CN106238090B - Preparation of mesoporous solid base catalyst and method for synthesizing biodiesel by catalyzing transesterification reaction - Google Patents
Preparation of mesoporous solid base catalyst and method for synthesizing biodiesel by catalyzing transesterification reaction Download PDFInfo
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Abstract
The invention discloses a composite solid-supported mesoporous solid alkali CaO/ZrO2‑La2O3According to the method for preparing the biodiesel by carrying out the ester exchange reaction of the SBA-15 catalytic oil and methanol, the prepared catalyst has a complete mesoporous structure, high catalytic activity, good reusability, is easy to separate from a reaction system, the molar ratio of the methanol to the oil as a reaction raw material is 5-20: 1, the mass ratio of the catalyst amount to the oil is 0.01-0.1: 1, the reaction temperature is 55-64 ℃, the reaction time is 30-50 min, and the reaction yield can reach 94.24%. Cooling to room temperature after the reaction is finished, evaporating the filtrate to recover unreacted methanol, stirring the concentrated solution obtained after evaporation, standing for separation, recovering the upper-layer liquid, namely the target product biodiesel, and obtaining a small amount of substances at the lower layer, namely the byproduct glycerol.
Description
The invention belongs to the technical field of fine chemical engineering, and relates to a preparation method of a mesoporous solid base catalyst and a method for catalyzing ester exchange reaction to synthesize biodiesel.
Background
Despite the recent fluctuations in petrochemical energy, the development of new alternative energy sources, such as solar energy, wind energy, tidal energy, biological energy, and the like, remains a significant social concern. Compared with petrochemical energy, the biodiesel is a renewable resource, has good combustion performance and safety, discharges few sulfur and nitrogen compounds, is green and environment-friendly, and is flexible and convenient to use. The biodiesel is prepared by esterification or ester exchange reaction of long-chain free fatty acid or animal and vegetable oil and methanol under the catalysis of acid or alkali to generate short-chain fatty acid methyl ester product. The industrial synthesis of biodiesel mostly adopts homogeneous acid-base catalysis. Are all made ofThe phase acid-base catalyst mainly comprises sulfuric acid, NaOH, sodium alkoxide, potassium alkoxide, tertiary amine and the like, the homogeneous catalysis acid-base strength is uniform, the catalysis efficiency is high, and the problems of complex separation, equipment corrosion, acid-base treatment, wastewater discharge and the like exist. The solid acid-base catalysis has the advantages of easy separation from products, no generation of industrial wastewater and cyclic utilization. Patent CN 101559359A discloses CaO-ZrO2Although the conversion rate of the biodiesel reaches 90 percent and the products are easy to separate, the preparation method of the-KOH solid base catalyst has the advantages of high pressure, high energy consumption and poor recycling property when the ester exchange reaction temperature reaches 140-180 ℃. Therefore, the invention discloses a composite solid-supported mesoporous solid alkali CaO/ZrO2-La2O3The method for preparing the biodiesel by carrying out the ester exchange reaction of the SBA-15 catalytic grease and the methanol has the advantages of high catalytic efficiency, good reusability and difficult loss of active components.
Disclosure of Invention
Objects of the invention
The invention aims to provide a preparation method of a mesoporous solid base catalyst and a method for catalyzing ester exchange reaction to synthesize biodiesel.
Technical scheme of the invention
A mesoporous solid base is used as a catalyst to catalyze the reaction of grease and methanol to synthesize biodiesel, the molar ratio of the methanol to the grease added in a reactor is 5-20: 1, the mass ratio of the mesoporous solid base to the grease is 0.01-0.1: 1, the reaction temperature is 50-64 ℃, preferably 55-60 ℃, the reaction time is 30-50 min, the reaction is finished and cooled to room temperature, the filtered and recovered mesoporous solid base catalyst is washed by ethanol for 3 times and dried at 60 ℃ for 12 hours for next use, filtrate is evaporated to recover unreacted methanol, concentrated solution obtained after evaporation is stirred and kept stand for separation, recovered upper-layer liquid is target product biodiesel, and a small amount of substance in the lower layer is byproduct glycerol;
the mesoporous solid base is CaO/ZrO2-La2O3SBA-15, wherein the molar ratio of Si, La, Zr, Ca is 1: 0.1-0.33: 0.03-0.4: 0.25-0.65, preferablySelecting Si, La, Zr and Ca in the molar ratio of 1: 0.1-0.25: 0.03-0.33: 0.35-0.57;
the mesoporous solid alkali is CaO/ZrO2-La2O3The SBA-15 is prepared by doping lanthanum and zirconium into the SBA-15 carrier skeleton at the same time and then adding Ca (CH)3COO)2·H2O impregnation and high-temperature calcination, and the preparation method comprises the following steps:
(1) stirring P123 and HCl solution with pH of 0.8 at 40 ℃ in a mass ratio of 1: 37.5 until P123 is completely dissolved to form mixed solution, and respectively adding ZrOCl2·gH2O、La(NO3)3·6H2O, TEOS is added into the mixed solution according to the mass ratio of P123 being 0.216: 0.866: 2.125: 1, the mixed solution is continuously stirred for 24 hours at 40 ℃, the pH value of the mixed solution is adjusted to be subacidity, the mixed solution is stirred for 4 hours, the mixed solution is transferred into a hydrothermal kettle to be crystallized for 24 hours at 100 ℃, white precipitate is formed, the white precipitate is filtered and washed, the filter cake is placed in a thermostat at 55 ℃ to be dried for 12 hours, then the filter cake is placed in a box type muffle furnace to be roasted, and ZrO is prepared after cooling2-La2O3-an SBA-15 vector;
the pH value of the mixed solution is adjusted to be weakly acidic, namely, an ethylenediamine solution is slowly added into the mixed solution to adjust the pH value of the solution to be 2-5, and the pH value is preferably 3-4;
the roasting in the box type muffle furnace is carried out by heating to 500-600 ℃ at the heating rate of 1-3 ℃/min, preferably 540-560 ℃, and keeping the temperature for 4-6 hours;
(2) different amounts of Ca (CH)3COO)2·H2O and ZrO2-La2O3Adding SBA-15 into 40ml of deionized water, heating, soaking and stirring until the water is completely evaporated, drying the obtained white powdery solid in a constant temperature box at 60 ℃ for 12 hours, then placing the dried white powdery solid in a box-type muffle furnace for high-temperature calcination, and cooling to obtain xCaO/ZrO2-La2O3-SBA-15 solid base, wherein x is CaO and ZrO2-La2O3-mass ratio of SBA-15;
the impregnation process is Ca (CH)3COO)2·H2O、ZrO2-La2O3-SBA-15The mass ratio of the deionized water to the deionized water is 0.25-0.4: 1: 40, the temperature is 45-60 ℃, and the dipping time is 12 hours;
the high-temperature calcination in the box-type muffle furnace is carried out by heating to 600-700 ℃ at a heating rate of 1-3 ℃/min, preferably 640-660 ℃, and keeping the temperature for 3-5 h.
Technical features and effects of the invention
The calcium source is cheap and easy to obtain, the cost is lower, the dosage of rare earth metals La and Zr is less, and the La is treated by the processes of roasting, dipping and the like2O3、ZrO2The catalyst is loaded in a covalent bond form in an SBA-15 mesoporous, Zr ions are doped to effectively protect a carrier structure from being damaged, La is doped to facilitate the dispersion of CaO on the surface of the SBA-15, the contact area of active sites and reactants is increased, the alkali strength of the catalyst is synergistically enhanced, the catalyst catalyzes the transesterification reaction of oil ester and methanol to synthesize the biodiesel, the reaction temperature is only 50-64 ℃, the reaction time is short, the reaction rate is high, the yield is high, the catalyst is repeatedly used for 5 times, and the yield is still 91%.
Drawings
FIG. 1 shows SBA-15 (a) and CaO/ZrO 0.25 (b)2-La2O3-SBA-15、(c)0.3CaO/ZrO2-La2O3-SBA-15、(d)0.35CaO/ZrO2-La2O3-SBA-15、(e)0.4CaO/ZrO2-La2O3-XRD spectrum of SBA-15. From FIG. 1, it can be seen that the ZrO-Si-O-Si2、La2O3After the modified SBA-15 carries basic group CaO, the regular mesoporous structure is still kept, but when the CaO carrying capacity is equal to the ZrO carrying capacity2-La2O3When the mass ratio of SBA-15 reaches 0.4, the pore structure of SBA-15 is destroyed.
FIG. 2 shows (a) SBA-15 and (b) ZrO2-La2O3-SBA-15、(c)0.25CaO/ZrO2-La2O3-SBA-15、(d)0.3CaO/ZrO2-La2O3-SBA-15、(e)0.35CaO/ZrO2-La2O3-SBA-15、(00.4CaO/ZrO2-La2O3-FT-IR spectrum of SBA-15. As can be seen from FIG. 2, the length of the groove is 1073cm-1The absorption peaks appear at the left and the right,this is attributed to the absorption peak of the symmetric stretching vibration of Si-O-Si, and as the CaO-supporting amount increases, the peak area becomes gradually broader, and the peak value tends to be red-shifted due to [ SiO ]4]The stretching vibration is caused. Curve (a)980cm-1The small peak of the Si-O stretching vibration in the original Si-OH group is in the passing ZrO2、La2O3The modifications disappeared, indicating that they were successfully doped into the support backbone. Curves (c), (d), (e) and (f) loaded with CaO are at 1459cm-1Produce a CO3 2-The symmetric vibration absorption peak of (1) is that calcium nitrate adsorbs CO in air during the calcination process2To produce CO3 2-For the sake of explanation, CaO was successfully introduced.
FIG. 3 shows SBA-15 (a) and CaO/ZrO 0.25 (b)2-La2O3-SBA-15、(c)0.3CaO/ZrO2-La2O3-SBA-15、(d)0.35CaO/ZrO2-La2O3-SBA-15、(e)0.4CaO/ZrO2-La2O3N of SBA-152Adsorption isotherm plot. As can be seen from fig. 3, the nitrogen adsorption-desorption curves of the curves a, b, c, and d all belong to a typical IV-type isotherm, and have an obviously closed hysteresis loop within a relative pressure range of 0.6 to 0.8, which indicates that the metal oxide before and after SBA-15 solid-supported has a good mesoporous structure. When the CaO loading reaches 0.4, the hysteresis loop becomes flat, and the relative pressure shifts to the left, which indicates that the SBA-15 structure is damaged to some extent.
FIG. 4 shows (a)0.35CaO/ZrO2-La2O3-SBA-15、(b)0.35CaO/ZrO2-SBA-15、(c)ZrO2-La2O3CO of SBA-152-a TPD profile. Weaker CO is detected around 160 ℃ in curve c2Desorption peak, indicating ZrO2-La2O3SBA-15 has a weak base centre. Curve b detects CO at about 100 ℃ and 550 ℃2Desorption peak, indicating 0.35CaO/ZrO2SBA-15 has a weak base center and a strong base center. The curve a detects CO at 100 ℃, 260 ℃ and 550 DEG2Desorption peak, indicating 0.35CaO/ZrO2-La2O3SBA-15 has 3 basic centers,wherein 550 ℃ corresponds to a strong base center. Comparing curves a and b, it can be seen that 0.35CaO/ZrO due to the doping with La2-La2O3Strong alkali content ratio of SBA-15 0.35CaO/ZrO2Much more SBA-15, so that the doping metal La promotes the increase of the number of basic groups CaO and the distribution on the surface of the support.
Detailed Description
The technical means and the mode of carrying out the present invention will be described below by way of examples, but the technical means and the mode of carrying out the present invention are not limited to the following examples.
Example 1
1. Mesoporous solid alkali CaO/Zr2O3-La2O3Preparation of-SBA-15
(1) Stirring P123 and HC1 solution with pH of 0.8 at 40 deg.C at a mass ratio of 1: 37.5 until P123 is completely dissolved to form mixed solution, and respectively adding ZrOCl2·8H2O、La(NO3)3·6H2O, TEOS is added into the mixed solution according to the mass ratio of P123 being 0.216: 0.866: 2.125: 1, the mixed solution is continuously stirred for 24 hours at 40 ℃, then the ethylenediamine solution is slowly added into the mixed solution to adjust the pH value of the solution to 4, then the mixed solution is stirred for 4 hours, the mixed solution is transferred into a hydrothermal kettle to be crystallized for 24 hours at 100 ℃ to form white precipitate, the white precipitate is filtered and washed, the filter cake is placed in a thermostat at 55 ℃ for drying for 12 hours, then the filter cake is placed in a box-type muffle furnace to be heated to 550 ℃ at the heating rate of 2 ℃/min, the temperature is kept for 5 hours, and the ZrO is prepared after cooling2-La2O3-SBA-15 vector.
Mixing Ca (CH)3COO)2·H2O and ZrO2-La2O3Adding deionized water into SBA-15, heating to 50 deg.C, soaking and stirring until water is completely evaporated, and adding Ca (CH)3COO)2·H2O、ZrO2-La2O3The mass ratio of SBA-15 to deionized water is 0.35: 1: 40, the obtained white powdery solid is dried in a thermostat at 60 ℃ for 12 hours, then is put in a box-type muffle furnace to be heated to 650 ℃ at the heating rate of 2 ℃/min, is kept at the temperature for 4 hours, and is cooled to obtain CaO and ZrO2-La2O3CaO/ZrO with a mass ratio of SBA-15 of 0.352-La2O3-SBA-15 solid base.
2. Catalytic synthesis of biodiesel
16.7g of 0.35CaO/ZrO prepared2-La2O3Adding SBA-15 solid base catalyst, 489g of methanol and 333g of glyceryl triacetate into a reactor, carrying out catalytic reaction at 60 ℃ for 40min, cooling to room temperature after the reaction is finished, washing the filtered and recovered mesoporous solid base catalyst with ethanol for 3 times, drying at 60 ℃ for 12 hours for next use, evaporating the filtrate to recover unreacted methanol, stirring the concentrated solution obtained after evaporation, standing for separation, recovering the upper-layer liquid, namely the target product biodiesel, obtaining the reaction product with the yield of 94.24%, and obtaining a small amount of substance in the lower layer, namely the byproduct glycerol.
EXAMPLE 2 the procedure was as in example 1, but the solid base CaO/ZrO was added2-La2O3CaO and ZrO in SBA-152-La2O3The mass ratio of SBA-15 was controlled to 0.25, giving a reaction product yield of 85.60%.
EXAMPLE 3 the procedure was as in example 1, but the solid base CaO/ZrO was added2-La2O3CaO and ZrO in SBA-152-La2O3The mass ratio of SBA-15 was controlled to 0.30, giving a reaction product yield of 90.70%.
EXAMPLE 4 the procedure of example 1 was followed, but the solid base CaO/ZrO was added2-La2O3CaO and ZrO in SBA-152-La2O3The mass ratio of SBA-15 was controlled to 0.40, giving a reaction product yield of 88.82%.
EXAMPLE 5 the procedure of example 1 was followed, except that the reaction time was 10min, to give a reaction product yield of 71.03%.
EXAMPLE 6 the procedure of example 1 was followed, except that the reaction time was 20min, to obtain 86.50% yield of the reaction product.
EXAMPLE 7 the procedure of example 1 was followed, except that the reaction time was 50min, to obtain a reaction product yield of 92.50%.
EXAMPLE 8 the procedure of example 1 was followed, except that the reaction temperature was 55 deg.C, to give a reaction product yield of 91.18%.
EXAMPLE 9 the procedure of example 1 was followed, except that the reaction temperature was 64 deg.C, to give a reaction product yield of 88.10%.
EXAMPLE 10 the procedure of example 1 was followed, except that the amount of the catalyst was 23.3g, to obtain a reaction product yield of 92.68%.
EXAMPLE 11 the procedure of example 1 was followed, except that the amount of the catalyst was 30.0g, to obtain a reaction product yield of 92.08%.
EXAMPLE 12 the procedure of example 1 was repeated, except that the amount of methanol was 245g, to obtain a reaction product yield of 81.67%.
EXAMPLE 13 the procedure of example 1 was repeated, except that the amount of methanol was 735g, to obtain a reaction product yield of 88.30%.
Example 14 the procedure is as in example 1, but the catalyst is recycled for the 2 nd cycle, resulting in a reaction product yield of 94.10%.
EXAMPLE 15 the procedure of example 1 was followed, except that the catalyst was recycled for the 3 rd time, resulting in a reaction product yield of 93.64%.
EXAMPLE 16 the procedure of example 1 was followed, except that the catalyst was recycled for the 4 th time, resulting in a reaction product yield of 92.17%.
EXAMPLE 17 the procedure of example 1 was followed, except that the catalyst was recycled for the 5 th time, resulting in a reaction product yield of 91.05%.
EXAMPLE 18 the procedure was as in EXAMPLE 1, but in the preparation of ZrO2-La2O3In the SBA-15 process, ethylenediamine is not added dropwise to adjust the pH value, and the yield of the reaction product is 83.63%.
EXAMPLE 19 the procedure of example 1 was followed, but La (NO) was not added during the preparation of the solid base3)3·6H2O, CaO and ZrO are produced2CaO/ZrO with a SBA-15 mass ratio of 0.352-SBA-15 solid base catalyst, yield of reaction product 42.12%.
EXAMPLE 20 the procedure of example 1 was followed, except that ZrOCl was not added during the preparation of the solid base2·6H2O to obtain CaO and La2O3-SBA-15CaO/La with mass ratio of 0.352O3SBA-15, giving a reaction product yield of 84.60%.
TABLE 1 operating conditions and reaction results of examples 1-20
CaO and ZrO2-La2O3-mass ratio of SBA-15;
b. preparation of ZrO2-La2O3No ethylene diamine is added dropwise to adjust the pH in the process of SBA-15 carrier;
c. no La (NO) is added in the preparation process of the solid alkali3)3·6H2O, CaO and ZrO2-a mass ratio of SBA-15 of 0.35;
d. ZrOCl is not added in the preparation process of the homobody alkali2·8H2O, CaO and La2O3The mass ratio of SBA-15 is 0.35.
Claims (1)
1. A preparation method of a mesoporous solid base catalyst and a method for synthesizing biodiesel by catalyzing transesterification reaction are disclosed, wherein mesoporous solid base is used as a catalyst to catalyze grease to react with methanol to synthesize biodiesel, the molar ratio of methanol to grease added in a reactor is 5-20: 1, the mass ratio of mesoporous solid base to grease is 0.01-0.1: 1, the reaction temperature is 50-64 ℃, the reaction time is 30-50 min, the reaction is cooled to room temperature after the reaction is finished, the filtered and recovered mesoporous solid base catalyst is washed by ethanol for 3 times and dried at 60 ℃ for 12 hours for next use, filtrate is evaporated to recover unreacted methanol, concentrated solution obtained after evaporation is stirred and kept stand for separation, the recovered upper layer liquid is target product biodiesel, and a small amount of substance in the lower layer is byproduct glycerol;
the mesoporous solid alkali is CaO/ZrO2-La2O3The SBA-15 is prepared by doping lanthanum and zirconium into the SBA-15 carrier skeleton at the same time and then adding Ca (CH)3COO)2·H2O impregnation and high-temperature calcination, and the preparation method comprises the following steps:
(1) at 40 ℃, mixingStirring P123 and HCl solution with pH of 0.8 according to the mass ratio of 1: 37.5 until P123 is completely dissolved to form mixed solution, and respectively adding ZrOCl2·8H2O、La(NO3)3·6H2O, TEOS is added into the mixed solution according to the mass ratio of P123 being 0.216: 0.866: 2.125: 1, the mixed solution is continuously stirred for 24 hours at 40 ℃, the pH value of the mixed solution is adjusted to be subacidity, the mixed solution is stirred for 4 hours, the mixed solution is transferred into a hydrothermal kettle to be crystallized for 24 hours at 100 ℃, white precipitate is formed, the white precipitate is filtered and washed, the filter cake is placed in a thermostat at 55 ℃ to be dried for 12 hours, then the filter cake is placed in a box type muffle furnace to be roasted, and ZrO is prepared after cooling2-La2O3-an SBA-15 vector;
the pH value of the mixed solution is adjusted to be weakly acidic by slowly adding an ethylenediamine solution into the mixed solution to adjust the pH value of the solution to be 3-4;
the roasting in a box-type muffle furnace is carried out by heating to 500-600 ℃ at the heating rate of 1-3 ℃/min and keeping the temperature for 4-6 h;
(2) mixing Ca (CH)3COO)2·H2O and Zr2O3-La2O3Adding SBA-15 into 40ml of deionized water, heating, soaking and stirring until the water is completely evaporated, drying the obtained white powdery solid in a constant temperature oven at 60 ℃ for 12 hours, then placing the dried white powdery solid in a box type muffle furnace for high-temperature calcination, and cooling to obtain CaO/ZrO2-La2O3-SBA-15 solid base;
the impregnation process is Ca (CH)3COO)2·H2O、ZrO2-La2O3The mass ratio of SBA-15 to deionized water is 0.25-0.4: 1: 40, the temperature is 45-60 ℃, and the dipping time is 12 hours;
the high-temperature calcination in the box-type muffle furnace is carried out by heating to 600-700 ℃ at a heating rate of 1-3 ℃/min and keeping the temperature for 3-5 h.
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| CN107051589B (en) * | 2017-02-12 | 2019-12-10 | 湘潭大学 | Method for catalytically synthesizing biodiesel by using short mesoporous DCNH-Zr-SBA-15 molecular sieve |
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