.
Preferably, the water bath stirring speed is 1000-1500r/min, preferably 1200r/min.
The technical scheme of the application is described below through specific examples.
Example 1
Calcining eggshells in a muffle furnace at 900 ℃ for 3 hours under an N2 atmosphere to obtain porous CaO serving as a catalyst;
when the temperature of the water bath reached 65 ℃, 5g of sheep oil, 0.3g of catalyst and 1.6g of methanol were added into the round-bottomed flask, and the mixture was maintained for 2.5 hours under continuous stirring at a water bath rotation speed of 1200 r/min. Removing unreacted methanol from the reaction product by rotary evaporation, separating the solid catalyst by a centrifuge, standing and layering the product in a centrifuge tube, wherein the lower layer is the catalyst middle layer and the glycerol upper layer, and the biodiesel yield is 54.6 percent as measured by gas chromatography.
Example 2
Calcining eggshells in a muffle furnace at 900 ℃ under an N2 atmosphere for 3 hours to obtain porous CaO; calcining poplar leaves for 4 hours at 600 ℃ in an N2 atmosphere in a muffle furnace to obtain biochar; mixing calcined biochar and concentrated sulfuric acid in a certain proportion (w: v 1:10), uniformly stirring in a high-pressure reaction kettle, keeping the temperature at 98 ℃ for 4 hours, cooling to room temperature, filtering a sample, washing the sample with hot deionized water until the pH value of the filtrate is close to 7, and drying the sample to obtain sulfonated biochar; dissolving 3g of CaO in 70ml of deionized water, stirring for 30min, adding 1g of sulfonated biochar, carrying out hydrothermal stirring until the water is evaporated to dryness, drying at 70 ℃ for 15h, and calcining the dried sample in a muffle furnace at 850 ℃ for 2h under the N2 atmosphere to obtain CaO/C-s;
When the temperature of the water bath reached 65 ℃, 5g of sheep oil, 0.3g of catalyst and 1.6g of methanol were added into the round-bottomed flask, and the mixture was maintained for 2.5 hours under continuous stirring at a water bath rotation speed of 1200 r/min. Removing unreacted methanol from the reaction product by rotary evaporation, separating the solid catalyst by a centrifuge, standing and layering the product in a centrifuge tube, wherein the lower layer is the catalyst middle layer and the glycerol upper layer, and the biodiesel yield is 83.6 percent as measured by gas chromatography.
Example 3
Calcining eggshells in a muffle furnace at 900 ℃ under an N2 atmosphere for 3 hours to obtain porous CaO; calcining poplar leaves for 4 hours at 600 ℃ in an N2 atmosphere in a muffle furnace to obtain biochar; mixing calcined biochar and concentrated sulfuric acid in a certain proportion (w: v 1:10), uniformly stirring in a high-pressure reaction kettle, keeping the temperature at 98 ℃ for 4 hours, cooling to room temperature, filtering a sample, washing the sample with hot deionized water until the pH value of the filtrate is close to 7, and drying the sample to obtain sulfonated biochar; dissolving 2g of CaO in 70ml of deionized water, stirring for 30min, adding 1g of sulfonated biochar, carrying out hydrothermal stirring until the water is evaporated to dryness, drying at 70 ℃ for 15h, and calcining the dried sample in a muffle furnace at 850 ℃ for 2h under the N2 atmosphere to obtain CaO/C-s;
When the temperature of the water bath reached 65 ℃, 5g of sheep oil, 0.3g of catalyst and 1.6g of methanol were added into the round-bottomed flask, and the mixture was maintained for 2.5 hours under continuous stirring at a water bath rotation speed of 1200 r/min. Removing unreacted methanol from the reaction product by rotary evaporation, separating the solid catalyst by a centrifuge, standing and layering the product in a centrifuge tube, wherein the lower layer is the catalyst middle layer and the glycerol upper layer, and the biodiesel yield is 92.4 percent as measured by gas chromatography.
Example 4
Calcining eggshells in a muffle furnace at 900 ℃ under an N2 atmosphere for 3 hours to obtain porous CaO; calcining poplar leaves for 4 hours at 600 ℃ in an N2 atmosphere in a muffle furnace to obtain biochar; mixing calcined biochar and concentrated sulfuric acid in a certain proportion (w: v 1:10), uniformly stirring in a high-pressure reaction kettle, keeping the temperature at 98 ℃ for 4 hours, cooling to room temperature, filtering a sample, washing the sample with hot deionized water until the pH value of the filtrate is close to 7, and drying the sample to obtain sulfonated biochar; dissolving 1g of CaO in 70ml of deionized water, stirring for 30min, adding 1g of sulfonated biochar, carrying out hydrothermal stirring until the water is evaporated to dryness, drying at 70 ℃ for 15h, and calcining the dried sample in a muffle furnace at 850 ℃ for 2h under the N2 atmosphere to obtain CaO/C-s;
When the temperature of the water bath reached 65 ℃, 5g of sheep oil, 0.3g of catalyst and 1.6g of methanol were added into the round-bottomed flask, and the mixture was maintained for 2.5 hours under continuous stirring at a water bath rotation speed of 1200 r/min. Removing unreacted methanol from the reaction product by rotary evaporation, separating the solid catalyst by a centrifuge, standing and layering the product in a centrifuge tube, wherein the lower layer is the catalyst middle layer and the glycerol upper layer, and the biodiesel yield is 98% as measured by gas chromatography.
Example 5
Calcining eggshells in a muffle furnace at 900 ℃ under an N2 atmosphere for 3 hours to obtain porous CaO; calcining poplar leaves for 4 hours at 600 ℃ in an N2 atmosphere in a muffle furnace to obtain biochar; mixing calcined biochar and concentrated sulfuric acid in a certain proportion (w: v 1:10), uniformly stirring in a high-pressure reaction kettle, keeping the temperature at 98 ℃ for 4 hours, cooling to room temperature, filtering a sample, washing the sample with hot deionized water until the pH value of the filtrate is close to 7, and drying the sample to obtain sulfonated biochar; dissolving 1g of CaO in 70ml of deionized water, stirring for 30min, adding 2g of sulfonated biochar, carrying out hydrothermal stirring until the water is evaporated to dryness, drying at 70 ℃ for 15h, and calcining the dried sample in a muffle furnace at 850 ℃ for 2h under the N2 atmosphere to obtain CaO/C-s;
When the temperature of the water bath reached 65 ℃, 5g of sheep oil, 0.3g of catalyst and 1.6g of methanol were added into the round-bottomed flask, and the mixture was maintained for 2.5 hours under continuous stirring at a water bath rotation speed of 1200 r/min. Removing unreacted methanol from the reaction product by rotary evaporation, separating the solid catalyst by a centrifuge, standing and layering the product in a centrifuge tube, wherein the lower layer is the catalyst middle layer and the glycerol upper layer, and the biodiesel yield is 87.7 percent as measured by gas chromatography.
Example 6
Calcining eggshells in a muffle furnace at 900 ℃ under an N2 atmosphere for 3 hours to obtain porous CaO; calcining poplar leaves for 4 hours at 600 ℃ in an N2 atmosphere in a muffle furnace to obtain biochar; mixing calcined biochar and concentrated sulfuric acid in a certain proportion (w: v 1:10), uniformly stirring in a high-pressure reaction kettle, keeping the temperature at 98 ℃ for 4 hours, cooling to room temperature, filtering a sample, washing the sample with hot deionized water until the pH value of the filtrate is close to 7, and drying the sample to obtain sulfonated biochar; dissolving 1g of CaO in 70ml of deionized water, stirring for 30min, adding 3g of sulfonated biochar, carrying out hydrothermal stirring until the water is evaporated to dryness, drying at 70 ℃ for 15h, and calcining the dried sample in a muffle furnace at 850 ℃ for 2h under the N2 atmosphere to obtain CaO/C-s;
When the temperature of the water bath reached 65 ℃, 5g of sheep oil, 0.3g of catalyst and 1.6g of methanol were added into the round-bottomed flask, and the mixture was maintained for 2.5 hours under continuous stirring at a water bath rotation speed of 1200 r/min. Removing unreacted methanol from the reaction product by rotary evaporation, separating the solid catalyst by a centrifuge, standing and layering the product in a centrifuge tube, wherein the lower layer is the catalyst middle layer and the glycerol upper layer, and the biodiesel yield is 67% as measured by gas chromatography.
Example 7
Calcining poplar leaves for 4 hours at 600 ℃ in an N2 atmosphere in a muffle furnace to obtain biochar; mixing calcined biochar and concentrated sulfuric acid in a certain proportion (w: v 1:10), uniformly stirring in a high-pressure reaction kettle, keeping the temperature for 4 hours at 98 ℃, cooling to room temperature, filtering a sample, washing the sample with hot deionized water until the pH value of the filtrate is close to 7, and drying the sample to obtain sulfonated biochar serving as a catalyst;
When the temperature of the water bath reached 65 ℃, 5g of sheep oil, 0.3g of catalyst and 1.6g of methanol were added into the round-bottomed flask, and the mixture was maintained for 2.5 hours under continuous stirring at a water bath rotation speed of 1200 r/min. Removing unreacted methanol from the reaction product by rotary evaporation, separating the solid catalyst by a centrifuge, standing and layering the product in a centrifuge tube, wherein the lower layer is the catalyst middle layer and the glycerol upper layer, and the biodiesel yield is 17 percent as measured by gas chromatography.
Example 8
The catalyst preparation was the same as in example 3
When the temperature of the water bath reached 65 ℃, 5g of KOH/g of acidified sheep oil (2% oleic acid was added to the sheep oil) with an acid value of 4.49mg, 0.3g of catalyst and 1.6g of methanol were initially introduced into the round-bottomed flask and maintained for 2.5 hours with continuous stirring at a water bath speed of 1200 r/min. Removing unreacted methanol from the reaction product by rotary evaporation, separating the solid catalyst by a centrifuge, standing and layering the product in a centrifuge tube, wherein the lower layer is the catalyst middle layer and the glycerol upper layer, and the biodiesel yield is 87.5 percent as measured by gas chromatography.
Example 9
The catalyst preparation was the same as in example 3
When the temperature of the water bath reached 65 ℃, 5g of KOH/g of acidified sheep oil (3% oleic acid was added to the sheep oil) with an acid value of 6.17mg, 0.3g of catalyst and 1.6g of methanol were initially introduced into the round-bottomed flask and maintained for 2.5 hours with continuous stirring at a water bath speed of 1200 r/min. Removing unreacted methanol from the reaction product by rotary evaporation, separating the solid catalyst by a centrifuge, standing and layering the product in a centrifuge tube, wherein the lower layer is the catalyst middle layer and the glycerol upper layer, and the biodiesel yield is 70% as measured by gas chromatography.
Example 10
The catalyst preparation was the same as in example 3
When the temperature of the water bath reached 65 ℃, 5g of KOH/g of acidified sheep oil (4% oleic acid was added to the sheep oil) with an acid value of 8.24mg, 0.3g of catalyst and 1.6g of methanol were initially introduced into the round-bottomed flask and maintained for 2.5 hours with continuous stirring at a water bath speed of 1200 r/min. Removing unreacted methanol from the reaction product by rotary evaporation, separating the solid catalyst by a centrifuge, standing and layering the product in a centrifuge tube, wherein the lower layer is the catalyst middle layer and the glycerol upper layer, and the biodiesel yield is 49.2 percent as measured by gas chromatography.
Example 11
The catalyst preparation was the same as in example 3
When the temperature of the water bath reached 65 ℃, 5g of acid value 9.98mg KOH/g of acidified sheep oil (5% oleic acid was added to the sheep oil), 0.3g of catalyst and 1.6g of methanol were initially introduced into the round-bottomed flask and maintained for 2.5 hours with continuous stirring at a water bath speed of 1200 r/min. Removing unreacted methanol from the reaction product by rotary evaporation, separating the solid catalyst by a centrifuge, standing and layering the product in a centrifuge tube, wherein the lower layer is the catalyst middle layer and the glycerol upper layer, and the biodiesel yield is 43.4 percent as measured by gas chromatography.
Claims (9)
1. The preparation method of the acid-base bifunctional heterogeneous catalyst is characterized by comprising the following steps of:
cleaning eggshells, drying and crushing, and then calcining for the first time in an atmosphere of N 2 to obtain porous CaO;
Cleaning, drying and crushing poplar leaves, and calcining for the first time in an atmosphere of N 2 to obtain biochar;
sulfonating the biochar with sulfuric acid to obtain sulfonated biochar;
Mixing the sulfonated biochar and the porous CaO in different proportions in deionized water, heating and stirring in a water bath until the water is evaporated to dryness, drying overnight, grinding, and calcining in the N 2 atmosphere for the second time to obtain the acid-base dual-function heterogeneous catalyst.
2. The method of claim 1, wherein the eggshell is calcined at a temperature of 800 to 950 ℃ for a time of 1 to 4 hours.
3. The method of claim 1, wherein the first calcination of the poplar leaf is carried out at 600 ℃ for 4 hours.
4. The method of claim 1, wherein the ratio of biochar to concentrated sulfuric acid during sulfonation is w: v (1:10), the temperature is 98 ℃, and the time is 4 hours.
5. The method of claim 1, wherein the mass ratio of the calcium oxide to the sulfonated biochar is 1: (0.3-3).
6. The method of claim 1, wherein the second calcination is carried out at a temperature of 800 to 900 ℃ for a period of 2 hours.
7. The use of the acid-base bifunctional heterogeneous catalyst of claim 1 for preparing biodiesel.
8. The method as set forth in claim 7, including: the biodiesel is prepared by uniformly mixing raw oil, alcohol and the mixture of the acid-base dual-function heterogeneous catalyst in claim 1, and performing transesterification.
9. The method for synthesizing biodiesel according to claim 8, wherein the catalyst is added in an amount of 4-10% by mass of the animal oil;
Or, the molar ratio of the methanol to the palm oil is 6-14:1;
or the transesterification temperature is 50-75 ℃;
or the time of the transesterification reaction is 1-3 h;
Or after the transesterification reaction is finished, centrifugally recovering the catalyst, layering a liquid-phase product, and obtaining biodiesel through the reaction on the upper layer.
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