CN108219973B - Method for preparing biodiesel by utilizing kitchen or slaughterhouse animal solid waste - Google Patents

Method for preparing biodiesel by utilizing kitchen or slaughterhouse animal solid waste Download PDF

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CN108219973B
CN108219973B CN201711391293.0A CN201711391293A CN108219973B CN 108219973 B CN108219973 B CN 108219973B CN 201711391293 A CN201711391293 A CN 201711391293A CN 108219973 B CN108219973 B CN 108219973B
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solid
biodiesel
kitchen
ceo
base catalyst
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CN108219973A (en
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王睿
乔森
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Shenzhen Research Institute Of Shandong University
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Shenzhen Research Institute Of Shandong University
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    • 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
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/83—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 rare earths or actinides
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33—Electric or magnetic properties
    • 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
    • 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)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a method for preparing biodiesel by utilizing kitchen or slaughterhouse animal solid waste. Adopts a novel solid catalyst, the solid base catalyst is a magnetic carrier loaded with KOH, and the magnetic carrier is Fe3O4With CeO2The composite material has a molar ratio of 1: 1.8-2.2. The method realizes the efficient utilization of the kitchen or slaughterhouse animal solid waste to prepare the biodiesel, and simultaneously realizes the efficient utilization of the catalyst so as to reduce the production cost of the biodiesel.

Description

Method for preparing biodiesel by utilizing kitchen or slaughterhouse animal solid waste
Technical Field
The invention relates to a method for preparing biodiesel, in particular to a method for preparing biodiesel by taking solid wastes of kitchen or slaughter house animals as raw materials and magnetic solid alkali as a catalyst on the basis of screening an optimal active component carrier, and belongs to the technical field of biological energy.
Background
Biodiesel (biodiesel), also known as fatty acid methyl ester, refers to a renewable diesel fuel that can replace petroleum diesel, which is prepared from oil crops such as soybean, rape, cotton, palm, etc., aquatic plant oil and fat such as wild oil plants and engineering microalgae, animal oil and fat, food and beverage waste oil, etc., as raw materials by ester exchange or thermochemical process.
The method for preparing the biodiesel mainly comprises a physical method, a chemical method, a biological enzyme method and a supercritical method, wherein the ester exchange method in the chemical method is the most used method for preparing the biodiesel in the prior art, namely animal and vegetable oil, microbial oil and the like are used as raw materials and are reacted with short-chain alcohol substances such as methanol or ethanol and the like under the action of a catalyst.
At present, the equipment and the process for producing the biodiesel by the ester exchange method are mature, but the method has the following defects: firstly, vegetable oil is mostly used as a raw material and is expensive; secondly, the recovery of the acid-base catalyst is difficult; thirdly, the esterification product is difficult to recover and has higher recovery cost; fourthly, the waste catalyst flows out in the production process, which influences the quality of the biodiesel.
Most of wastes of kitchen and slaughter house animals are treated as garbage, which pollutes the environment and wastes resources, and the wastes contain abundant fat, protein and mineral substances, and the research in the current stage is mainly focused on how to carry out secondary utilization on the wastes. The animal waste, especially the livestock viscera, contains a large amount of fat, and can be used as raw materials for producing biodiesel.
Therefore, how to effectively utilize the waste of the kitchen or slaughterhouse animals and produce the biodiesel in a green and high-efficiency manner is a problem to be solved urgently in the field.
Disclosure of Invention
In order to solve the defects of the prior art, one of the purposes of the invention is to provide the application of the solid base catalyst in the preparation of the biodiesel by utilizing the kitchen or slaughter house animal solid waste, which not only can secondarily utilize the cheap kitchen or slaughter house animal solid waste, but also can efficiently prepare the biodiesel and improve the utilization times of the catalyst.
In order to achieve the purpose, the technical scheme of the invention is as follows:
application of solid base catalyst in preparation of biodiesel by utilizing kitchen or slaughterhouse animal solid waste, wherein the solid base catalyst is a magnetic carrier loaded with KOH, and the magnetic carrier is Fe3O4With CeO2The composite material has a molar ratio of 1: 1.8-2.2.
In the prior research, the traditional solid base catalyst is basically used for preparing the biodiesel by using the soybean oil, but the cost of preparing the biodiesel by using the soybean oil is higher, so that the inventor of the application places the research into the solid waste of the kitchen or slaughter house, finds that the traditional solid base catalyst with natural graphite powder and bamboo charcoal as carriers has higher recovery rate of the biodiesel prepared by using the soybean oil in the research process, but the recovery rate of the traditional solid base catalyst for preparing the biodiesel by using the solid waste of the kitchen or slaughter house is lower, and aims at solving the problem that the solid waste of the kitchen or slaughter house is lower in the preparation of the biodiesel by using the traditional solid base catalystThe research on the novel solid base catalyst shows that when Fe is used3O4With CeO2When the composite material with the molar ratio of 1: 1.8-2.2 is a magnetic carrier material loaded with potassium hydroxide, the biodiesel can be efficiently prepared, and the utilization times of the catalyst can be increased.
The invention also aims to provide a method for preparing biodiesel by utilizing the solid wastes of the kitchen or slaughter house animals.
The invention has the beneficial effects that:
1) the raw materials used by the invention are kitchen or slaughterhouse animal solid wastes which are cheap and easy to obtain, and the biodiesel can be produced while garbage is treated, thereby belonging to an environment-friendly green process.
2) In the solid catalyst of the present invention, when Fe3O4With CeO2When the composite material with the molar ratio of 1: 1.8-2.2 is a magnetic carrier material loaded with potassium hydroxide, the biodiesel can be efficiently prepared, and the utilization times of the catalyst can be increased, so that the biodiesel can be efficiently prepared by efficiently utilizing the kitchen or slaughterhouse animal solid waste, and the catalyst can be efficiently utilized, so that the production cost of the biodiesel is reduced.
3) The invention has simple process and does not need high-pressure equipment. The adopted equipment has universality, the manufacturing is simple, and the investment cost can be reduced.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The solid waste of the kitchen or slaughterhouse animals in the invention is solid animal fat, such as fat meat and the like.
The salt of the invention is a compound which can be dissolved in water to ionize anions and cations.
As introduced in the background art, the prior art has the defect that it is difficult to effectively utilize kitchen or slaughterhouse animal waste to prepare biodiesel in a green and efficient manner.
The application provides an application of a solid base catalyst in preparation of biodiesel by utilizing solid wastes of kitchen or slaughter house animals, wherein the solid base catalyst is a magnetic carrier loaded with KOH, and the magnetic carrier is Fe3O4With CeO2The composite material has a molar ratio of 1: 1.8-2.2.
In the present application, the solid waste of kitchen or slaughter house animals is solid animal fat, in the existing research, the traditional solid base catalyst is basically used for preparing the biodiesel from the soybean oil, however, the cost for preparing the biodiesel from the soybean oil is high, so the inventor of the present application places the research emphasis on the solid waste of kitchen or slaughter house animals, and finds that the traditional solid base catalyst with natural graphite powder and bamboo charcoal as carriers has high recovery rate of the biodiesel from the soybean oil in the research process, but the recovery rate of the biodiesel from the solid waste of kitchen or slaughter house animals is low, based on the discovery, the inventor of the present application researches a new solid base catalyst for the solid waste of kitchen or slaughter house animals, and finds that when Fe is used, when Fe is used as the solid waste of kitchen or slaughterhouse animals3O4With CeO2When the composite material with the molar ratio of 1: 1.8-2.2 is used as a magnetic carrier material to load potassium hydroxide, the biodiesel can be efficiently prepared, and the content of the biodiesel can be improvedNumber of times of utilization of catalyst.
Preferably, the mass of KOH in the solid base catalyst is 20-40% of that of the magnetic carrier.
Preferably, the preparation method of the solid base catalyst comprises the following steps:
(1) taking polyoxyethylene ether (Brij35) as a template, adding cerium salt, adjusting the pH value to generate precipitation, aging, drying and calcining to obtain mesoporous CeO2A material;
(2) mesoporous CeO2The mixture of the material, ferric salt and ferrous salt is adjusted with pH value, aged and dried to obtain the magnetic carrier CeO2-Fe3O4A precursor;
(3) mixing a magnetic carrier CeO2-Fe3O4Dispersing the precursor and KOH in water, standing, drying and calcining to obtain the solid base catalyst.
The cerium salt is a compound having a cation containing cerium ion, for example, ammonium cerium nitrate.
The iron salt is a compound whose cation contains iron ions, such as ferric chloride, ferric nitrate, and the like.
The ferrous salt is a compound whose cation contains ferrous ions, such as ferrous chloride, ferrous nitrate, and the like.
More preferably, the molar ratio of the polyoxyethylene ether to cerium ions in the cerium salt is 1.7 to 2.3: 1.
Further preferably, the specific steps of step (1) are as follows: dissolving polyoxyethylene ether and cerium salt in 50% ethanol solution, stirring for 1 hr, and adding ammonia water (NH)3·H2O) adjusting the pH value to 10, stirring for 3h to generate precipitate, standing and aging for 2d, respectively washing with ethanol and water for 2 times, then vacuum drying at 80 ℃, and calcining to obtain mesoporous CeO2A material.
Further preferably, the calcining temperature in the step (1) is 350-550 ℃, and the calcining time is 2-5 h.
Further preferably, the specific steps of step (2) are as follows: adding ferric salt and ferrous salt into the mesoporous CeO2Stirring for 1h, dropwise adding ammonia water until pH is 11.0, stirring for 1h, and standingAging for 2h, absorbing black suspended particles in the solution at the bottom of the reaction container by using a magnet to achieve the effect of accelerating coagulation, filtering, repeatedly washing the solution to be neutral by using distilled water, freeze-drying the obtained solid, and finally obtaining the powdered magnetic carrier CeO2-Fe3O4And (3) precursor.
Still more preferably, the CeO2The material solution comprises the following specific steps: mesoporous CeO2The material was added to water, stirred for 2h, sonicated for 0.5 h.
Further preferably, the specific steps of step (3) are: magnetic carrier CeO2-Fe3O4Dispersing the precursor and KOH in water, stirring for 1h, standing for 2h, drying at 80 ℃, calcining in a muffle furnace, and cooling to room temperature to obtain the magnetic solid base K-CeO2-Fe3O4。
Further preferably, the calcining temperature in the step (3) is 300-500 ℃, and the calcining time is 1-4 h.
According to another embodiment of the application, the method for preparing the biodiesel by utilizing the kitchen or slaughter house animal solid waste is provided, the solid alkali catalyst is mixed with methanol, the kitchen or slaughter house animal solid waste is added, and the biodiesel is obtained by heating reaction after sealing.
In order to remove impurities in the solid wastes of the kitchen or slaughter house animals, the solid wastes of the kitchen or slaughter house animals are preferably subjected to ultrasonic treatment. Further preferably, the ultrasonic power is 15-100 w/L, the temperature is room temperature, and the processing time is 5-30 min.
Preferably, the mass of the solid base catalyst is 1-5% of the mass of the solid waste of the kitchen or slaughterhouse animals.
Preferably, the amount of the methanol is 20 to 60 percent of the mass of the raw materials.
Preferably, the reaction temperature is 80-200 ℃, and the reaction time is 10-120 min.
Preferably, the reacted materials are centrifuged to obtain layered materials, and the supernatant of the layered materials is distilled to obtain the biodiesel. Further preferably, the centrifugal rotating speed of the centrifugal treatment is 8000-15000 r/min, and the centrifugal time is 5-20 min. Further preferably, the distillation temperature is 50-90 ℃, and the distillation time is 5-20 min.
Preferably, the middle of the adopted reaction kettle is provided with a screen, the reaction kettle is divided into an upper layer and a lower layer, the kitchen or slaughterhouse animal solid waste is placed on the screen, and the methanol and the solid base catalyst are placed on the lower layer of the reaction kettle.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
Example 1
Magnetic carrier NGP-Fe3O4The preparation of (1):
(1) grinding 8 g of Natural Graphite Powder (NGP) by using a mechanical grinder, sieving by using a 80-mesh sieve to obtain natural graphite powder particles, dissolving the natural graphite powder particles in 500mL of distilled water, and stirring for 2 hours to obtain a natural graphite powder solution;
(2) 9.731g of ferric chloride hexahydrate (FeCl) were weighed out3﹒6H2O) and 3.5786g of ferrous chloride tetrahydrate (FeCl)2﹒4H2O) (the molar ratio of the two is 2:1), adding the mixture into the natural graphite powder solution, and stirring for dissolving; stirring for 2h by using a stirring rod made of polytetrafluoroethylene, and dropwise adding ammonia water by using a dropping funnel until the pH value is 11.0; after the reaction is finished (after ammonia water is added dropwise), stirring vigorously for 2h, and then standing and aging for 2 h; absorbing black suspended particles in the solution at the bottom of the reaction container by a strong magnet to achieve the purpose of rapid coagulation, repeatedly washing the magnetic carrier to neutrality (pH 7.0) by distilled water, performing suction filtration, and drying at 80 ℃ to obtain the magnetic carrier NGP-Fe3O4And is ready for use;
magnetic solid alkali K/NGP-Fe3O4The preparation of (1):
the magnetic carrier NGP-Fe3O4Placing in a container, and adding KOH according to 30% (mass percent) (the loading refers to KOH and the magnetic carrier NGP-Fe)3O4Mass ratio of) and adding KOH solid, and adding 300mL of distilled water to dissolve, stirring for 1h, standing for 2h, and then drying at 80 ℃ to obtain the final productDrying the water at the temperature of 80 ℃, calcining the mixture for 3 hours at the temperature of 500 ℃ in a muffle furnace, and cooling the calcined mixture to the room temperature to obtain the bifunctional magnetic solid base catalyst K/NGP-Fe3O4And storing in sealed bag and drying in a drier.
Example 2
Magnetic carrier BC-Fe3O4The preparation of (1):
(1) grinding 8 g of Bamboo Charcoal (BC) by using a mechanical grinder, sieving by using a 80-mesh sieve to obtain bamboo charcoal particles, dissolving the bamboo charcoal particles in 500mL of distilled water, and stirring for 2 hours to obtain a bamboo charcoal solution;
(2) 9.731g of ferric chloride hexahydrate (FeCl) were weighed out3﹒6H2O) and 3.5786g of ferrous chloride tetrahydrate (FeCl)2﹒4H2O) (the molar ratio of the two is 2:1), adding the bamboo charcoal solution into the bamboo charcoal solution, and stirring for dissolving; stirring for 2h by using a stirring rod made of polytetrafluoroethylene, and dropwise adding ammonia water by using a dropping funnel until the pH value is 11.0; after the reaction is finished (after ammonia water is added dropwise), stirring vigorously for 2h, and then standing and aging for 2 h; absorbing black suspended particles in the solution at the bottom of the reaction container by a strong magnet to achieve the purpose of rapid coagulation, repeatedly washing the magnetic carrier to neutrality (pH 7.0) by distilled water, performing suction filtration, and drying at 80 ℃ to obtain the magnetic carrier BC-Fe3O4And is ready for use;
magnetic solid alkali K/BC-Fe3O4The preparation of (1):
mixing magnetic carrier BC-Fe3O4Placing in a container, and adding KOH according to 30% (mass percent) (the loading refers to KOH and magnetic carrier BC-Fe)3O4The mass ratio of the components to the components in the solution), adding KOH solid, adding 300mL of distilled water for dissolving, stirring for 1h, standing for 2h, drying at 80 ℃, drying moisture at 80 ℃, calcining in a muffle furnace at 500 ℃ for 3h, and cooling to room temperature to obtain the bifunctional magnetic solid base catalyst K/BC-Fe3O4And storing in sealed bag and drying in a drier.
Example 3
Magnetic carrier CeO2-Fe3O4The preparation of (1):
(1) respectively taking polyoxyethylene ether (Brij35) asTemplate is cerium ammonium nitrate (Ce (NH)4)2(NO3)6) Is cerium source at a molar ratio of 2:1, and is dissolved in 50% ethanol solution, stirred for 1 hr, and then treated with ammonia (NH)3·H2O) adjusting the pH value to 10, stirring for 3h to generate precipitate, standing and aging for 2d, respectively washing with ethanol and water for 2 times, then vacuum drying at 80 ℃, calcining for 4h at 400 ℃ to obtain mesoporous CeO2A material.
(2) 6.2g of the prepared CeO were weighed2Dissolving the material in 300mL of distilled water, stirring for 2h, and performing ultrasonic treatment for 0.5h to obtain CeO2And (3) solution.
(3) 9.731g of iron trichloride hexahydrate (FeCl) were weighed out in a molar ratio of 2:13·6H2O) and 3.5786g of ferrous chloride tetrahydrate (FeCl)2·4H2O) to the above CeO2In solution (as Fe)3O4With CeO2Adding the mixture according to a molar ratio of 1: 2), stirring the mixture for 1 hour by using a polytetrafluoroethylene stirring rod, dropwise adding ammonia water by using a dropping funnel until the pH value is 11.0, then stirring the mixture vigorously for 1 hour, standing and aging the mixture for 2 hours, absorbing black suspended particles in the solution at the bottom of a reaction vessel by using a strong magnet to achieve an effect of accelerating coagulation, filtering the mixture, repeatedly washing the mixture by using distilled water until the mixture is neutral, freeze-drying the obtained solid, and finally obtaining a powdery magnetic carrier CeO2-Fe3O4And (3) precursor.
(4) The precursor CeO of the magnetic carrier2-Fe3O4Putting the mixture into a 500mL beaker, adding KOH solid with 30% (mass percentage) of KOH load, adding 300mL of distilled water for dissolving, stirring for 1h, standing for 2h, drying at 80 ℃, calcining in a muffle furnace at 500 ℃ for 3h, and cooling to room temperature to obtain the magnetic solid alkali K/CeO2-Fe3O4And stored in a sample bottle and put into a desiccator for later use.
Example 4
Magnetic carrier CeO2-Fe3O4The preparation of (1):
(1) respectively using polyoxyethylene ether (Brij35) as template and cerium ammonium nitrate (Ce (NH)4)2(NO3)6) Is cerium source with the molar ratio of 2:1, mixingMixing the two solutions, stirring for 1 hr, and adding ammonia (NH)3·H2O) adjusting the pH value to 10, stirring for 3h to generate precipitate, standing and aging for 2d, respectively washing with ethanol and water for 2 times, then vacuum drying at 80 ℃, calcining for 4h at 400 ℃ to obtain mesoporous CeO2A material.
(2) 3.1g of the prepared CeO were weighed2Dissolving the material in 300mL of distilled water, stirring for 2h, and performing ultrasonic treatment for 0.5h to obtain CeO2And (3) solution.
(3) 9.731g of iron trichloride hexahydrate (FeCl) were weighed out in a molar ratio of 2:13·6H2O) and 3.5786g of ferrous chloride tetrahydrate (FeCl)2·4H2O) to the above CeO2In solution (as Fe)3O4With CeO2Adding with a molar ratio of 1: 1), stirring for 1h by using a polytetrafluoroethylene stirring rod, dropwise adding ammonia water by using a dropping funnel until the pH value is 11.0, then stirring vigorously for 1h, standing and aging for 2h, absorbing black suspended particles in the solution at the bottom of a reaction vessel by using a strong magnet to achieve an effect of accelerating coagulation, filtering, repeatedly washing with distilled water to be neutral, freeze-drying the obtained solid, and finally obtaining a powdery magnetic carrier CeO2-Fe3O4And (3) precursor.
(4) The precursor CeO of the magnetic carrier2-Fe3O4Putting the mixture into a 500mL beaker, adding KOH solid with 30% (mass percentage) of KOH load, adding 300mL of distilled water for dissolving, stirring for 1h, standing for 2h, drying at 80 ℃, calcining in a muffle furnace at 500 ℃ for 3h, and cooling to room temperature to obtain the magnetic solid alkali K/CeO2-Fe3O4And stored in a sample bottle and put into a desiccator for later use.
Example 5
Magnetic carrier CeO2-Fe3O4The preparation of (1):
(1) respectively using polyoxyethylene ether (Brij35) as template and cerium ammonium nitrate (Ce (NH)4)2(NO3)6) Is cerium source at a molar ratio of 2:1, and is dissolved in 50% ethanol solution, stirred for 1 hr, and then treated with ammonia (NH)3·H2O) adjusting the pH value to 10, stirring for 3h to generate precipitateThen standing and aging for 2d, respectively washing with ethanol and water for 2 times, then vacuum drying at 80 ℃, calcining for 4h at 400 ℃ to obtain mesoporous CeO2A material.
(2) 9.3g of the prepared CeO were weighed2Dissolving the material in 300mL of distilled water, stirring for 2h, and performing ultrasonic treatment for 0.5h to obtain CeO2And (3) solution.
(3) 9.731g of iron trichloride hexahydrate (FeCl) were weighed out in a molar ratio of 2:13·6H2O) and 3.5786g of ferrous chloride tetrahydrate (FeCl)2·4H2O) to the above CeO2In solution (as Fe)3O4With CeO2Adding the mixture according to a molar ratio of 1: 3), stirring the mixture for 1 hour by using a polytetrafluoroethylene stirring rod, dropwise adding ammonia water by using a dropping funnel until the pH value is 11.0, then stirring the mixture vigorously for 1 hour, standing and aging the mixture for 2 hours, absorbing black suspended particles in the solution at the bottom of a reaction vessel by using a strong magnet to achieve an effect of accelerating coagulation, filtering the mixture, repeatedly washing the mixture by using distilled water until the mixture is neutral, freeze-drying the obtained solid, and finally obtaining a powdery magnetic carrier CeO2-Fe3O4And (3) precursor.
(4) The precursor CeO of the magnetic carrier2-Fe3O4Putting the mixture into a 500mL beaker, adding KOH solid with 30% (mass percentage) of KOH load, adding 300mL of distilled water for dissolving, stirring for 1h, standing for 2h, drying at 80 ℃, calcining in a muffle furnace at 500 ℃ for 3h, and cooling to room temperature to obtain the magnetic solid alkali K/CeO2-Fe3O4And stored in a sample bottle and put into a desiccator for later use.
In order to conveniently separate and recycle the catalyst for multiple times, the method adopts a heterogeneous magnetic catalyst, namely, potassium nitrate with catalytic activity is loaded on a carbon material with high specific surface area, in view of the particularity of raw materials, a carrier with optimal specificity needs to be screened, and 3 different carbon materials with high specific surface areas are respectively adopted as carriers to carry out experiments and carry out two times of recovery experiments to compare catalytic performances, namely natural graphite powder, bamboo charcoal and mesoporous cerium oxide. By experimental comparison (see Table 1 below)
TABLE 1 biodiesel recovery rates for solid base catalysts prepared in examples 1-3
Solid base catalyst Example 1 Example 2 Example 3
Initial yield 83.25％ 89.33％ 93.86％
Primary recovery yield 70.32％ 78.45％ 88.65％
Secondary recovery yield 59.41％ 66.24％ 80.35％
Finally, based on the fact that the loss of the catalyst is low and the reduction of the catalytic efficiency is low, a cerium oxide material is finally selected as an optimal carrier, and a series of comparison experiments are carried out.
Test example 1
Taking 100g of fat meat purchased from a chilled fresh meat store, carrying out ultrasonic treatment for 10min at the power of 30w/L by using an ultrasonic instrument in a laboratory, putting the obtained mixture on a screen of a reaction kettle, adding 2g of the magnetic solid base catalyst in the embodiment 3 into the lower part of the reaction kettle, adding 40g of methanol, heating the reaction kettle to 100 ℃ after sealing, reacting for 60min, then recovering the catalyst, taking out a product, centrifuging for 10min at the speed of 10000r/min, distilling the centrifuged supernatant, distilling at the temperature of 60 ℃ for 15min, and finally calculating the yield of the obtained product by using a gas chromatography internal standard method.
The recovered catalyst is used to replace the catalyst used in the previous step, and the operation is repeated to obtain the yield of the second use.
Biodiesel production was continued using the recovered catalyst until the yield was below 60%.
Test example 2
Taking 100g of kitchen waste purchased from a canteen, carrying out ultrasonic treatment for 10min at the power of 30w/L by using an ultrasonic instrument for a laboratory, putting the obtained mixture on a screen of a reaction kettle, adding 2g of the magnetic solid base catalyst of the embodiment 2 into the lower part of the reaction kettle, adding 40g of methanol, heating the reaction kettle to 100 ℃ after sealing, reacting for 60min, then recovering the catalyst, taking out a product, centrifuging for 10min at the speed of 10000r/min, distilling the centrifuged supernatant, distilling for 15min at the temperature of 60 ℃, and finally calculating the yield of the obtained product by using a gas chromatography internal standard method.
The recovered catalyst is used to replace the catalyst used in the previous step, and the operation is repeated to obtain the yield of the second use.
Biodiesel production was continued using the recovered catalyst until the yield was below 60%.
Test example 3
Taking 100g of animal internal organs purchased from a slaughterhouse, carrying out ultrasonic treatment for 10min at the power of 30w/L by using an ultrasonic instrument in a laboratory, putting the obtained mixture on a screen of a reaction kettle, adding 2g of the magnetic solid base catalyst in the embodiment 1 into the lower part of the reaction kettle, adding 40g of methanol, sealing, heating the reaction kettle to 100 ℃, reacting for 60min, then recovering the catalyst, taking out a product, centrifuging for 10min at the speed of 10000r/min, distilling the centrifuged supernatant, distilling for 15min at the temperature of 60 ℃, and finally calculating the yield of the obtained product by using a gas chromatography internal standard method.
The recovered catalyst is used to replace the catalyst used in the previous step, and the operation is repeated to obtain the yield of the second use.
Biodiesel production was continued using the recovered catalyst until the yield was below 60%.
The yields of the biodiesel obtained in examples 1 to 5 and the recovered biodiesel were calculated, and the data shown in the following table 2 were obtained.
Test example 4
Taking 100g of animal internal organs purchased from a slaughterhouse, carrying out ultrasonic treatment for 10min at the power of 30w/L by using an ultrasonic instrument in a laboratory, putting the obtained mixture on a screen of a reaction kettle, adding 2g of the magnetic solid base catalyst in the embodiment 4 into the lower part of the reaction kettle, adding 40g of methanol, sealing, heating the reaction kettle to 100 ℃, reacting for 60min, then recovering the catalyst, taking out a product, centrifuging for 10min at the speed of 10000r/min, distilling the centrifuged supernatant, distilling for 15min at the temperature of 60 ℃, and finally calculating the yield of the obtained product by using a gas chromatography internal standard method.
The recovered catalyst is used to replace the catalyst used in the previous step, and the operation is repeated to obtain the yield of the second use.
Biodiesel production was continued using the recovered catalyst until the yield was below 60%.
The yields of the biodiesel obtained in examples 1 to 5 and the recovered biodiesel were calculated, and the data shown in the following table 2 were obtained.
Test example 5
Taking 100g of animal internal organs purchased from a slaughterhouse, carrying out ultrasonic treatment for 10min at the power of 30w/L by using an ultrasonic instrument in a laboratory, putting the obtained mixture on a screen of a reaction kettle, adding 2g of the magnetic solid base catalyst in the embodiment 5 into the lower part of the reaction kettle, adding 40g of methanol, sealing, heating the reaction kettle to 100 ℃, reacting for 60min, then recovering the catalyst, taking out a product, centrifuging for 10min at the speed of 10000r/min, distilling the centrifuged supernatant, distilling for 15min at the temperature of 60 ℃, and finally calculating the yield of the obtained product by using a gas chromatography internal standard method.
The recovered catalyst is used to replace the catalyst used in the previous step, and the operation is repeated to obtain the yield of the second use.
Biodiesel production was continued using the recovered catalyst until the yield was below 60%.
The following data in Table 2 were obtained by calculating the yields of test examples 1 to 5 and the recovered biodiesel.
TABLE 2 test examples 1-5 and their biodiesel yields after recovery
Test example 1 Test example 2 Test example 3 Test example 4 Test example 5
For the first time 93.86％ 88.45％ 83.29％ 81.28％ 84.12％
For the second time 88.65％ 82.28％ 75.66％ 73.41％ 72.59％
The third time 82.35％ 75.77％ 68.69％ 66.40％ 61.38％
Fourth time 73.43％ 67.64％ 57.49％ 54.81％ 49.89％
Fifth time 61.97％ 58.35％
The sixth time 55.49％
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (12)

1. The application of the solid base catalyst in the preparation of biodiesel by utilizing kitchen or slaughterhouse animal solid waste is characterized in that the solid base catalyst is a magnetic carrier loaded with KOH, and the magnetic carrier is Fe3O4With CeO2The composite material has a molar ratio of 1: 1.8-2.2;
the preparation method of the solid base catalyst comprises the following steps:
(1) taking polyoxyethylene ether as a template, adding cerium salt, adjusting the pH value to generate precipitation, aging, drying and calcining to obtain mesoporous CeO2A material;
(2) mesoporous CeO2The mixture formed by mixing the material, ferric salt and ferrous salt is used for adjusting the pH value, and the magnetic carrier CeO is obtained after aging and drying2-Fe3O4A precursor;
(3) mixing a magnetic carrier CeO2-Fe3O4Dispersing the precursor and KOH in water, standing, drying and calcining to obtain a solid base catalyst;
the mol ratio of the polyoxyethylene ether to cerium ions in the cerium salt is 1.7-2.3: 1;
the calcining temperature in the step (1) is 350-550 ℃, and the calcining time is 2-5 h;
the calcining temperature in the step (3) is 300-500 ℃, and the calcining time is 1-4 h.
2. The use according to claim 1, wherein the mass of KOH in the solid base catalyst is 20 to 40% of the mass of the magnetic carrier.
3. A method for preparing biodiesel by utilizing solid wastes of kitchen or slaughter houses, which is characterized in that the solid base catalyst in the application of claim 1 or 2 is mixed with methanol, then the solid wastes of kitchen or slaughter houses are added, and the mixture is sealed and heated for reaction to obtain the biodiesel.
4. A method according to claim 3, characterized in that kitchen or slaughterhouse animal solid waste is subjected to ultrasound treatment.
5. The method according to claim 4, wherein the ultrasonic treatment power is 15 to 100w/L, the temperature is room temperature, and the treatment time is 5 to 30 min.
6. The method according to claim 3, wherein the mass of the solid base catalyst is 1-5% of the mass of the solid waste of the kitchen or slaughterhouse animals.
7. The method according to claim 3, wherein the amount of methanol is 20 to 60% by mass of the raw material.
8. The method according to claim 3, wherein the reaction temperature is 80 to 200 ℃ and the reaction time is 10 to 120 min.
9. The method as set forth in claim 3, wherein the reacted material is centrifuged to obtain a stratified material, and the supernatant of the stratified material is distilled to obtain biodiesel.
10. The method according to claim 9, wherein the centrifugation is carried out at a centrifugation speed of 8000 to 15000r/min for 5 to 20 min.
11. The method according to claim 9, wherein the distillation temperature is 50 to 90 ℃ and the distillation time is 5 to 20 min.
12. The method as claimed in claim 3, wherein a screen is provided in the middle of the reaction kettle to divide the reaction kettle into an upper layer and a lower layer, the kitchen or slaughterhouse animal solid waste is placed on the screen, and the methanol and the solid alkali catalyst are placed in the lower layer of the reaction kettle.
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