CN113926459A - Magnetic carbon-based catalyst and method for preparing biodiesel by using same - Google Patents
Magnetic carbon-based catalyst and method for preparing biodiesel by using same Download PDFInfo
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- CN113926459A CN113926459A CN202111536200.5A CN202111536200A CN113926459A CN 113926459 A CN113926459 A CN 113926459A CN 202111536200 A CN202111536200 A CN 202111536200A CN 113926459 A CN113926459 A CN 113926459A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 77
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000003225 biodiesel Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000000428 dust Substances 0.000 claims abstract description 35
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 239000012263 liquid product Substances 0.000 claims description 12
- 230000009471 action Effects 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 125000003158 alcohol group Chemical group 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 239000010902 straw Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 3
- 239000010803 wood ash Substances 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 238000004064 recycling Methods 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 235000012424 soybean oil Nutrition 0.000 description 9
- 239000003549 soybean oil Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- 239000013543 active substance Substances 0.000 description 7
- 239000002638 heterogeneous catalyst Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000010457 zeolite 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention discloses a magnetic carbon-based catalyst, which is prepared by the following method: grinding the electric furnace dust by using a ball mill, and drying at 75-105 ℃ to obtain pretreated electric furnace dust; taking pretreated electric furnace dust, adding concentrated hydrochloric acid, adding deionized water and a carbon source after reaction, stirring, filtering and washing until the pH value of the solution is neutral, and drying; calcining the dried sample at 600-800 ℃ for more than 2h to obtain the magnetic carbon carrier; mixing the obtained magnetic carbon carrier and sodium methoxide, adding deionized water, mixing at constant temperature, magnetically stirring, drying, and heating the dried sample to 600 ℃ at a heating rate of 5-7 ℃/min under inert gasoC‑700oC, keeping for more than 2h, and cooling to obtain the magnetic carbon-based catalystAn oxidizing agent. The catalyst has good catalytic effect and high biodiesel yield>98% of catalyst recovery rate>90 percent. The recycling capability is excellent, and the yield of the biodiesel can reach more than 80 percent after 7 times of reactions.
Description
Technical Field
The invention relates to a catalyst for biodiesel and a preparation method of the biodiesel, in particular to a magnetic carbon-based catalyst and a method for preparing the biodiesel by using the catalyst.
Background
With the rapid development of global industrialization, the consumption of fossil resources is also continuously increased. Excessive development and utilization of fossil fuels not only cause energy shortage, but also cause destruction of ecological environment and atmospheric pollution, thereby threatening human health and survival. How to develop and effectively utilize clean, environment-friendly and green renewable energy has profound economic and social benefits. Biodiesel is a renewable fuel prepared by transesterification of vegetable oil, animal oil, waste food oil and low-valent alcohol under the action of acidic and basic catalysts, and has attracted much attention in recent years. The biodiesel has physical and chemical properties similar to those of petroleum diesel, can be directly added into an engine for use, and does not need to modify the engine. The combustion process of the biodiesel has the advantages of low content of incombustibles such as carbon smoke, polymer particles and the like, low content of sulfides and aromatic hydrocarbons in gas, nearly zero emission of carbon dioxide and the like, so that the biodiesel becomes one of the best alternatives of the petroleum diesel.
The yield and quality of the biodiesel can be greatly improved by adding the acidic or basic catalyst in the ester exchange reaction process. Therefore, it is crucial to find a wide and sustainable source of catalyst feedstock and to prepare catalyst processes that are cost effective and efficient. The common catalysts comprise homogeneous catalysts and heterogeneous catalysts, and most of the homogeneous catalysts have the defects of pollution, high preparation cost, difficulty in product separation, low reusability and the like. Heterogeneous catalysts can overcome these problems, and in particular, catalysts having magnetic properties are preferred by most researchers. Commonly used heterogeneous catalysts are supported metal oxide catalysts, zeolites, kaolin, and the like. However, most heterogeneous catalysts have poor structural characteristics, such as low specific surface area and pores, resulting in fewer active sites and long catalytic reaction time. Therefore, the preparation of a supported heterogeneous catalyst which is efficient, reusable, low in cost and environmentally friendly is a very potential and challenging problem.
Disclosure of Invention
In order to solve the problems, the invention aims to realize high conversion rate of the biodiesel and recycling of electric furnace dust by preparing the catalyst with high catalytic activity and recycling rate.
All percentages used in the present invention are mass percentages unless otherwise indicated.
One of the purposes of the invention is to provide a preparation method of a magnetic carbon-based catalyst, which comprises the following steps:
(1) electric furnace dust pretreatment:
grinding the electric furnace dust by using a ball mill, and drying at 75-105 ℃ to obtain pretreated electric furnace dust;
(2) preparing a magnetic carbon-based catalyst:
firstly, taking pretreated electric furnace dust, adding concentrated hydrochloric acid, adding deionized water and a carbon source after reaction, stirring, filtering and washing until the pH value of the solution is neutral, and drying;
secondly, calcining the dried sample at 600-800 ℃ for more than 2h to obtain the magnetic carbon carrier;
thirdly, mixing the magnetic carbon carrier obtained in the second step with sodium methoxide, adding deionized water, mixing at constant temperature, magnetically stirring, drying, and then heating the dried sample to 600-700 ℃ at the heating rate of 5-7 ℃/min under inert gasoAnd C, keeping for more than 2 hours, and cooling to obtain the magnetic carbon-based catalyst.
Further, the components of the magnetic carbon-based catalyst comprise, by element: 30-40% of C, Si: 4% -5%, Na: 21% -22%, Fe: 6% -7%, Mg: less than or equal to 1 percent.
Further, the carbon source comprises at least one of straw ash, rice hull ash, waste wood ash and seed hull ash.
Furthermore, the adding amount of the carbon source is 1-2 times of the electric furnace dust.
Further, the addition amount of sodium methoxide is 60-100% of the mass of the magnetic carbon carrier.
Further, the time for constant-temperature mixing and magnetic stirring is more than 1 h.
Further, the constant temperature is 55-95 ℃, wherein when the temperature is controlled to be 55-60 ℃, the adding amount of sodium methoxide is 90-100% of the mass of the magnetic carbon carrier, and the time of constant temperature mixing and magnetic stirring is more than 2 h.
Another object of the present invention is to provide a carbon-based catalyst prepared by the foregoing method.
The invention further aims to provide application of the carbon-based catalyst in preparation of biodiesel.
The invention also aims to provide a preparation method of biodiesel, which specifically comprises the following steps:
(1) mixing oil with lower alcoholn Oil: n Alcohol(s)= 1: 9-1: 15 in a reaction vessel and then adding the aforementioned catalyst in a dosage of 3-9% with respect to the oil;
(2) sealing the reaction container, and reacting for 1-5h at the temperature of 45-95 ℃;
(3) after the reaction is finished, the upper layer is alcohol and byproducts, the middle layer is biodiesel, the catalyst is positioned at the lower layer, the catalyst and the liquid product are separated under the action of an external magnetic field after standing, the liquid product is removed, and the catalyst is left in the reaction container for reuse.
Further, the oil is commercially available or commercially available and edible (including but not limited to soybean oil).
Further, the lower alcohol includes, but is not limited to, methanol.
Research shows that the catalyst carrier has rich pore structure, great specific surface area, high corrosion resistance and high stability. Therefore, the catalyst can be well used as a catalyst carrier, and after the active substance is loaded, the active substance has better uniformity and stability. In order to sufficiently improve the catalytic efficiency of the catalyst, the present application unexpectedly found that when the calcined magnetic carbon-based carrier is impregnated with sodium methoxide, the impregnation amount is controlled within the interval of 60% to 100%, active substances on the surface of the catalyst show an increasing trend as the impregnation amount increases, and when the impregnation amount is higher than 100%, the specific surface area begins to decrease due to the change of the surface of the carbon carrier, so that the active substances cannot be attached to the surface of the carrier, and the addition amount of sodium methoxide is preferably controlled within the range of 60% to 100% as required based on the actual catalytic effect of the present invention.
Research shows that when the impregnation temperature of the catalyst carrier is within 60-75 ℃, the adsorption effect of the catalyst carrier on active substances is obvious, when the impregnation temperature exceeds 75 ℃, the adsorption effect of the carrier on the active substances starts to be reduced, so that the activity starts to be reduced, but the initial reduction change is not obvious, and the obvious reduction trend starts to appear until the temperature reaches 95 ℃. Meanwhile, the invention unexpectedly discovers that when the temperature is controlled to be 55-60 ℃, the adding amount of the methanol is 90-100% of the mass of the magnetic carbon carrier, and the constant-temperature mixing and magnetic stirring time is more than 2h, the ideal catalyst activity can also be obtained. Based on the actual catalytic effect requirement of the invention, the impregnation temperature is controlled to be 55-95 ℃, wherein when the temperature is controlled to be 55-60 ℃, the addition amount of the methanol is 90-100% of the mass of the magnetic carbon carrier, and the time of constant-temperature mixing and magnetic stirring is preferably more than 2 h.
Compared with the prior art, the invention has the following advantages:
1. the method takes electric furnace dust as a raw material, carbon source is introduced under the condition of inert gas, high-temperature calcination is carried out, then sodium methoxide is loaded by a wet impregnation method, and then calcination is carried out to obtain the catalyst with high catalytic activity, and the catalyst is sufficiently separated from catalytic products under the action of an external magnetic field.
2. The magnetic carbon carrier synthesized by the method can be separated from a liquid product after reaction under the action of an external magnetic field, and the primary catalyst yield is more than or equal to 90%.
3. The magnetic carbon carrier synthesized by the method can ensure that active substances are uniformly distributed on the surface, so that sufficient active sites are provided for catalytic reaction, the prepared magnetic carbon-based catalyst has very good catalytic activity and application value, and the yield of the biodiesel is more than or equal to 98%.
4. The magnetic catalyst synthesized by the method has excellent recycling capability, and the yield of the biodiesel can reach more than 80% after 7 reactions under the optimized impregnation condition.
5. This patent is through recycle electric stove dust and straw, rice husk, shell, abandonment timber etc. realized that resource recovery recycles simultaneously, effectively reduces environmental pollution.
Detailed Description
The present invention will be described in further detail by way of examples and comparative examples.
Examples 1 to 12
A method for preparing a magnetic carbon-based catalyst, the method comprising the steps of:
(1) electric furnace dust pretreatment:
grinding the electric furnace dust by using a ball mill, and drying at 80 ℃ to obtain pretreated electric furnace dust;
(2) preparing a magnetic carbon-based catalyst:
firstly, adding concentrated hydrochloric acid into pretreated electric furnace dust, adding deionized water and straw ash with the mass 1 time that of the electric furnace dust after reaction, stirring for 8 hours, filtering and washing until the pH value of the solution is neutral, and drying;
secondly, calcining the dried sample at 600 ℃ for more than 2 hours to obtain the magnetic carbon carrier;
taking the magnetic carbon carrier obtained in the step II, mixing the magnetic carbon carrier with sodium methoxide according to the proportion shown in the table 1, adding deionized water, mixing and magnetically stirring at constant temperature shown in the table 1, drying, heating the dried sample to 600 ℃ at the heating rate of 5 ℃/min under nitrogen gas, keeping for 2h, and cooling to obtain the magnetic carbon-based catalyst, wherein the magnetic carbon-based catalyst comprises the following components in terms of elements through determination: 30.2% of C, Si: 4.5%, Na: 21.2%, Fe: 6.4%, Mg: 0.2 percent.
The method for preparing the biodiesel by using the catalyst comprises the following steps:
(1) mixing 7g of soybean oil and 4.8g of methanol in a reaction vessel, and then adding the magnetic carbon-based catalyst in a dose of 6wt% with respect to the soybean oil;
(2) sealing the reaction container, and reacting for 2h at 65 ℃;
(3) after the reaction is finished, the upper layer is alcohol and byproducts, the middle layer is biodiesel, the catalyst is positioned at the lower layer, the catalyst and the liquid product are separated under the action of an external magnetic field after standing, the liquid product is removed, and the catalyst is left in the reaction container for reuse.
The catalyst is magnetically separated, and the catalyst is not treated, and the catalytic experiment is continued until the catalyst is obviously deactivated. When the yield of the tested biodiesel drops below 80 percent, stopping the cycle test experiment, wherein the cycle number is the recyclable number of the catalyst:
example 13
A method for preparing a magnetic carbon-based catalyst, the method comprising the steps of:
(1) electric furnace dust pretreatment:
grinding the electric furnace dust by using a ball mill, and drying at 100 ℃ to obtain pretreated electric furnace dust;
(2) preparing a magnetic carbon-based catalyst:
firstly, taking pretreated electric furnace dust, adding concentrated hydrochloric acid, adding deionized water and rice hulls with the mass of 1.5 times that of the electric furnace dust after reaction, stirring for 8 hours, filtering and washing until the pH value of the solution is neutral, and drying;
secondly, calcining the dried sample at 700 ℃ for more than 2h to obtain the magnetic carbon carrier;
mixing the magnetic carbon carrier obtained in the step (c) with sodium methoxide, wherein the addition amount of the sodium methoxide is 70 percent of that of the magnetic carbon carrier, adding deionized water, and adding the deionized water to 80 percent of that of the magnetic carbon carrieroC, mixing at constant temperature, magnetically stirring for 3h, drying, and heating the dried sample to 600 ℃ at a heating rate of 6 ℃/min under nitrogen gasoAnd C, keeping for 3 hours, and cooling to obtain the magnetic carbon-based catalyst, wherein the magnetic carbon-based catalyst comprises the following components in terms of elements: 39.1% of C, Si: 4.2%, Na: 21.1%, Fe: 6%, Mg: 0.18 percent.
The method for preparing the biodiesel by using the catalyst comprises the following steps:
(1) mixing 7g of soybean oil and 3.2g of methanol in a reaction vessel, and then adding the magnetic carbon-based catalyst in a dose of 9wt% with respect to the soybean oil;
(2) sealing the reaction container, and reacting for 3h at 90 ℃;
(3) after the reaction is finished, the upper layer is alcohol and byproducts, the middle layer is biodiesel, the catalyst is positioned at the lower layer, the catalyst and the liquid product are separated under the action of an external magnetic field after standing, the liquid product is removed, and the catalyst is left in the reaction container for reuse.
The catalyst is magnetically separated, and the catalyst is not treated, and the catalytic experiment is continued until the catalyst is obviously deactivated. And when the yield of the tested biodiesel drops below 80 percent, stopping the cycle test experiment, wherein the cycle number is the recyclable number of the catalyst. The biodiesel yield for this example was determined to be 98.72% and the catalyst cycle time was 8.
Example 14
A method for preparing a magnetic carbon-based catalyst, the method comprising the steps of:
(1) electric furnace dust pretreatment:
grinding the electric furnace dust by using a ball mill, and drying at 105 ℃ to obtain pretreated electric furnace dust;
(2) preparing a magnetic carbon-based catalyst:
firstly, adding concentrated hydrochloric acid into pretreated electric furnace dust, adding deionized water and shell ash with the mass 2 times that of the electric furnace dust after reaction, stirring, filtering and washing until the pH value of the solution is neutral, and drying;
secondly, calcining the dried sample at 800 ℃ for 4h to obtain the magnetic carbon carrier;
thirdly, the magnetic carbon carrier obtained in the second step and sodium methoxide are carried outAfter mixing, deionized water was added at 95 deg.CoC, mixing at constant temperature, magnetically stirring for more than 4h, drying, and heating the dried sample to 700 ℃ at a heating rate of 7 ℃/min under nitrogen gasoAnd C, keeping for 4h, and cooling to obtain the magnetic carbon-based catalyst, wherein the magnetic carbon-based catalyst comprises the following components in terms of elements: 39.8% of C, Si: 4.9%, Na: 21.7%, Fe: 6.8%, Mg: 0.6 percent.
The method for preparing the biodiesel by using the catalyst comprises the following steps:
(1) mixing 7g of soybean oil and 4.8g of methanol in a reaction vessel, and then adding the magnetic carbon-based catalyst in a dosage of 9wt% relative to the soybean oil;
(2) sealing the reaction container, and reacting for 5h at 95 ℃;
(3) after the reaction is finished, the upper layer is alcohol and byproducts, the middle layer is biodiesel, the catalyst is positioned at the lower layer, the catalyst and the liquid product are separated under the action of an external magnetic field after standing, the liquid product is removed, and the catalyst is left in the reaction container for reuse.
The catalyst is magnetically separated, and the catalyst is not treated, and the catalytic experiment is continued until the catalyst is obviously deactivated. And when the yield of the tested biodiesel drops below 80 percent, stopping the cycle test experiment, wherein the cycle number is the recyclable number of the catalyst. The biodiesel yield for this example was determined to be 98.45% and the catalyst cycle time was 8.
Comparative examples 1 to 7
A method for preparing a magnetic carbon-based catalyst, the method comprising the steps of:
(1) electric furnace dust pretreatment:
grinding the electric furnace dust same as that in the example 1 by using a ball mill, and drying at 80 ℃ to obtain pretreated electric furnace dust;
(2) preparing a magnetic carbon-based catalyst:
firstly, taking pretreated electric furnace dust, adding concentrated hydrochloric acid, adding deionized water and straws after reaction, stirring, filtering and washing until the pH value of the solution is neutral, and drying;
secondly, calcining the dried sample at 600 ℃ for more than 2 hours to obtain the magnetic carbon carrier;
mixing the magnetic carbon carrier obtained in the step (II) with sodium methoxide according to the proportion shown in the table 2, adding deionized water, mixing and magnetically stirring at constant temperature shown in the table 2, drying, heating the dried sample to 600 ℃ at the heating rate of 5 ℃/min under nitrogen gas, keeping for 2h, and cooling to obtain the magnetic carbon-based catalyst.
The method for preparing the biodiesel by using the catalyst comprises the following steps:
(1) 4g of soybean oil and 2.74g of methanol were mixed in a reaction vessel, and then the aforementioned magnetic carbon-based catalyst was added in a dose of 6wt% with respect to soybean oil;
(2) sealing the reaction container, and reacting for 2h at 65 ℃;
(3) after the reaction is finished, the upper layer is alcohol and byproducts, the middle layer is biodiesel, the catalyst is positioned at the lower layer, the catalyst and the liquid product are separated under the action of an external magnetic field after standing, the liquid product is removed, and the catalyst is left in the reaction container for reuse.
The catalyst is magnetically separated, and the catalyst is not treated, and the catalytic experiment is continued until the catalyst is obviously deactivated. When the yield of the tested biodiesel drops below 80 percent, stopping the cycle test experiment, wherein the cycle number is the recyclable number of the catalyst:
the above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of a magnetic carbon-based catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) electric furnace dust pretreatment:
grinding the electric furnace dust by using a ball mill, and drying at 75-105 ℃ to obtain pretreated electric furnace dust;
(2) preparing a magnetic carbon-based catalyst:
firstly, taking pretreated electric furnace dust, adding concentrated hydrochloric acid, adding deionized water and a carbon source after reaction, stirring, filtering and washing until the pH value of the solution is neutral, and drying;
secondly, calcining the dried sample at 600-800 ℃ for more than 2h to obtain the magnetic carbon carrier;
thirdly, mixing the magnetic carbon carrier obtained in the second step with sodium methoxide, adding deionized water, mixing at constant temperature, magnetically stirring, drying, and then heating the dried sample to 600 ℃ at the heating rate of 5-7 ℃/min under inert gasoC -700oAnd C, keeping for more than 2 hours, and cooling to obtain the magnetic carbon-based catalyst.
2. The method of claim 1, wherein: the magnetic carbon-based catalyst comprises the following components in terms of elements: 30-40% of C, Si: 4-5%, Na: 21-22%, Fe: 6-7%, Mg: less than or equal to 1 percent.
3. The method of claim 1, wherein: the carbon source comprises at least one of straw ash, rice hull ash, waste wood ash and seed hull ash.
4. The method of claim 1, wherein: the adding amount of the carbon source is 1-2 times of the electric furnace dust.
5. The method of claim 1, wherein: the addition amount of sodium methoxide is 60-100% of the mass of the magnetic carbon carrier.
6. The method of claim 1, wherein: the time of constant-temperature mixing and magnetic stirring is more than 1 h.
7. The method of any one of claims 1-6, wherein: the constant temperature is 55-95 ℃, wherein when the temperature is controlled to be 55-60 ℃, the adding amount of the sodium methoxide is 90-100% of the mass of the magnetic carbon carrier, and the time of constant temperature mixing and magnetic stirring is more than 2 h.
8. A magnetic carbon-based catalyst characterized by: the catalyst is prepared by the method of any one of claims 1 to 7.
9. Use of a catalyst according to claim 8 in the preparation of biodiesel.
10. The preparation method of the biodiesel is characterized by comprising the following steps:
(1) mixing oil with lower alcoholn Oil: n Alcohol(s)= 1: 9-1: 15 in a reaction vessel and then adding the aforementioned catalyst in a dosage of 3% to 9% with respect to the oil;
(2) sealing the reaction container, and reacting for 1-5h at the temperature of 45-95 ℃;
(3) after the reaction is finished, the upper layer is alcohol and byproducts, the middle layer is biodiesel, the catalyst is positioned at the lower layer, and the catalyst and the liquid product are separated under the action of an external magnetic field after standing.
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