CN112156767B - Wollastonite loaded strontium and lanthanum solid base catalyst, and preparation method and application thereof - Google Patents

Wollastonite loaded strontium and lanthanum solid base catalyst, and preparation method and application thereof Download PDF

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CN112156767B
CN112156767B CN202011203409.5A CN202011203409A CN112156767B CN 112156767 B CN112156767 B CN 112156767B CN 202011203409 A CN202011203409 A CN 202011203409A CN 112156767 B CN112156767 B CN 112156767B
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solid base
base catalyst
catalyst according
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biodiesel
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CN112156767A (en
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牛胜利
曲同鑫
韩奎华
李英杰
路春美
程世庆
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Shandong University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

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Abstract

The invention discloses a wollastonite supported strontium and lanthanum solid base catalyst and a preparation method and application thereof. In the process of loading strontium oxide and lanthanum oxide on wollastonite, not only can active sites be uniformly distributed on the surface of a carrier, but also the agglomeration phenomenon of the active sites is effectively avoided, the effective contact of reactant molecules and the active sites is strengthened, the catalyst has higher catalytic activity, the existence of the wollastonite carrier enhances the mechanical strength of the catalyst, the loss of the active sites caused by the mechanical stress of the collision of catalyst particles with other particles or the wall of a container is reduced, and strontium oxide (SrO) reacts with the wollastonite to generate a new phase CaSrSiO4Thereby improving the solid supporting rate of the active site and leading the catalyst to show good repeated use stability.

Description

Wollastonite loaded strontium and lanthanum solid base catalyst, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a wollastonite supported strontium and lanthanum solid base catalyst, and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Biodiesel (biodiesel) is a liquid fuel which is obtained by carrying out ester exchange reaction on animal and vegetable oil serving as a raw material and low-carbon alcohol (methanol or ethanol) and mainly contains long-chain fatty acid methyl ester, has the advantages of reproducibility, no toxicity, biodegradability, no sulfur and aromatic components and the like, and is considered as an excellent substitute of fossil diesel. Compared with the traditional fossil diesel, the biodiesel has similar or even better physicochemical indexes, has higher cetane number and flash point and lower emission of CO, PM and UHC, and can be directly used or mixed with the fossil diesel according to a certain proportion. The popularization and development of the biodiesel can effectively relieve the energy crisis caused by the shortage of fossil fuels and the problem of environmental pollution caused by combustion of the fossil fuels.
At present, the industrial production is generally carried out by HCl and H2SO4Strong acid or strong base such as KOH, NaOH and the like are used as catalysts to catalyze the ester exchange reaction to prepare the biodiesel. However, HCl, H2SO4Homogeneous catalysts such as KOH and NaOH have high catalytic activity, but are limited by problems of equipment corrosion, wastewater pollution, complex separation and purification and the like. In contrast, heterogeneous catalysts have received much attention and research because of their advantages of being less corrosive, easily separable, and recyclable. However, the high-activity heterogeneous catalyst also has the problems of complex process, high cost, leaching inactivation, high requirement on the quality of raw oil and the like, and needs to be further researched and solved.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a wollastonite supported strontium and lanthanum solid base catalyst, and a preparation method and application thereof. The stability of the solid base catalyst in an ester exchange system is further improved, the catalytic activity and the acid resistance of the solid base catalyst are improved, the solid base catalyst has wide applicability to raw materials, and the commercial practicability of the solid base catalyst is improved.
To solve the above technical problem, one or more of the following embodiments of the present invention provide the following technical solutions:
in a first aspect, the invention provides a wollastonite supported strontium and lanthanum solid base catalyst, which comprises a wollastonite carrier and strontium oxide and lanthanum oxide supported on wollastonite.
In a second aspect, the present invention provides a method for preparing the solid base catalyst, comprising the steps of:
adding a strontium source, a lanthanum source and wollastonite powder into water, and stirring and dipping;
and drying, calcining and activating the product to obtain the solid base catalyst.
In a third aspect, the application of the solid base catalyst in the catalytic preparation of biodiesel is provided.
Compared with the prior art, one or more technical schemes of the invention have the following beneficial effects:
(1) the solid base catalyst has wide raw material sources, and the preparation method is simple and feasible, thereby having important significance for the commercial production of the biodiesel.
(2) Strontium oxide (SrO) is one of the alkaline earth metal oxides with the highest activity, is not easy to dissolve in vegetable oil, methanol and fatty acid methyl ester, and has the advantages of high alkali density and strong catalytic capability. Lanthanum oxide (La)2O3) Belongs to transition metal oxide, contains difunctional basic acid active sites, can selectively catalyze esterification and ester exchange reaction simultaneously, and is particularly suitable for low-cost raw materials with high Free Fatty Acid (FFA) content.
Wollastonite is a natural calcium silicate mineral (CaSiO) with a needle-like crystal structure3) Widely distributed in the world, and is commonly used in the industries of ceramics, cement, rubber, plastics, paint and the like. Wollastonite has the advantages of no toxicity, strong acid and alkali resistance, high thermal stability and the like.
In the process of loading strontium oxide and lanthanum oxide on wollastonite, not only can active sites be uniformly distributed on the surface of the carrier, but also the agglomeration phenomenon of the active sites is effectively avoided, the effective contact of reactant molecules and the active sites is strengthened, the catalyst is ensured to have higher catalytic activity, and the existence of the wollastonite carrier enhances the mechanical strength of the catalyst, and the loss of the active sites caused by the mechanical stress of the collision of catalyst particles with other particles or the wall of a container is reducedAnd strontium oxide (SrO) and wollastonite (CaSiO)3) Reaction to generate new phase CaSrSiO4Thereby improving the solid supporting rate of the active site and leading the catalyst to show good repeated use stability. Meanwhile, the strontium oxide and the lanthanum oxide are used as active sites, and can generate a synergistic effect in the process of catalyzing ester exchange, so that the catalytic performance is effectively improved compared with a single catalyst loaded with the strontium oxide or the lanthanum oxide.
(3) Since the Free Fatty Acid (FFA) content of the raw oil during transesterification is too high to cause saponification side reactions, complicating the separation of glycerin and reducing the yield of biodiesel, there is a high quality requirement for the raw oil used for the transesterification reaction. However, refined feed stock (FFA)<0.5%) would result in increased costs and hinder commercial application. Aiming at the problem of high requirement of raw oil in ester exchange reaction, lanthanum oxide (La) with acid-base double nature sites is used in the invention2O3) The modification is used for improving the acid resistance of the catalyst, so that the raw material cost of biodiesel production is reduced, and the practicability of the solid base catalyst is improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a graph showing a comparison of the reusability of the high-stability solid base catalyst obtained in example 1 at a reaction temperature of 150 deg.C, a catalyst addition of 8wt.%, an alcohol-oil molar ratio of 15:1, and a reaction time of 3 hours.
FIG. 2 is an XRD pattern of a highly stable solid base catalyst supported on wollastonite and having a strontium/lanthanum molar ratio of 7/3 as obtained in example 1.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. 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 invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. 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.
In a first aspect, the invention provides a wollastonite supported strontium and lanthanum solid base catalyst, which comprises a wollastonite carrier and strontium oxide and lanthanum oxide supported on wollastonite.
In some embodiments, the molar ratio of strontium and lanthanum metal cations in the solid base catalyst is from 9/1 to 1/9.
In some embodiments, the solid base catalyst has a mass ratio of wollastonite, strontium oxide, and lanthanum oxide of 1/0.91 to 1/1.31.
In a second aspect, the present invention provides a method for preparing the solid base catalyst, comprising the steps of:
adding a strontium source, a lanthanum source and wollastonite powder into water, and stirring and dipping;
and drying, calcining and activating the impregnated product to obtain the solid base catalyst.
In some embodiments, the strontium source is a compound that is soluble in water and has a cation that is a strontium ion, such as strontium chloride, strontium nitrate, and the like.
In some embodiments, the lanthanum source is a compound that is soluble in water and the cation is lanthanum ion, such as lanthanum chloride, lanthanum nitrate, and the like.
In order to reduce the influence of anions on the preparation process and the catalytic effect of the catalyst, the strontium source and the lanthanum source are preferably nitrates.
In some embodiments, the concentration of the strontium salt solution during impregnation is 0.9-0.1 mol/L; the concentration of the lanthanum salt solution is 0.1-0.9 mol/L.
In some embodiments, the wollastonite powder has a particle size of 50 to 400 mesh, preferably 200 mesh.
In some embodiments, the drying step comprises a water bath evaporation and drying step. The evaporation in the water bath is carried out in a water bath kettle with magnetic stirring, and the evaporation of water is accompanied by stirring. If the direct drying is carried out, the strontium nitrate and lanthanum nitrate crystals are unevenly distributed on the surface of wollastonite due to the overhigh temperature and static evaporation, so that agglomeration is caused, and the catalytic effect is further reduced.
Further, the temperature for evaporating the water bath to dryness is 80-90 ℃, and preferably 80 ℃.
Further, the drying temperature is 110-.
In some embodiments, the temperature of the calcination is 850-950 ℃, and the calcination time is 4-6 h; preferably, the calcination temperature is 900 ℃ and the calcination time is 5 hours.
In a third aspect, the application of the solid base catalyst in the catalytic preparation of biodiesel is provided.
The method for preparing the biodiesel by catalyzing ester exchange by the solid base catalyst comprises the following steps:
mixing raw oil, alcohol and the solid base catalyst in proportion, and carrying out ester exchange reaction in a high-pressure reaction kettle to prepare the biodiesel.
In some embodiments, the raw oil is a vegetable oil or an animal fat, preferably a vegetable oil, and further, the vegetable oil is palm oil.
In some embodiments, the alcohol is an alcohol capable of participating in a transesterification reaction, preferably methanol.
In some embodiments, the temperature of the transesterification reaction is 140 ℃ to 160 ℃, preferably 150 ℃.
Further, the pressure of the transesterification reaction is changed in a self-adaptive manner while the temperature in the autoclave is kept constant.
In some embodiments, the molar ratio of the alcohol to the feedstock oil is from 6:1 to 21:1, preferably 15: 1.
In some embodiments, the solid base catalyst is added in an amount of 1-10wt.%, preferably 8wt.% based on the mass of the raw oil.
In some embodiments, the transesterification reaction time is 2 to 4 hours, preferably 3 hours.
The reaction conditions have obvious influence on the ester exchange process, and the reaction rate can be obviously promoted to increase by increasing the reaction temperature. The molar ratio of the alcohol to the raw oil is also an important influence factor, and the transesterification reaction is reversible, so that the increase of the molar ratio can drive the forward reaction and promote the increase of the yield of the biodiesel; however, too high a molar ratio also dilutes the reactant concentration, resulting in a decrease in biodiesel yield. The addition amount of the catalyst also has obvious influence on the yield of the biodiesel, and the improved concentration of the catalyst can effectively increase the number of catalytic activity sites, thereby promoting the ester exchange reaction and improving the yield of the biodiesel; but the upper limit of the efficiency of the ester exchange is limited by chemical equilibrium, the effect of the excessively high catalyst addition amount is not obvious any more, and the difficulty of subsequent separation and purification of the product is increased. Meanwhile, the influence of the length of the ester exchange reaction time is obvious, the yield of the biodiesel can gradually reach the optimal state along with the prolonging of the time, and the improvement effect of the ester exchange efficiency is weakened if the time is continuously prolonged.
Example 1
Weighing 12g of natural wollastonite ore powder and 14.81g of strontium nitrate (Sr (NO) in sequence3)2·4H2O) and 9.75g lanthanum nitrate (La (NO)3)3·xH2O) is added into 100mL deionized water, and the mixture is stirred and dipped for 0.5h to obtain a mixed solution. Putting the beaker of the mixed solution into a water bath kettle with a stirring device, and evaporating the beaker to dryness in the water bath at 80 ℃. Drying the obtained catalyst precursor at 120 ℃ for 12h, and then calcining and activating the catalyst precursor for 5h from 20 ℃ to 900 ℃ within the heating rate of 5 ℃/min to obtain the wollastonite-supported strontium and lanthanum high-stability solid base catalyst with the strontium/lanthanum molar ratio of 7/3.
10.5g of methanol, 20g of palm oil and 1.6g of catalyst are added into a high-pressure reaction kettle in sequence, and the mixture is heated to 150 ℃ and maintained for 3 hours under the continuous stirring at the rotating speed of 1200 r/min. And separating the reaction product to obtain the solid catalyst by a centrifugal machine, pouring the liquid product into a separating funnel, standing and layering the solid catalyst by the action of gravity, removing the lower layer of glycerin, and washing the biodiesel to be neutral by deionized water. The biodiesel was then placed in a 105 ℃ dry box and evaporated to remove residual methanol and deionized water from the biodiesel. Finally, the yield of biodiesel was 95.35% as determined by gas chromatograph using internal standard method.
After the transesterification, the catalyst separated off was washed twice with methanol, dried at 120 ℃ and transesterified again according to the above parameters. After the catalyst is recycled for 5 times, the yield of the biodiesel is still maintained to be 86.14 percent.
Fig. 1 shows the reusability of the high-stability solid base catalyst prepared in example 1 under the conditions of reaction temperature of 150 ℃, catalyst addition of 8wt.%, alcohol-oil molar ratio of 15:1, and reaction time of 3h, wherein the yield of biodiesel when the catalyst is used for the first time is 95.35%, and after the catalyst is recycled for 5 times, the yield of biodiesel still reaches 86.14%, and the reusability stability is good.
FIG. 2 is the XRD pattern of the solid base catalyst prepared in example 1 and having wollastonite as a carrier and a strontium/lanthanum molar ratio of 7/3, and the result shows that the main phase component of the solid base catalyst is CaSrSiO4And La2O3Wherein, CaSrSiO4Is SrO and CaSiO in the process of calcination and activation3The reaction product shows that SrO is not loaded on the surface of wollastonite in a simple physical attachment form, but is bonded with the wollastonite chemically, so that leaching of the SrO is effectively reduced. The presence of CaO is attributed to the small amount of CaCO present in the wollastonite3Or Ca (OH)2And (4) decomposing the impurities.
Example 2
Weighing 12g of natural wollastonite ore powder and 19.05g of strontium nitrate (Sr (NO) in sequence3)2·4H2O) and 3.25g lanthanum nitrate (La (NO)3)3·xH2O) is added into 100mL deionized water, and the mixture is stirred and dipped for 0.5h to obtain a mixed solution. Putting the beaker of the mixed solution into a water bath kettle with a stirring device, and evaporating the beaker to dryness in the water bath at 80 ℃. Drying the obtained catalyst precursor at 120 ℃ for 12h, and then calcining and activating the catalyst precursor for 5h from 20 ℃ to 900 ℃ within the heating rate of 5 ℃/min to obtain the wollastonite-supported strontium and lanthanum high-stability solid base catalyst with the strontium/lanthanum molar ratio of 9/1.
10.5g of methanol, 20g of palm oil and 1.6g of catalyst are added into a high-pressure reaction kettle in sequence, and the mixture is heated to 150 ℃ and maintained for 3 hours under the continuous stirring at the rotating speed of 1200 r/min. And separating the reaction product to obtain the solid catalyst by a centrifugal machine, pouring the liquid product into a separating funnel, standing and layering the solid catalyst by the action of gravity, removing the lower layer of glycerin, and washing the biodiesel to be neutral by deionized water. The biodiesel was then placed in a 105 ℃ dry box and evaporated to remove residual methanol and deionized water from the biodiesel. Finally, the biodiesel yield was 86.36% as determined by gas chromatograph using internal standard method.
Example 3
Weighing 12g of natural wollastonite ore powder and 10.58g of strontium nitrate (Sr (NO) in sequence3)2·4H2O) and 16.25g lanthanum nitrate (La (NO)3)3·xH2O) is added into 100mL deionized water, and the mixture is stirred and dipped for 0.5h to obtain a mixed solution. Putting the beaker of the mixed solution into a water bath kettle with a stirring device, and evaporating the beaker to dryness in the water bath at 80 ℃. Drying the obtained catalyst precursor at 120 ℃ for 12h, and then calcining and activating the catalyst precursor for 5h from 20 ℃ to 900 ℃ within the heating rate of 5 ℃/min to obtain the wollastonite-supported strontium and lanthanum high-stability solid base catalyst with the strontium/lanthanum molar ratio of 5/5.
10.5g of methanol, 20g of palm oil and 1.6g of catalyst are added into a high-pressure reaction kettle in sequence, and the mixture is heated to 150 ℃ and maintained for 3 hours under the continuous stirring at the rotating speed of 1200 r/min. And separating the reaction product to obtain the solid catalyst by a centrifugal machine, pouring the liquid product into a separating funnel, standing and layering the solid catalyst by the action of gravity, removing the lower layer of glycerin, and washing the biodiesel to be neutral by deionized water. The biodiesel was then placed in a 105 ℃ dry box and evaporated to remove residual methanol and deionized water from the biodiesel. Finally the biodiesel yield was 91.34% as determined by gas chromatograph using internal standard method.
Example 4
Weighing 12g of natural wollastonite ore powder and 6.35g of strontium nitrate (Sr (NO) in sequence3)2·4H2O) and 22.74g lanthanum nitrate (La (NO)3)3·xH2O) is added into 100mL deionized water, and the mixture is stirred and dipped for 0.5h to obtain a mixed solution. Putting the beaker of the mixed solution into a water bath with a stirring deviceThe mixture was evaporated to dryness in a water bath at 80 ℃ in a pan. Drying the obtained catalyst precursor at 120 ℃ for 12h, and then calcining and activating the catalyst precursor for 5h from 20 ℃ to 900 ℃ within the heating rate of 5 ℃/min to obtain the wollastonite-supported strontium and lanthanum high-stability solid base catalyst with the strontium/lanthanum molar ratio of 5/5.
10.5g of methanol, 20g of palm oil and 1.6g of catalyst are added into a high-pressure reaction kettle in sequence, and the mixture is heated to 150 ℃ and maintained for 3 hours under the continuous stirring at the rotating speed of 1200 r/min. And separating the reaction product to obtain the solid catalyst by a centrifugal machine, pouring the liquid product into a separating funnel, standing and layering the solid catalyst by the action of gravity, removing the lower layer of glycerin, and washing the biodiesel to be neutral by deionized water. The biodiesel was then placed in a 105 ℃ dry box and evaporated to remove residual methanol and deionized water from the biodiesel. Finally the biodiesel yield was 89.85% as determined by gas chromatograph using internal standard method.
Example 5
Weighing 12g of natural wollastonite ore powder and 2.12g of strontium nitrate (Sr (NO) in sequence3)2·4H2O) and 29.24g of lanthanum nitrate (La (NO)3)3·xH2O) is added into 100mL deionized water, and the mixture is stirred and dipped for 0.5h to obtain a mixed solution. Putting the beaker of the mixed solution into a water bath kettle with a stirring device, and evaporating the beaker to dryness in the water bath at 80 ℃. Drying the obtained catalyst precursor at 120 ℃ for 12h, and then calcining and activating the catalyst precursor for 5h from 20 ℃ to 900 ℃ within the heating rate of 5 ℃/min to obtain the wollastonite-supported strontium and lanthanum high-stability solid base catalyst with the strontium/lanthanum molar ratio of 1/9.
10.5g of methanol, 20g of palm oil and 1.6g of catalyst are added into a high-pressure reaction kettle in sequence, and the mixture is heated to 150 ℃ and maintained for 3 hours under the continuous stirring at the rotating speed of 1200 r/min. And separating the reaction product to obtain the solid catalyst by a centrifugal machine, pouring the liquid product into a separating funnel, standing and layering the solid catalyst by the action of gravity, removing the lower layer of glycerin, and washing the biodiesel to be neutral by deionized water. The biodiesel was then placed in a 105 ℃ dry box and evaporated to remove residual methanol and deionized water from the biodiesel. Finally, the biodiesel yield was 86.40% as determined by gas chromatograph using internal standard method.
Example 6
The differences from example 1 are: the catalyst preparation procedure was the same as in example 1. 10.5g of methanol, 20g of palm oil, 1.6g of catalyst and 0.2g of oleic acid (oleic acid is used for simulating free fatty acid in raw oil to detect the acid resistance of the catalyst) are sequentially added into a high-pressure reaction kettle, and the mixture is heated to 150 ℃ under the continuous stirring at the rotating speed of 1200r/min and is maintained for 3 hours. And separating the reaction product to obtain the solid catalyst by a centrifugal machine, pouring the liquid product into a separating funnel, standing and layering the solid catalyst by the action of gravity, removing the lower layer of glycerin, and washing the biodiesel to be neutral by deionized water. The biodiesel was then placed in a 105 ℃ dry box and evaporated to remove residual methanol and deionized water from the biodiesel. Finally, the biodiesel yield was found to be 94.17% by gas chromatography using internal standard method.
Example 7
The differences from example 1 are: the catalyst preparation procedure was the same as in example 1. 10.5g of methanol, 20g of palm oil, 1.6g of catalyst and 0.6g of oleic acid are added into a high-pressure reaction kettle in sequence, and the mixture is heated to 150 ℃ and maintained for 3 hours under the continuous stirring at the rotating speed of 1200 r/min. And separating the reaction product to obtain the solid catalyst by a centrifugal machine, pouring the liquid product into a separating funnel, standing and layering the solid catalyst by the action of gravity, removing the lower layer of glycerin, and washing the biodiesel to be neutral by deionized water. The biodiesel was then placed in a 105 ℃ dry box and evaporated to remove residual methanol and deionized water from the biodiesel. Finally, the biodiesel yield was 92.59% as determined by gas chromatograph using internal standard method.
Example 8
The differences from example 1 are: the catalyst preparation procedure was the same as in example 1. 10.5g of methanol, 20g of palm oil, 1.6g of catalyst and 1.0g of oleic acid are added into a high-pressure reaction kettle in sequence, and the mixture is heated to 150 ℃ and maintained for 3 hours under the continuous stirring at the rotating speed of 1200 r/min. And separating the reaction product to obtain the solid catalyst by a centrifugal machine, pouring the liquid product into a separating funnel, standing and layering the solid catalyst by the action of gravity, removing the lower layer of glycerin, and washing the biodiesel to be neutral by deionized water. The biodiesel was then placed in a 105 ℃ dry box and evaporated to remove residual methanol and deionized water from the biodiesel. Finally the biodiesel yield was 91.62% as determined by gas chromatograph using internal standard method.
Example 9
The differences from example 1 are: the catalyst preparation procedure was the same as in example 1. 10.5g of methanol, 20g of palm oil, 1.6g of catalyst and 1.4g of oleic acid are added into a high-pressure reaction kettle in sequence, and the mixture is heated to 150 ℃ and maintained for 3 hours under the continuous stirring at the rotating speed of 1200 r/min. And separating the reaction product to obtain the solid catalyst by a centrifugal machine, pouring the liquid product into a separating funnel, standing and layering the solid catalyst by the action of gravity, removing the lower layer of glycerin, and washing the biodiesel to be neutral by deionized water. The biodiesel was then placed in a 105 ℃ dry box and evaporated to remove residual methanol and deionized water from the biodiesel. Finally the biodiesel yield was 83.73% as determined by gas chromatograph using internal standard method.
Example 10
The differences from example 1 are: the catalyst preparation procedure was the same as in example 1. 10.5g of methanol, 20g of palm oil, 1.6g of catalyst and 1.8g of oleic acid are added into a high-pressure reaction kettle in sequence, and the mixture is heated to 150 ℃ and maintained for 3 hours under the continuous stirring at the rotating speed of 1200 r/min. And separating the reaction product to obtain the solid catalyst by a centrifugal machine, pouring the liquid product into a separating funnel, standing and layering the solid catalyst by the action of gravity, removing the lower layer of glycerin, and washing the biodiesel to be neutral by deionized water. The biodiesel was then placed in a 105 ℃ dry box and evaporated to remove residual methanol and deionized water from the biodiesel. Finally the biodiesel yield was 66.21% as determined by gas chromatograph using internal standard method.
Comparative example 1
Weighing 12g of natural wollastonite ore powder and 21.16g of strontium nitrate (Sr (NO) in sequence3)2·4H2O) is added into 100mL deionized water, and the mixture is stirred and dipped for 0.5h to obtain a mixed solution. Putting the beaker of the mixed solution into a water bath kettle with a stirring device, and evaporating the beaker to dryness in the water bath at 80 ℃. Drying the obtained catalyst precursor at 120 ℃ for 12h, and then calcining and activating the catalyst precursor from 20 ℃ to 900 ℃ within the heating rate of 5 ℃/min for 5h to obtain the wollastonite supported strontium solid base catalyst.
10.5g of methanol, 20g of palm oil and 1.6g of catalyst are added into a high-pressure reaction kettle in sequence, and the mixture is heated to 150 ℃ and maintained for 3 hours under the continuous stirring at the rotating speed of 1200 r/min. And separating the reaction product to obtain the solid catalyst by a centrifugal machine, pouring the liquid product into a separating funnel, standing and layering the solid catalyst by the action of gravity, removing the lower layer of glycerin, and washing the biodiesel to be neutral by deionized water. The biodiesel was then placed in a 105 ℃ dry box and evaporated to remove residual methanol and deionized water from the biodiesel. Finally the biodiesel yield was 83.22% as determined by gas chromatograph using internal standard method.
Comparative example 2
Weighing 12g of natural wollastonite ore powder and 32.49g of lanthanum nitrate (La (NO) in sequence3)3·xH2O) is added into 100mL deionized water, and the mixture is stirred and dipped for 0.5h to obtain a mixed solution. Putting the beaker of the mixed solution into a water bath kettle with a stirring device, and evaporating the beaker to dryness in the water bath at 80 ℃. Drying the obtained catalyst precursor at 120 ℃ for 12h, and then calcining and activating the catalyst precursor from 20 ℃ to 900 ℃ within the heating rate of 5 ℃/min for 5h to obtain the wollastonite-supported lanthanum solid base catalyst.
10.5g of methanol, 20g of palm oil and 1.6g of catalyst are added into a high-pressure reaction kettle in sequence, and the mixture is heated to 150 ℃ and maintained for 3 hours under the continuous stirring at the rotating speed of 1200 r/min. And separating the reaction product to obtain the solid catalyst by a centrifugal machine, pouring the liquid product into a separating funnel, standing and layering the solid catalyst by the action of gravity, removing the lower layer of glycerin, and washing the biodiesel to be neutral by deionized water. The biodiesel was then placed in a 105 ℃ dry box and evaporated to remove residual methanol and deionized water from the biodiesel. Finally the biodiesel yield was 82.51% as determined by gas chromatograph using internal standard method.
Comparative example 3
The difference from comparative example 1 is: the catalyst preparation procedure was the same as in comparative example 1. 10.5g of methanol, 20g of palm oil, 1.6g of catalyst and 1.0g of oleic acid are added into a high-pressure reaction kettle in sequence, and the mixture is heated to 150 ℃ and maintained for 3 hours under the continuous stirring at the rotating speed of 1200 r/min. And separating the reaction product to obtain the solid catalyst by a centrifugal machine, pouring the liquid product into a separating funnel, standing and layering the solid catalyst by the action of gravity, removing the lower layer of glycerin, and washing the biodiesel to be neutral by deionized water. The biodiesel was then placed in a 105 ℃ dry box and evaporated to remove residual methanol and deionized water from the biodiesel. Finally the biodiesel yield was 71.33% as determined by gas chromatograph using internal standard method.
Comparative example 4
The difference from comparative example 2 is: the catalyst preparation procedure was the same as in comparative example 2. 10.5g of methanol, 20g of palm oil, 1.6g of catalyst and 1.0g of oleic acid are added into a high-pressure reaction kettle in sequence, and the mixture is heated to 150 ℃ and maintained for 3 hours under the continuous stirring at the rotating speed of 1200 r/min. And separating the reaction product to obtain the solid catalyst by a centrifugal machine, pouring the liquid product into a separating funnel, standing and layering the solid catalyst by the action of gravity, removing the lower layer of glycerin, and washing the biodiesel to be neutral by deionized water. The biodiesel was then placed in a 105 ℃ dry box and evaporated to remove residual methanol and deionized water from the biodiesel. Finally the biodiesel yield was 83.89% as determined by gas chromatograph using internal standard method.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (30)

1. A wollastonite supported strontium and lanthanum solid base catalyst is characterized in that: comprises a wollastonite carrier and strontium oxide and lanthanum oxide loaded on wollastonite;
the mass ratio of the wollastonite to the strontium oxide to the lanthanum oxide in the solid base catalyst is 1:0.91-1: 1.31.
2. A process for preparing a solid base catalyst according to claim 1, characterized in that: the method comprises the following steps:
adding a strontium source, a lanthanum source and wollastonite powder into water, and stirring and dipping;
and drying, calcining and activating the impregnated product to obtain the solid base catalyst.
3. The method for preparing a solid base catalyst according to claim 2, characterized in that: the strontium source is a compound which is soluble in water and has strontium ions as cations.
4. The method for preparing a solid base catalyst according to claim 2, characterized in that: the lanthanum source is a compound that is soluble in water and has cations that are lanthanum ions.
5. The method for preparing a solid base catalyst according to claim 2, characterized in that: in the dipping process, the concentration of the strontium salt solution is 0.9-0.1 mol/L; the concentration of the lanthanum salt solution is 0.1-0.9 mol/L.
6. The method for preparing a solid base catalyst according to claim 2, characterized in that: the particle size of the wollastonite powder is 50 to 400 meshes.
7. The method for preparing a solid base catalyst according to claim 2, characterized in that: the wollastonite powder has a particle size of 200 mesh.
8. The method for preparing a solid base catalyst according to claim 2, characterized in that: the drying step comprises the steps of water bath evaporation and drying.
9. The method for preparing a solid base catalyst according to claim 8, characterized in that: the temperature for evaporating the water bath to dryness is 80-90 ℃.
10. The method for preparing a solid base catalyst according to claim 8, characterized in that: the temperature for evaporating the water bath to dryness is 80 ℃.
11. The method for preparing a solid base catalyst according to claim 8, characterized in that: the drying temperature is 110-130 ℃.
12. The method for preparing a solid base catalyst according to claim 8, characterized in that: the drying temperature is 120 ℃.
13. The method for preparing a solid base catalyst according to claim 2, characterized in that: the calcining temperature is 850 ℃ and 950 ℃, and the calcining time is 4-6 h.
14. The method for preparing a solid base catalyst according to claim 2, characterized in that: the calcining temperature is 900 ℃, and the calcining time is 5 h.
15. Use of the solid base catalyst of claim 1 for the catalytic production of biodiesel.
16. The method for preparing biodiesel by ester exchange catalyzed by the solid base catalyst as claimed in claim 1, wherein: the method comprises the following steps:
mixing raw oil, alcohol and the solid base catalyst in proportion, and carrying out ester exchange reaction in a high-pressure reaction kettle to prepare the biodiesel.
17. The method for preparing biodiesel by ester exchange catalyzed by solid base catalyst according to claim 16, wherein: the raw oil is vegetable oil or animal fat.
18. The method for preparing biodiesel by ester exchange catalyzed by solid base catalyst according to claim 17, wherein: the raw oil is vegetable oil.
19. The method for preparing biodiesel by ester exchange catalyzed by solid base catalyst according to claim 17, wherein: the vegetable oil is palm oil.
20. The method for preparing biodiesel by ester exchange catalyzed by solid base catalyst according to claim 16, wherein: the alcohol is an alcohol capable of participating in a transesterification reaction.
21. The method for preparing biodiesel by ester exchange catalyzed by solid base catalyst according to claim 16, wherein: the alcohol is methanol.
22. The method for preparing biodiesel by ester exchange catalyzed by solid base catalyst according to claim 16, wherein: the temperature of the transesterification reaction is 140 ℃ and 160 ℃.
23. The method for preparing biodiesel by ester exchange catalyzed by solid base catalyst according to claim 16, wherein: the temperature of the transesterification reaction was 150 ℃.
24. The method for preparing biodiesel by ester exchange catalyzed by solid base catalyst according to claim 16, wherein: under the condition of keeping the temperature in the high-pressure reaction kettle constant, the pressure intensity of the ester exchange reaction is changed by self-adaptation.
25. The method for preparing biodiesel by ester exchange catalyzed by solid base catalyst according to claim 16, wherein: the molar ratio of the alcohol to the raw oil is 6:1-21: 1.
26. The method for preparing biodiesel by ester exchange catalyzed by solid base catalyst according to claim 16, wherein: the molar ratio of the alcohol to the raw oil is 15: 1.
27. The method for preparing biodiesel by ester exchange catalyzed by solid base catalyst according to claim 16, wherein: the addition amount of the solid base catalyst accounts for 1-10 wt% of the mass of the raw oil.
28. The method for preparing biodiesel by ester exchange catalyzed by solid base catalyst according to claim 16, wherein: the addition amount of the solid base catalyst accounts for 8 wt% of the mass of the raw oil.
29. The method for preparing biodiesel by ester exchange catalyzed by solid base catalyst according to claim 16, wherein: the time of the ester exchange reaction is 2-4 h.
30. The method for preparing biodiesel by ester exchange catalyzed by solid base catalyst according to claim 16, wherein: the transesterification time was 3 h.
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