CN114950479A - Biochar-based solid acid catalyst prepared by low-temperature sulfonation, preparation method thereof and application of biochar-based solid acid catalyst in catalytic esterification reaction - Google Patents
Biochar-based solid acid catalyst prepared by low-temperature sulfonation, preparation method thereof and application of biochar-based solid acid catalyst in catalytic esterification reaction Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 239000011973 solid acid Substances 0.000 title claims abstract description 61
- 238000006277 sulfonation reaction Methods 0.000 title claims abstract description 22
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 230000003197 catalytic effect Effects 0.000 title description 8
- 229920002488 Hemicellulose Polymers 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000197 pyrolysis Methods 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000003763 carbonization Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 35
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 35
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 35
- 239000005642 Oleic acid Substances 0.000 claims description 35
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 35
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 35
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000001914 filtration Methods 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 31
- 239000011541 reaction mixture Substances 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000003225 biodiesel Substances 0.000 abstract description 4
- 239000002154 agricultural waste Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 33
- 239000000047 product Substances 0.000 description 29
- 238000003756 stirring Methods 0.000 description 28
- 240000008042 Zea mays Species 0.000 description 15
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 15
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 15
- 235000005822 corn Nutrition 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000004140 cleaning Methods 0.000 description 14
- 238000007865 diluting Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 14
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 14
- 239000000706 filtrate Substances 0.000 description 14
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 14
- 229940073769 methyl oleate Drugs 0.000 description 14
- 238000002390 rotary evaporation Methods 0.000 description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000811 xylitol Substances 0.000 description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 2
- 229960002675 xylitol Drugs 0.000 description 2
- 235000010447 xylitol Nutrition 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing a biochar-based solid acid catalyst by low-temperature sulfonation, which comprises the steps of carrying out pyrolysis carbonization on a corncob raw material without hemicellulose for 3-4h under the conditions of nitrogen atmosphere and 350 ℃ of 300-; then mixing concentrated sulfuric acid with the mass fraction of 95-98% with biochar obtained by pyrolysis in a proportion of 15-20 ml: 1g of the raw materials are mixed according to a proportion, stirred for 2-4h at 25-90 ℃ for sulfonation, filtered, washed by hot deionized water and dried to obtain the biochar-based solid acid catalyst. The invention takes agricultural wastes as raw materials, is cheap and easy to obtain, reduces the production cost of the solid acid catalyst and the biodiesel, and improves the utilization value of renewable resources. The sulfonation process of the catalyst preparation in the invention is carried out at low temperature, thus saving energy. The catalyst prepared by the method is solid and is easy to separate from the product in the esterification reaction mixture.
Description
Technical Field
The invention relates to the field of waste resource utilization technology and renewable energy, in particular to a biochar-based solid acid catalyst prepared by low-temperature sulfonation, a preparation method thereof and application of the biochar-based solid acid catalyst in catalytic esterification reaction.
Background
Coal, petroleum, natural gas and the like are indispensable energy sources in life, and due to the defects that the coal, the petroleum, the natural gas and the like cannot be regenerated and the substances such as excessive carbon dioxide generated by combustion have great influence on the environment, the coal, the petroleum, the natural gas and the like are gradually replaced by clean renewable resources, and the biodiesel is a clean fuel taken from the renewable resources and is a high-quality substitute for the petroleum diesel. At present, one of the main methods for producing biodiesel is esterification reaction, and liquid acid is usually adopted to catalyze the esterification reaction to produce biodiesel, but the liquid acid catalyst which is not completely reacted is difficult to separate from the product, while the solid acid catalyst has the advantage of easy separation from the reaction mixture, and is more convenient to apply. The catalyst for catalyzing esterification reaction mostly adopts diatomite, macroporous resin, graphene oxide and the like as carriers, but has the defects of high price, high-temperature inactivation of resin and the like, and the resource utilization of waste has important significance for realizing green agriculture and sustainable development. After the corncobs are used for preparing sugar by extracting hemicellulose, the lignocellulose structure is looser, the price is lower, and the corncobs are ideal catalyst carrier materials.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a biochar-based solid acid catalyst prepared by low-temperature sulfonation, a preparation method thereof and application of the biochar-based solid acid catalyst in catalytic esterification reaction.
The method for preparing the biochar-based solid acid catalyst through sulfonation at low temperature is characterized in that corncobs without hemicellulose are pyrolyzed and carbonized in nitrogen atmosphere, the biochar obtained through pyrolysis is mixed with concentrated sulfuric acid and stirred for sulfonation, solid is collected through filtration, washed with hot deionized water and dried, and the biochar-based solid acid catalyst is obtained.
The method for preparing the biochar-based solid acid catalyst by low-temperature sulfonation is characterized in that the pyrolysis carbonization temperature is 300-350 ℃, and the pyrolysis carbonization time is 3-4 h.
The method for preparing the biochar-based solid acid catalyst by low-temperature sulfonation is characterized in that the mass fraction of concentrated sulfuric acid is 95-98%, and the feeding ratio of the concentrated sulfuric acid to biochar is 15-20 ml: 1g of the total weight of the composition.
The method for preparing the biochar-based solid acid catalyst by low-temperature sulfonation is characterized in that the sulfonation temperature is 25-90 ℃, and the sulfonation time is 2-4 hours.
The biochar-based solid acid catalyst prepared by the invention can be well applied to catalytic esterification reaction, and specifically comprises the following components: and (3) uniformly mixing the biochar-based solid acid catalyst, methanol and oleic acid, and reacting at normal pressure to generate ester. The esterification reaction temperature is 65-75 ℃, the reaction time is 3-6h, and the molar ratio of methanol to oleic acid is 12-15: 1, the adding amount of the biochar-based solid acid catalyst is 2-4wt% of oleic acid.
The beneficial effects obtained by the invention are as follows:
the method takes the waste corncobs without hemicellulose as raw materials, takes concentrated sulfuric acid as a sulfonating agent, and prepares the biochar-based solid acid catalyst for catalyzing esterification reaction through two steps of carbonization and sulfonation, and has the advantages of easily obtained raw materials, low price, high resource utilization rate, low reaction temperature, energy conservation and the like. The invention carries out resource utilization on the corncobs without hemicellulose to prepare the catalyst which has low price and easy separation, the acid content of the catalyst is high, the catalytic activity applied to the catalytic esterification reaction is good, the catalyst is easy to separate and recycle, and the wastewater generated by the esterification reaction process is less. Compared with the conventional corncob raw material, the corncob without hemicellulose is the waste for preparing xylitol, so the cost is lower, the invention utilizes the corncob without hemicellulose, and the solid acid catalyst prepared by taking the waste corncob without hemicellulose as the raw material has better catalytic activity, thereby meeting the industrial target of green development.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
The corn cob for removing the hemicellulose used in the embodiments 2 to 14 of the invention is purchased from Zhejiang Huakang pharmaceutical industry Co., Ltd, and is a hemicellulose-removing waste obtained by deep processing of corn cob as a raw material to produce xylitol. The mass fraction of the concentrated sulfuric acid is 95-98%.
Example 1:
pyrolyzing corncobs (without hemicellulose removed) in a muffle furnace for 3 hours at 300 ℃ in a nitrogen atmosphere, mixing 4g of biochar obtained by pyrolysis with 60ml of concentrated sulfuric acid, stirring in an oil bath at 150 ℃ for 12 hours, filtering, cleaning filter residues with hot deionized water, and drying to obtain the biochar-based solid acid catalyst. Uniformly mixing 0.1g of biochar-based solid acid catalyst, 6.8g of methanol and 5g of oleic acid (with an acid value of 200), stirring and reacting for 3 hours in an oil bath at 65 ℃, detecting and calculating the conversion rate of the oleic acid after the reaction is finished, centrifuging the reaction mixture, filtering and recovering the catalyst, carrying out rotary evaporation on the filtrate to obtain a methyl oleate product, diluting the product with absolute ethyl alcohol, and titrating with 0.01mol/L KOH to obtain the acid value.
Example 2:
pyrolyzing the corn cob with hemicellulose removed in a muffle furnace for 3h at 300 ℃ in a nitrogen atmosphere, mixing 4g of biochar obtained by pyrolysis with 60ml of concentrated sulfuric acid, stirring for 12h in an oil bath at 150 ℃, cleaning filter residue with hot deionized water after filtering, and drying to obtain the biochar-based solid acid catalyst. Uniformly mixing 0.1g of biochar-based solid acid catalyst, 6.8g of methanol and 5g of oleic acid (with an acid value of 200), stirring and reacting for 3 hours in an oil bath at 65 ℃, detecting and calculating the conversion rate of the oleic acid after the reaction is finished, centrifuging the reaction mixture, filtering and recovering the catalyst, carrying out rotary evaporation on the filtrate to obtain a methyl oleate product, diluting the product with absolute ethyl alcohol, and titrating with 0.01mol/L KOH to obtain the acid value.
Example 3:
pyrolyzing the corn cob with hemicellulose removed in a muffle furnace for 3h at 350 ℃ in nitrogen atmosphere, mixing 4g of biochar obtained by pyrolysis with 60ml of concentrated sulfuric acid, stirring for 12h in 150 ℃ oil bath, filtering, cleaning filter residue with hot deionized water, and drying to obtain the biochar-based solid acid catalyst. Uniformly mixing 0.1g of biochar-based solid acid catalyst, 6.8g of methanol and 5g of oleic acid (with an acid value of 200), stirring and reacting for 3 hours in an oil bath at 65 ℃, detecting and calculating the conversion rate of the oleic acid after the reaction is finished, centrifuging the reaction mixture, filtering and recovering the catalyst, carrying out rotary evaporation on the filtrate to obtain a methyl oleate product, diluting the product with absolute ethyl alcohol, and titrating with 0.01mol/L KOH to obtain the acid value.
Example 4:
pyrolyzing the corn cobs without hemicellulose in a muffle furnace for 4 hours at 300 ℃ in a nitrogen atmosphere, mixing 4g of biochar obtained by pyrolysis with 60ml of concentrated sulfuric acid, stirring in an oil bath at 150 ℃ for 12 hours, filtering, cleaning filter residues with hot deionized water, and drying to obtain the biochar-based solid acid catalyst. Uniformly mixing 0.1g of biochar-based solid acid catalyst, 6.8g of methanol and 5g of oleic acid (with an acid value of 200), stirring and reacting for 3 hours in an oil bath at 65 ℃, detecting and calculating the conversion rate of the oleic acid after the reaction is finished, centrifuging the reaction mixture, filtering and recovering the catalyst, carrying out rotary evaporation on the filtrate to obtain a methyl oleate product, diluting the product with absolute ethyl alcohol, and titrating with 0.01mol/L KOH to obtain the acid value.
Example 5:
pyrolyzing the corn cob with hemicellulose removed in a muffle furnace for 3h at 300 ℃ in a nitrogen atmosphere, mixing 4g of biochar obtained by pyrolysis with 80ml of concentrated sulfuric acid, stirring for 12h in an oil bath at 150 ℃, cleaning filter residue with hot deionized water after filtering, and drying to obtain the biochar-based solid acid catalyst. Uniformly mixing 0.1g of biochar-based solid acid catalyst, 6.8g of methanol and 5g of oleic acid (with an acid value of 200), stirring and reacting for 3 hours in an oil bath at 65 ℃, detecting and calculating the conversion rate of the oleic acid after the reaction is finished, centrifuging the reaction mixture, filtering and recovering the catalyst, carrying out rotary evaporation on the filtrate to obtain a methyl oleate product, diluting the product with absolute ethyl alcohol, and titrating with 0.01mol/L KOH to obtain the acid value.
Example 6:
pyrolyzing the corn cobs without hemicellulose in a muffle furnace for 3 hours at 300 ℃ in a nitrogen atmosphere, mixing 4g of biochar obtained by pyrolysis with 60ml of concentrated sulfuric acid, stirring in an oil bath at 90 ℃ for 12 hours, filtering, cleaning filter residues with hot deionized water, and drying to obtain the biochar-based solid acid catalyst. Uniformly mixing 0.1g of biochar-based solid acid catalyst, 6.8g of methanol and 5g of oleic acid (with an acid value of 200), stirring and reacting for 3 hours in an oil bath at 65 ℃, detecting and calculating the conversion rate of the oleic acid after the reaction is finished, centrifuging the reaction mixture, filtering and recovering the catalyst, carrying out rotary evaporation on the filtrate to obtain a methyl oleate product, diluting the product with absolute ethyl alcohol, and titrating with 0.01mol/L KOH to obtain the acid value.
Example 7:
pyrolyzing the corn cob with hemicellulose removed in a muffle furnace for 3h at 300 ℃ in a nitrogen atmosphere, mixing 4g of biochar obtained by pyrolysis with 60ml of concentrated sulfuric acid, stirring for 12h in an oil bath at 50 ℃, cleaning filter residue with hot deionized water after filtering, and drying to obtain the biochar-based solid acid catalyst. Uniformly mixing 0.1g of biochar-based solid acid catalyst, 6.8g of methanol and 5g of oleic acid (with an acid value of 200), stirring and reacting for 3 hours in an oil bath at 65 ℃, detecting and calculating the conversion rate of the oleic acid after the reaction is finished, centrifuging the reaction mixture, filtering and recovering the catalyst, carrying out rotary evaporation on the filtrate to obtain a methyl oleate product, diluting the product with absolute ethyl alcohol, and titrating with 0.01mol/L KOH to obtain the acid value.
Example 8:
pyrolyzing the corn cob with hemicellulose removed in a muffle furnace for 3h at 300 ℃ in a nitrogen atmosphere, mixing 4g of biochar obtained by pyrolysis with 60ml of concentrated sulfuric acid, stirring for 12h in an oil bath at 25 ℃, cleaning filter residue with hot deionized water after filtering, and drying to obtain the biochar-based solid acid catalyst. Uniformly mixing 0.1g of biochar-based solid acid catalyst, 6.8g of methanol and 5g of oleic acid (with an acid value of 200), stirring and reacting for 3 hours in an oil bath at 65 ℃, detecting and calculating the conversion rate of the oleic acid after the reaction is finished, centrifuging the reaction mixture, filtering and recovering the catalyst, carrying out rotary evaporation on the filtrate to obtain a methyl oleate product, diluting the product with absolute ethyl alcohol, and titrating with 0.01mol/L KOH to obtain the acid value.
Example 9:
pyrolyzing the corn cob with hemicellulose removed in a muffle furnace for 3h at 300 ℃ in a nitrogen atmosphere, mixing 4g of biochar obtained by pyrolysis with 60ml of concentrated sulfuric acid, stirring for 4h in an oil bath at 25 ℃, cleaning filter residue with hot deionized water after filtering, and drying to obtain the biochar-based solid acid catalyst. Uniformly mixing 0.1g of biochar-based solid acid catalyst, 6.8g of methanol and 5g of oleic acid (with an acid value of 200), stirring and reacting for 3 hours in an oil bath at 65 ℃, detecting and calculating the conversion rate of the oleic acid after the reaction is finished, centrifuging the reaction mixture, filtering and recovering the catalyst, carrying out rotary evaporation on the filtrate to obtain a methyl oleate product, diluting the product with absolute ethyl alcohol, and titrating with 0.01mol/L KOH to obtain the acid value.
Example 10:
pyrolyzing the corn cob with hemicellulose removed in a muffle furnace for 3h at 300 ℃ in a nitrogen atmosphere, mixing 4g of biochar obtained by pyrolysis with 60ml of concentrated sulfuric acid, stirring for 2h in an oil bath at 25 ℃, cleaning filter residue with hot deionized water after filtering, and drying to obtain the biochar-based solid acid catalyst. Uniformly mixing 0.1g of biochar-based solid acid catalyst, 6.8g of methanol and 5g of oleic acid (with an acid value of 200), stirring and reacting for 3 hours in an oil bath at 65 ℃, detecting and calculating the conversion rate of the oleic acid after the reaction is finished, centrifuging the reaction mixture, filtering and recovering the catalyst, carrying out rotary evaporation on the filtrate to obtain a methyl oleate product, diluting the product with absolute ethyl alcohol, and titrating with 0.01mol/L KOH to obtain the acid value.
Example 11:
pyrolyzing the corn cob with hemicellulose removed in a muffle furnace for 3h at 300 ℃ in a nitrogen atmosphere, mixing 4g of biochar obtained by pyrolysis with 60ml of concentrated sulfuric acid, stirring for 4h in an oil bath at 25 ℃, cleaning filter residue with hot deionized water after filtering, and drying to obtain the biochar-based solid acid catalyst. Uniformly mixing 0.1g of biochar-based solid acid catalyst, 6.8g of methanol and 5g of oleic acid (with an acid value of 200), stirring and reacting for 3 hours in an oil bath at 75 ℃, detecting and calculating the conversion rate of the oleic acid after the reaction is finished, centrifuging the reaction mixture, filtering and recovering the catalyst, carrying out rotary evaporation on the filtrate to obtain a methyl oleate product, diluting the product with absolute ethyl alcohol, and titrating with 0.01mol/L KOH to obtain the acid value.
Example 12:
pyrolyzing the corn cob with hemicellulose removed in a muffle furnace for 3h at 300 ℃ in a nitrogen atmosphere, mixing 4g of biochar obtained by pyrolysis with 60ml of concentrated sulfuric acid, stirring for 4h in an oil bath at 25 ℃, cleaning filter residue with hot deionized water after filtering, and drying to obtain the biochar-based solid acid catalyst. Uniformly mixing 0.1g of biochar-based solid acid catalyst, 6.8g of methanol and 5g of oleic acid (with an acid value of 200), stirring and reacting for 6 hours in an oil bath at 65 ℃, detecting and calculating the conversion rate of the oleic acid after the reaction is finished, centrifuging the reaction mixture, filtering and recovering the catalyst, carrying out rotary evaporation on the filtrate to obtain a methyl oleate product, diluting the product with absolute ethyl alcohol, and titrating with 0.01mol/L KOH to obtain the acid value.
Example 13:
pyrolyzing the corn cob with hemicellulose removed in a muffle furnace for 3h at 300 ℃ in a nitrogen atmosphere, mixing 4g of biochar obtained by pyrolysis with 60ml of concentrated sulfuric acid, stirring for 4h in an oil bath at 25 ℃, cleaning filter residue with hot deionized water after filtering, and drying to obtain the biochar-based solid acid catalyst. Uniformly mixing 0.1g of biochar-based solid acid catalyst, 8.5g of methanol and 5g of oleic acid (with an acid value of 200), stirring and reacting for 5 hours in an oil bath at 65 ℃, detecting and calculating the conversion rate of the oleic acid after the reaction is finished, centrifuging the reaction mixture, filtering and recovering the catalyst, carrying out rotary evaporation on the filtrate to obtain a methyl oleate product, diluting the product with absolute ethyl alcohol, and titrating with 0.01mol/L KOH to obtain the acid value.
Example 14:
pyrolyzing the corn cob with hemicellulose removed in a muffle furnace for 3h at 300 ℃ in a nitrogen atmosphere, mixing 4g of biochar obtained by pyrolysis with 60ml of concentrated sulfuric acid, stirring for 4h in an oil bath at 25 ℃, cleaning filter residue with hot deionized water after filtering, and drying to obtain the biochar-based solid acid catalyst. Uniformly mixing 0.2g of biochar-based solid acid catalyst, 8.5g of methanol and 5g of oleic acid (with an acid value of 200), stirring and reacting for 5 hours in an oil bath at 65 ℃, detecting and calculating the conversion rate of the oleic acid after the reaction is finished, centrifuging the reaction mixture, filtering and recovering the catalyst, carrying out rotary evaporation on the filtrate to obtain a methyl oleate product, diluting the product with absolute ethyl alcohol, and titrating with 0.01mol/L KOH to obtain the acid value.
In examples 1 to 14, the conversion of oleic acid after the esterification reaction is shown in Table 1.
The biochar-based solid acid catalysts of examples 1-14 were tested for acid content by the following method: mixing the catalyst with 2mol/L NaCl solution according to the solid-to-liquid ratio of 1 g: 800ml of the mixture was ultrasonically displaced for 30min, and the amount of acid was determined by titration with 0.005mol/L NaOH. The results of testing the amount of biochar-based solid acid catalyst acid in examples 1-14 are summarized in table 1.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (8)
1. A method for preparing a biochar-based solid acid catalyst through sulfonation at a low temperature is characterized in that corncobs from which hemicellulose is removed are pyrolyzed and carbonized in a nitrogen atmosphere, the biochar obtained through pyrolysis is mixed with concentrated sulfuric acid and stirred for sulfonation, solid is collected through filtration, washed by hot deionized water and dried, and the biochar-based solid acid catalyst is obtained.
2. The method for preparing the biochar-based solid acid catalyst by low-temperature sulfonation as claimed in claim 1, wherein the temperature for pyrolysis and carbonization is 300-350 ℃, and the time for pyrolysis and carbonization is 3-4 h.
3. The method for preparing the biochar-based solid acid catalyst through low-temperature sulfonation as claimed in claim 1, wherein the mass fraction of concentrated sulfuric acid is 95-98%, and the charging ratio of the concentrated sulfuric acid to biochar is 15-20 ml: 1g of the total weight of the composition.
4. The method for preparing the biochar-based solid acid catalyst by low-temperature sulfonation as claimed in claim 1, wherein the sulfonation temperature is 25-90 ℃ and the sulfonation time is 2-4 h.
5. The biochar-based solid acid catalyst prepared by the method of any one of claims 1 to 4.
6. Use of the biochar-based solid acid catalyst according to claim 5 for catalyzing esterification reactions.
7. The use of claim 6, wherein the biochar-based solid acid catalyst, methanol and oleic acid are uniformly mixed and reacted at normal pressure to form an ester.
8. The use as claimed in claim 7, wherein the reaction temperature is 65-75 ℃, the reaction time is 3-6h, and the molar ratio of methanol to oleic acid is 12-15: 1, the adding amount of the biochar-based solid acid catalyst is 2-4wt% of oleic acid.
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| CN104028294A (en) * | 2014-06-26 | 2014-09-10 | 江南大学 | Solid acid catalyst suitable for microwave-assisted reaction and preparation method of solid acid catalyst |
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| CN113198548A (en) * | 2021-05-13 | 2021-08-03 | 齐鲁工业大学 | Ginger straw-based solid acid catalyst and preparation method and application thereof |
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| CN104028294A (en) * | 2014-06-26 | 2014-09-10 | 江南大学 | Solid acid catalyst suitable for microwave-assisted reaction and preparation method of solid acid catalyst |
| CN107890874A (en) * | 2017-10-30 | 2018-04-10 | 山东大学 | A kind of coal based solid acid catalyst of catalysis for preparing biodiesel oil and preparation method thereof |
| CN113198548A (en) * | 2021-05-13 | 2021-08-03 | 齐鲁工业大学 | Ginger straw-based solid acid catalyst and preparation method and application thereof |
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