CN102218308A - KOH-supported Xanthoceras sorbifolia husk active carbon catalyst and preparation method and application thereof - Google Patents
KOH-supported Xanthoceras sorbifolia husk active carbon catalyst and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 264
- 244000248162 Xanthoceras sorbifolium Species 0.000 title claims abstract description 147
- 235000009240 Xanthoceras sorbifolium Nutrition 0.000 title claims abstract description 147
- 239000003054 catalyst Substances 0.000 title claims abstract description 141
- 239000010903 husk Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 title abstract 4
- 239000003225 biodiesel Substances 0.000 claims abstract description 76
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000004806 packaging method and process Methods 0.000 claims abstract description 11
- 125000004185 ester group Chemical group 0.000 claims abstract 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- 239000003921 oil Substances 0.000 claims description 33
- 235000019198 oils Nutrition 0.000 claims description 33
- 239000000047 product Substances 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 22
- 235000011187 glycerol Nutrition 0.000 claims description 20
- 239000002699 waste material Substances 0.000 claims description 17
- 238000005303 weighing Methods 0.000 claims description 15
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 14
- 239000008158 vegetable oil Substances 0.000 claims description 14
- 241000612118 Samolus valerandi Species 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 235000019737 Animal fat Nutrition 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 235000019197 fats Nutrition 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 235000019482 Palm oil Nutrition 0.000 claims description 3
- 235000019483 Peanut oil Nutrition 0.000 claims description 3
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 3
- 239000002540 palm oil Substances 0.000 claims description 3
- 239000000312 peanut oil Substances 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- 235000020238 sunflower seed Nutrition 0.000 claims description 3
- 239000008162 cooking oil Substances 0.000 claims description 2
- 238000005809 transesterification reaction Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 83
- 150000002148 esters Chemical group 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002585 base Substances 0.000 description 6
- 239000003925 fat Substances 0.000 description 5
- 239000002815 homogeneous catalyst Substances 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000007172 homogeneous catalysis Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000001149 (9Z,12Z)-octadeca-9,12-dienoate Substances 0.000 description 2
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 description 2
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- -1 sodium alkoxide Chemical class 0.000 description 2
- WTTJVINHCBCLGX-UHFFFAOYSA-N (9trans,12cis)-methyl linoleate Natural products CCCCCC=CCC=CCCCCCCCC(=O)OC WTTJVINHCBCLGX-UHFFFAOYSA-N 0.000 description 1
- DVWSXZIHSUZZKJ-UHFFFAOYSA-N 18:3n-3 Natural products CCC=CCC=CCC=CCCCCCCCC(=O)OC DVWSXZIHSUZZKJ-UHFFFAOYSA-N 0.000 description 1
- LNJCGNRKWOHFFV-UHFFFAOYSA-N 3-(2-hydroxyethylsulfanyl)propanenitrile Chemical compound OCCSCCC#N LNJCGNRKWOHFFV-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- PKIXXJPMNDDDOS-UHFFFAOYSA-N Methyl linoleate Natural products CCCCC=CCCC=CCCCCCCCC(=O)OC PKIXXJPMNDDDOS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 1
- ZYNDJIBBPLNPOW-UHFFFAOYSA-N eurucic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCCCCCC(=O)OC ZYNDJIBBPLNPOW-UHFFFAOYSA-N 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- ZYNDJIBBPLNPOW-KHPPLWFESA-N methyl erucate Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(=O)OC ZYNDJIBBPLNPOW-KHPPLWFESA-N 0.000 description 1
- DVWSXZIHSUZZKJ-YSTUJMKBSA-N methyl linolenate Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(=O)OC DVWSXZIHSUZZKJ-YSTUJMKBSA-N 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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- Fats And Perfumes (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a KOH-supported Xanthoceras sorbifolia husk active carbon catalyst and a preparation method and application thereof. The preparation method comprises the following steps of: (1) pretreating Xanthoceras sorbifolia husk active carbon; (2) preparing the KOH-supported Xanthoceras sorbifolia husk active carbon catalyst; (3) calcining at high temperature; and (4) packaging finished products. A method for preparing biodiesel by using the catalyst comprises the following steps of: (1) performing ester exchange reaction; (2) recycling glycerol; and (3) preparing a finished product of biodiesel. The invention has the advantages that: the cost of the catalyst is reduced, the catalytic efficiency is improved, the catalyst is easily separated from the product, is easy to regenerate and cannot seriously corrode reaction equipment, reaction conditions are mild, the automatic and continuous operation is easy to realize and the like.
Description
The technical field is as follows:
the invention relates to a catalyst, a preparation method and application thereof, in particular to a xanthoceras sorbifolia seed shell activated carbon supported KOH catalyst, a preparation method and application thereof.
Background art:
in the preparation process of biodiesel, most of catalysts in the ester exchange process are homogeneous catalysts, and NaOH, KOH, sodium alkoxide and concentrated sulfuric acid are generally adopted. NaOH and the like are used as catalysts which are mainly low in price and easy to obtain, but have serious defects such as complex post-treatment, difficult separation, easy corrosion of equipment, easy generation of three wastes and environmental pollution. In addition, when a homogeneous base is used as a catalyst, the water content and the free fatty acid content of the raw material must be strictly limited, and it is usually required that the water content is less than 0.06% and the acid value AV is less than 1 mgKOH/g. In order to overcome the defects of the homogeneous base catalyst in the process of synthesizing the biodiesel, solid base catalysts have been researched more and more. Therefore, the development of a novel solid catalyst to replace the existing homogeneous catalyst has important significance in catalytic reaction.
γ-Al2O3The crystal belongs to a cubic face center close packing configuration, aluminum atoms are irregularly arranged in octahedron and tetrahedron holes formed by oxygen atoms, and the crystal is used as a catalyst carrier, has the characteristics of porosity, high dispersity, high specific surface area, good adsorbability, thermal stability, surface acidity and the like, and is often called as active alumina. KOH, CH3OK、NaOH、CH3The homogeneous base catalysts such as ONa and the like are all commonly used catalysts in the process of synthesizing biodiesel by ester exchange reaction, wherein the catalytic activity of K-type base is obviously higher than that of Na-type base catalyst, and gamma-Al is used2O3As carriers, by loading potassium salts (e.g. potassium salts)KI、KNO3、K2CO3Etc.) to prepare solid alkali and is used for synthesizing biodiesel through ester exchange reaction.
At present, xanthoceras sorbifolia bunge oil is used for synthesizing biodiesel through ester exchange reaction, a plurality of homogeneous catalysts are mainly used, and the problems that the catalyst and the biodiesel are difficult to separate, complex in post-treatment, incapable of being recycled, harsh in requirements on raw materials, easy to corrode equipment, easy to cause three wastes, and environment-friendly can also occur.
Homogeneous catalyst: the reaction in which the catalyst and the reactant are in the same phase and no phase boundary exists is called homogeneous catalysis, and the catalyst with homogeneous catalysis is called homogeneous catalyst.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a xanthoceras sorbifolia seed shell activated carbon supported KOH catalyst.
The second purpose of the invention is to provide a xanthoceras sorbifolia seed shell activated carbon supported KOH catalyst.
The third purpose of the invention is to provide the application of the xanthoceras sorbifolia seed shell activated carbon supported KOH catalyst in preparation of biodiesel.
The fourth purpose of the invention is to provide a method for preparing biodiesel by using a KOH-supported xanthoceras sorbifolia seed shell activated carbon catalyst.
The first object of the invention is implemented by the following technical scheme, a preparation method of a xanthoceras sorbifolia husk activated carbon supported KOH catalyst sequentially comprises the following steps of (1) pretreating xanthoceras sorbifolia husk activated carbon; (2) preparing a KOH catalyst loaded with activated carbon of xanthoceras sorbifolia seed shells; (3) calcining the activated carbon KOH-loaded catalyst of the xanthoceras sorbifolia shells at the temperature of 300-600 ℃; (4) packaging a finished product; wherein,
(1) pretreating xanthoceras sorbifolia seed shells by using activated carbon: putting the xanthoceras sorbifolia seed shell activated carbon into a drying box, drying for 2-4h at the temperature of 100-;
(2) preparing a xanthoceras sorbifolia seed shell activated carbon supported KOH catalyst: weighing pretreated xanthoceras sorbifolia seed shell activated carbon, adding 10-40% of KOH solution by mass fraction, continuously stirring for 1-2h to uniformly mix the activated carbon and the KOH solution, then putting the activated carbon into a drying box to remove water at the temperature of 100 ℃ and 120 ℃, drying the activated carbon to constant weight, and obtaining the activated carbon supported KOH catalyst with the KOH load of 10-30% by mass fraction after drying;
(3) weighing the catalyst obtained in the step (2), adding the catalyst into a box-type resistance furnace, introducing nitrogen, and calcining at the high temperature of 600 ℃ for 2h at 300 ℃ to obtain a final product;
(4) packaging a finished product: and (3) cooling to room temperature, placing the mixture into a self-sealing bag for storage to obtain a black solid xanthoceras sorbifolia seed shell activated carbon supported KOH catalyst, and placing the black solid xanthoceras sorbifolia seed shell activated carbon supported KOH catalyst into a dryer for storage.
The second purpose of the invention is implemented by the following technical scheme: a KOH-supported xanthoceras sorbifolia seed shell activated carbon catalyst prepared by a method for preparing the KOH-supported xanthoceras sorbifolia seed shell activated carbon catalyst.
The third object of the invention is implemented by the following technical scheme: the use of activated carbon loaded KOH catalyst of xanthoceras sorbifolia shells for preparing biodiesel.
The fourth purpose of the invention is implemented by the following technical scheme: the method for preparing the biodiesel by using the activated carbon supported KOH catalyst of the xanthoceras sorbifolia shells comprises the following steps of (1) performing ester exchange reaction; (2) recovering the catalyst; (3) recovering the glycerol; (4) preparing a finished product of the biodiesel; wherein,
(1) ester exchange reaction: weighing any one of vegetable oil, animal fat or waste fat, adding methanol and shinyleaf yellowhorn shell activated carbon supported KOH catalyst into any one of the vegetable oil, the animal fat or the waste fat, and placing the mixture into a container, wherein the molar ratio of the methanol to the vegetable oil to the any one of the animal fat or the waste fat is (6-12) to 1, and the amount of the shinyleaf yellowhorn shell activated carbon supported KOH catalyst is 1.5-3.5% of the weight of any one of the vegetable oil, the animal fat or the waste fat according to mass fraction; heating the container in which any one of the vegetable oil, the animal fat or the waste fat, the methanol and the shinyleaf yellowhorn seed shell activated carbon loaded KOH catalyst are placed to 55-75 ℃ in a water bath, and reacting to obtain the biodiesel and the byproduct glycerol;
(2) recovering the catalyst: reducing the pressure in a suction filter bottle by the extraction rate of the mixture after the final ester exchange reaction in the step (1) by using an air pump, separating solid from liquid to obtain the activated carbon supported KOH catalyst of the shinyleaf yellowhorn shells, and drying and storing the activated carbon supported KOH catalyst for later use;
(3) and (3) recovering the glycerol: putting the filtrate obtained after the liquid-solid separation in the step (2) into a separating funnel for separating liquid, precipitating and layering, and recovering crude glycerin at the lower layer to obtain a biodiesel product at the upper layer;
(4) preparing a finished biodiesel product: the upper layer product, biodiesel, is firstly cleaned by distilled water, and then the water is removed by anhydrous sodium sulfate, and finally the light yellow and clear biodiesel is obtained.
In the step (1), in the ester exchange reaction, a container in which the xanthoceras sorbifolia oil, the methanol and the activated carbon supported KOH catalyst of the xanthoceras sorbifolia seed shells are placed is subjected to water bath for at least 10 min.
The catalyst of the xanthoceras sorbifolia seed shell activated carbon supported KOH is prepared by the method for preparing the catalyst of the xanthoceras sorbifolia seed shell activated carbon supported KOH.
The vegetable oil is any one of peanut oil, soybean oil, rapeseed oil, sunflower seed oil, palm oil and shinyleaf yellowhorn oil.
The waste grease is illegal cooking oil.
The invention has the advantages that the catalyst prepared by taking the xanthoceras sorbifolia bunge seed shell activated carbon as the carrier utilizes the fact that the xanthoceras sorbifolia seed shell activated carbon has large specific surface area and pore size, so that KOH can be impregnated into the pore size to generate KOH and K2The O active group improves the activity of the catalyst. (1) The activated carbon of xanthoceras sorbifolia shells is used as a carrier to reduce the catalyst contentThe cost is low, and the reaction catalysis efficiency is improved due to the porous structure of the activated carbon; (2) the solid-liquid dual-phase system of the catalyst of the xanthoceras sorbifolia seed shell activated carbon loaded with KOH and the product is easy to separate; (3) the catalyst is easy to regenerate after reaction and can be reused; (4) and does not cause serious corrosion to reaction equipment; (5) the catalyst is mild in reaction conditions, easy to operate, automatic and continuous, and reusable, and has the advantages of high activity, easiness in separation, small corrosion to equipment, no wastewater generation and the like compared with the traditional homogeneous catalysis for preparing biodiesel in a heterogeneous catalysis reaction, so that the raw material source can be effectively widened, the economic competitiveness of the biodiesel is improved, and the pollution is reduced.
Drawings
FIG. 1 is a process flow diagram of the process for synthesizing biodiesel from xanthoceras sorbifolia oil in examples 1, 2 and 3.
FIG. 2 is an infrared spectrum of activated carbon support and calcined xanthoceras sorbifolia seed shell activated carbon supported KOH catalyst. (a represents the infrared spectrogram of the catalyst of the xanthoceras sorbifolia fruit shell activated carbon supported KOH, and b represents the infrared spectrogram of the xanthoceras sorbifolia fruit shell activated carbon).
Fig. 3 is an infrared spectrum of biodiesel prepared from xanthoceras sorbifolia bunge oil and a catalyst of activated carbon supported KOH of xanthoceras sorbifolia shells (1 represents an infrared spectrum of xanthoceras sorbifolia bunge oil, and 2 represents an infrared spectrum of biodiesel).
FIG. 4 is a gas chromatogram of xanthoceras sorbifolia bunge oil for preparing biodiesel.
Detailed Description
Example 1: a preparation method of a xanthoceras sorbifolia husk activated carbon supported KOH catalyst sequentially comprises the following steps of (1) pretreating xanthoceras sorbifolia husk activated carbon; (2) preparing a KOH catalyst loaded with activated carbon of xanthoceras sorbifolia seed shells; (3) calcining the activated carbon KOH-loaded xanthoceras sorbifolia seed shell catalyst at 300 ℃; (4) packaging a finished product; wherein,
(1) pretreating xanthoceras sorbifolia seed shells by using activated carbon: putting the xanthoceras sorbifolia seed shell activated carbon into a drying oven, and drying for 2h at 100 ℃ to remove impurities and water on the surface of the xanthoceras sorbifolia seed shell activated carbon;
(2) preparing a xanthoceras sorbifolia seed shell activated carbon supported KOH catalyst: weighing 500g of pretreated xanthoceras sorbifolia seed shell activated carbon, adding 55ml of 10% KOH solution, continuously stirring for 1-2h to uniformly mix the mixture, then putting the mixture into a drying box to remove water at the temperature of 100 ℃ and 120 ℃, drying the mixture to constant weight, and obtaining the activated xanthoceras sorbifolia seed shell supported KOH catalyst with the KOH load of 10% by mass fraction after drying;
(3) weighing the catalyst obtained in the step (2), adding the catalyst into a box-type resistance furnace (FSX2-12-15N), introducing nitrogen, and calcining at the high temperature of 300 ℃ for 2 hours to obtain a final product;
(4) packaging a finished product: and (3) cooling to room temperature, placing the mixture into a self-sealing bag for storage to obtain a black solid xanthoceras sorbifolia seed shell activated carbon supported KOH catalyst, and placing the black solid xanthoceras sorbifolia seed shell activated carbon supported KOH catalyst into a dryer for storage.
The yellowhorn seed shell activated carbon supported KOH catalyst can be used for preparing biodiesel.
The method for preparing the biodiesel by using the activated carbon supported KOH catalyst of the xanthoceras sorbifolia shells comprises the following steps of (1) performing ester exchange reaction; (2) recovering the catalyst; (3) recovering the glycerol; (4) preparing a finished product of the biodiesel; wherein,
(1) ester exchange reaction: weighing 500ml of shinyleaf yellowhorn oil, adding methanol and the shinyleaf yellowhorn seed shell activated carbon supported KOH catalyst prepared by the method into the shinyleaf yellowhorn oil, and placing the shinyleaf yellowhorn seed shell activated carbon supported KOH catalyst into a container, wherein the molar ratio of the methanol to the shinyleaf yellowhorn oil is 6: 1, and the using amount of the shinyleaf yellowhorn seed shell activated carbon supported KOH catalyst is 1.5% of the weight of the shinyleaf yellowhorn oil according to mass fraction; heating the container in which the xanthoceras sorbifolia Bunge oil, methanol and activated carbon of xanthoceras sorbifolia Bunge seed shells loaded with a KOH catalyst to 55 ℃ in water bath for 100min, and reacting to obtain biodiesel and a byproduct glycerol;
(2) recovering the catalyst: reducing the pressure in a suction filter bottle by the extraction rate of the mixture after the final ester exchange reaction in the step (1) by using an air pump, separating solid from liquid to obtain the activated carbon supported KOH catalyst of the shinyleaf yellowhorn shells, and drying and storing the activated carbon supported KOH catalyst for later use;
(3) and (3) recovering the glycerol: putting the filtrate obtained after the liquid-solid separation in the step (2) into a separating funnel for separating liquid, precipitating and layering, and recovering crude glycerin at the lower layer to obtain a biodiesel product at the upper layer;
(4) preparing a finished biodiesel product: the upper layer product, biodiesel, is firstly cleaned by distilled water, and then the water is removed by anhydrous sodium sulfate, and finally the light yellow and clear biodiesel is obtained.
Example 2: a preparation method of a xanthoceras sorbifolia husk activated carbon supported KOH catalyst sequentially comprises the following steps of (1) pretreating xanthoceras sorbifolia husk activated carbon; (2) preparing a KOH catalyst loaded with activated carbon of xanthoceras sorbifolia seed shells; (3) calcining the activated carbon KOH-loaded xanthoceras sorbifolia seed shell catalyst at 600 ℃; (4) packaging a finished product; wherein,
(1) pretreating xanthoceras sorbifolia seed shells by using activated carbon: putting the xanthoceras sorbifolia seed shell activated carbon into a drying oven, and drying for 4h at 200 ℃ to remove impurities and water on the surface of the xanthoceras sorbifolia seed shell activated carbon;
(2) preparing a xanthoceras sorbifolia seed shell activated carbon supported KOH catalyst: weighing 500g of pretreated xanthoceras sorbifolia shell activated carbon, adding 125ml of 40% KOH solution, continuously stirring for 1-2h to uniformly mix the mixture, then putting the mixture into a drying oven to remove water at 120 ℃, drying the mixture to constant weight, and drying the mixture to obtain a KOH catalyst loaded with 20% of the xanthoceras sorbifolia shell activated carbon;
(3) weighing the catalyst obtained in the step (2), adding the catalyst into a box-type resistance furnace (FSX2-12-15N), introducing nitrogen, and calcining at 600 ℃ for 2h at high temperature to obtain a final product;
(4) packaging a finished product: and (3) cooling to room temperature, placing the mixture into a self-sealing bag for storage to obtain a black solid xanthoceras sorbifolia seed shell activated carbon supported KOH catalyst, and placing the black solid xanthoceras sorbifolia seed shell activated carbon supported KOH catalyst into a dryer for storage.
The yellowhorn seed shell activated carbon supported KOH catalyst can be used for preparing biodiesel.
The method for preparing the biodiesel by using the activated carbon supported KOH catalyst of the xanthoceras sorbifolia shells comprises the following steps of (1) performing ester exchange reaction; (2) recovering the catalyst; (3) recovering the glycerol; (4) preparing a finished product of the biodiesel; wherein,
(1) ester exchange reaction: weighing 500ml of shinyleaf yellowhorn oil, adding methanol and a shinyleaf yellowhorn seed shell activated carbon supported KOH catalyst into the shinyleaf yellowhorn oil, and placing the shinyleaf yellowhorn oil into a container, wherein the molar ratio of the methanol to the shinyleaf yellowhorn seed shell activated carbon supported KOH catalyst is 12: 1, and the using amount of the shinyleaf yellowhorn seed shell activated carbon supported KOH catalyst is 3.5% of the weight of the shinyleaf yellowhorn oil according to mass fraction; heating a container in which the xanthoceras sorbifolia Bunge oil, methanol and activated carbon of xanthoceras sorbifolia Bunge seed shells loaded with a KOH catalyst to 75 ℃ in water bath for 150min, and reacting to obtain biodiesel and a byproduct glycerol;
(2) and (3) simultaneous catalyst recovery: reducing the pressure in a suction filter bottle by the extraction rate of the mixture after the final ester exchange reaction in the step (1) by using an air pump, separating solid from liquid to obtain the activated carbon supported KOH catalyst of the shinyleaf yellowhorn shells, and drying and storing the activated carbon supported KOH catalyst for later use;
(3) and (3) recovering the glycerol: putting the filtrate obtained after the liquid-solid separation in the step (2) into a separating funnel for separating liquid, precipitating and layering, and recovering crude glycerin at the lower layer to obtain a biodiesel product at the upper layer;
(4) preparing a finished biodiesel product: the upper layer product, biodiesel, is firstly cleaned by distilled water, and then the water is removed by anhydrous sodium sulfate, and finally the light yellow and clear biodiesel is obtained.
Example 3: a preparation method of a xanthoceras sorbifolia husk activated carbon supported KOH catalyst sequentially comprises the following steps of (1) pretreating xanthoceras sorbifolia husk activated carbon; (2) preparing a KOH catalyst loaded with activated carbon of xanthoceras sorbifolia seed shells; (3) calcining the activated carbon KOH-loaded xanthoceras sorbifolia seed shell catalyst at 500 ℃; (4) packaging a finished product; wherein,
(1) pretreating xanthoceras sorbifolia seed shells by using activated carbon: putting the xanthoceras sorbifolia seed shell activated carbon into a drying oven, and drying for 3h at 150 ℃ to remove impurities and water on the surface of the xanthoceras sorbifolia seed shell activated carbon;
(2) preparing a xanthoceras sorbifolia seed shell activated carbon supported KOH catalyst: weighing 500g of pretreated xanthoceras sorbifolia shell activated carbon, adding 214ml of 30% KOH solution, continuously stirring for 1-2h to uniformly mix the mixture, then putting the mixture into a drying oven to remove water at 110 ℃, drying the mixture to constant weight, and drying the mixture to obtain a KOH catalyst loaded with 30% of the xanthoceras sorbifolia shell activated carbon by mass fraction;
(3) weighing the catalyst obtained in the step (2), adding the catalyst into a box-type resistance furnace (FSX2-12-15N), introducing nitrogen, and calcining at 450 ℃ for 2h to obtain a final product;
(4) packaging a finished product: and (3) cooling to room temperature, placing the mixture into a self-sealing bag for storage to obtain a black solid xanthoceras sorbifolia seed shell activated carbon supported KOH catalyst, and placing the black solid xanthoceras sorbifolia seed shell activated carbon supported KOH catalyst into a dryer for storage.
The KOH-supported xanthoceras sorbifolia seed shell activated carbon catalyst prepared by the method can be used for preparing biodiesel.
The method for preparing the biodiesel by using the activated carbon supported KOH catalyst of the xanthoceras sorbifolia shells comprises the following steps of (1) performing ester exchange reaction; (2) recovering the catalyst; (3) recovering the glycerol; (4) preparing a finished product of the biodiesel; wherein,
(1) ester exchange reaction: weighing shinyleaf yellowhorn oil, adding methanol and a shinyleaf yellowhorn seed shell activated carbon supported KOH catalyst into the shinyleaf yellowhorn oil, and placing the shinyleaf yellowhorn oil into a container, wherein the molar ratio of the methanol to the vegetable oil to the animal oil or the waste oil is 9: 1, and the using amount of the shinyleaf yellowhorn seed shell activated carbon supported KOH catalyst is 2.5% of the weight of the shinyleaf yellowhorn oil according to mass fraction; heating the container in which the xanthoceras sorbifolia Bunge oil, methanol and activated carbon of xanthoceras sorbifolia Bunge seed shells loaded with a KOH catalyst to 60 ℃ in water bath for 50min, and reacting to obtain biodiesel and a byproduct glycerol;
(2) recovering the catalyst: reducing the pressure in a suction filter bottle by the extraction rate of the mixture after the final ester exchange reaction in the step (1) by using an air pump, separating solid from liquid to obtain the activated carbon supported KOH catalyst of the shinyleaf yellowhorn shells, and drying and storing the activated carbon supported KOH catalyst for later use;
(3) and (3) recovering the glycerol: putting the filtrate obtained after the liquid-solid separation in the step (2) into a separating funnel for separating liquid, precipitating and layering, and recovering crude glycerin at the lower layer to obtain a biodiesel product at the upper layer;
(4) preparing a finished biodiesel product: the upper layer product, biodiesel, is firstly cleaned by distilled water, and then the water is removed by anhydrous sodium sulfate, and finally the light yellow and clear biodiesel is obtained.
The xanthoceras sorbifolia oil of the above examples 1, 2 and 3 can be prepared from vegetable oil: peanut oil, soybean oil, rapeseed oil, sunflower seed oil, palm oil and the like. The xanthoceras sorbifolia oil of the above examples 1, 2 and 3 can be replaced by waste oils and fats such as waste oils.
Example 4: activated carbon supports and KOH-supported xanthoceras sorbifolia seed shell activated carbon catalysts calcined at 3500 ℃ in the examples were characterized by TENSOR 27 type infrared spectroscopy, and the results are shown in FIG. 2. The activated carbon carrier is 3224cm-1And 1635cm-1The absorption peak is assigned as OH-stretching vibration absorption peak formed by adsorbing water in the air; 3406cm-1The absorption peak is assigned as the hydroxyl vibration peak of KOH; 1058cm-1、881cm-1And 703cm-1The absorption peak at is K2CO3CO3 (2)2-So as to generate; at 550cm-1The absorption peak appeared here is K-O stretching vibration absorption peak.
Example 5: the infrared spectra of the biodiesel produced by the methods of examples 1, 2 and 3. As can be seen from FIG. 3, the distance is 1742.5cm-1A stretching vibration absorption peak of 3015cm with obvious ester bond-1An expansion and contraction vibration absorption peak of 2930cm, with C ═ C bond appearing nearby-1And 2854.8cm-1The absorption peaks are the stretching vibration absorption peaks of C-H bonds, and the characteristic absorption peaks indicate the main functional groups contained in the biodiesel prepared by the catalyst of activated carbon loaded with KOH of the xanthoceras sorbifolia shells, so that the structure of the biodiesel is verified to be an ester structure.
Example 6: FIG. 4 is a gas chromatogram of biodiesel produced by the methods of examples 1, 2 and 3, the xanthoceras sorbifolia oil biodiesel being mainly composed of 6 components, each being 1.85% by mass of palmitic acid methyl ester (C17: 0); methyl linoleate (C19: 2) 42.52%; 16.02% of methyl linolenate (C19: 3); 35.91% of methyl oleate (C19: 1); 2.46 percent of methyl stearate (C19: 0); 1.23 percent of methyl erucate (C23: 1).
Example 7: table 1 shows a comparison of the properties of biodiesel and 0# diesel produced by the methods of examples 1, 2 and 3. The flash point of the biodiesel is much higher than that of the 0# diesel, because the average length of the carbon chain of the biodiesel molecule is longer than that of the mineral diesel molecule, the flash point of the biodiesel is higher than that of the mineral diesel, so that the biodiesel is not easy to cause fire, and compared with the common 0# diesel, the biodiesel has good safety in storage, transportation and use; the biodiesel basically meets the condensation point requirement of 0# diesel, which shows that the biodiesel has better low-temperature performance and can be used except winter in northern areas; the biodiesel is derived from natural plant resources or animal resources, does not contain mechanical impurities, and has little corrosion to an engine; the viscosity, acidity, density and cold filter plugging point of the biodiesel sample basically meet the indexes of 0# diesel.
TABLE 1 comparison of biodiesel and 0# Diesel
Claims (8)
1. A preparation method of a xanthoceras sorbifolia husk activated carbon supported KOH catalyst is characterized by sequentially comprising the following steps of (1) pretreating xanthoceras sorbifolia husk activated carbon; (2) preparing a KOH catalyst loaded with activated carbon of xanthoceras sorbifolia seed shells; (3) calcining the activated carbon KOH-loaded catalyst of the xanthoceras sorbifolia shells at the temperature of 300-600 ℃; (4) packaging a finished product; wherein,
(1) pretreating xanthoceras sorbifolia seed shells by using activated carbon: placing the activated carbon of the seed shell of the shinyleaf yellowhorn in a drying box for drying for 2-4h at the temperature of 100-;
(2) preparing a xanthoceras sorbifolia seed shell activated carbon supported KOH catalyst: weighing pretreated xanthoceras sorbifolia seed shell activated carbon, adding 10-40% of KOH solution by mass fraction, continuously stirring for 1-2h to uniformly mix the activated carbon and the KOH solution, then putting the activated carbon into a drying box to remove water at the temperature of 100 ℃ and 120 ℃, drying the activated carbon to constant weight, and obtaining the activated carbon supported KOH catalyst with the KOH load of 10-30% by mass fraction after drying;
(3) weighing the catalyst obtained in the step (2), adding the catalyst into a box-type resistance furnace, introducing nitrogen, and calcining at the high temperature of 600 ℃ for 2h at 300 ℃ to obtain a final product;
(4) packaging a finished product: and (3) cooling to room temperature, placing the mixture into a self-sealing bag for storage to obtain a black solid xanthoceras sorbifolia seed shell activated carbon supported KOH catalyst, and placing the black solid xanthoceras sorbifolia seed shell activated carbon supported KOH catalyst into a dryer for storage.
2. A KOH-supported xanthoceras sorbifolia seed shell activated carbon catalyst prepared by a method for preparing the KOH-supported xanthoceras sorbifolia seed shell activated carbon catalyst.
3. The use of activated carbon loaded KOH catalyst of xanthoceras sorbifolia shells for preparing biodiesel.
4. The method for preparing the biodiesel by using the activated carbon supported KOH catalyst of the xanthoceras sorbifolia shells is characterized by comprising the following steps of (1) carrying out ester exchange reaction; (2) recovering the catalyst; (3) recovering the glycerol; (4) preparing a finished product of the biodiesel; wherein,
(1) ester exchange reaction: weighing any one of vegetable oil, animal fat or waste fat, adding methanol and shinyleaf yellowhorn shell activated carbon supported KOH catalyst into any one of the vegetable oil, the animal fat or the waste fat, and placing the mixture into a container, wherein the molar ratio of the methanol to the vegetable oil to the any one of the animal fat or the waste fat is (6-12) to 1, and the amount of the KOH catalyst supported by the shinyleaf yellowhorn shell activated carbon is 1.5-3.5% of the weight of any one of the vegetable oil, the animal fat or the waste fat according to mass fraction; heating the container in which any one of the vegetable oil, the animal fat or the waste fat, the methanol and the shinyleaf yellowhorn seed shell activated carbon loaded KOH catalyst are placed to 55-75 ℃ in a water bath, and reacting to obtain the biodiesel and the byproduct glycerol;
(2) recovering the catalyst: reducing the pressure in a suction filter bottle by the extraction rate of the mixture after the final ester exchange reaction in the step (1) by using an air pump, separating solid from liquid to obtain the activated carbon supported KOH catalyst of the shinyleaf yellowhorn shells, and drying and storing the activated carbon supported KOH catalyst for later use;
(3) and (3) recovering the glycerol: putting the filtrate obtained after the liquid-solid separation in the step (2) into a separating funnel for separating liquid, precipitating and layering, and recovering crude glycerin at the lower layer to obtain a biodiesel product at the upper layer;
(4) preparing a finished biodiesel product: the upper layer product, biodiesel, is firstly cleaned by distilled water, and then the water is removed by anhydrous sodium sulfate, and finally the light yellow and clear biodiesel is obtained.
5. The method for preparing biodiesel according to claim 4, wherein in the step (1) of transesterification, the container in which the xanthoceras sorbifolia oil, methanol and the activated carbon-supported KOH catalyst are placed is subjected to water bath for at least 10 min.
6. The method for preparing biodiesel by using the activated carbon-supported KOH catalyst of the xanthoceras sorbifolia shells, as claimed in claim 4, wherein the activated carbon-supported KOH catalyst of the xanthoceras sorbifolia shells is prepared by the method for preparing the activated carbon-supported KOH catalyst of the xanthoceras sorbifolia shells.
7. The method for preparing biodiesel by using the activated carbon supported KOH catalyst of the xanthoceras sorbifolia shells as claimed in claim 4, wherein the vegetable oil is any one of peanut oil, soybean oil, rapeseed oil, sunflower seed oil, palm oil and xanthoceras sorbifolia Bunge oil.
8. The method for preparing biodiesel by using the activated carbon supported KOH catalyst of the xanthoceras sorbifolia shells as claimed in claim 4, wherein the waste oil is illegal cooking oil.
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