CN111375431B - Solid acid catalyst, preparation method thereof and application thereof in esterification transesterification - Google Patents

Solid acid catalyst, preparation method thereof and application thereof in esterification transesterification Download PDF

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CN111375431B
CN111375431B CN202010195500.0A CN202010195500A CN111375431B CN 111375431 B CN111375431 B CN 111375431B CN 202010195500 A CN202010195500 A CN 202010195500A CN 111375431 B CN111375431 B CN 111375431B
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solid acid
acid catalyst
graphene oxide
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catalyst
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CN111375431A (en
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孙士权
胡文涛
欧吉
何天豪
李雪凝
曾小康
曾欣
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Changsha University of Science and Technology
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    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • 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
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/035—Precipitation on carriers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10—Ester interchange
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

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  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

The invention discloses a solid acid catalyst, a preparation method thereof and application thereof in esterification and transesterification. The preparation method of the solid acid catalyst comprises the steps of carrying out liquid phase deposition reaction on graphene oxide suspension dissolved with aluminum salt to obtain alumina modified graphene oxide, and carrying out mixed reaction on the alumina modified graphene oxide and concentrated sulfuric acid to obtain the solid acid catalyst. The preparation method is simple to operate and mild in condition, the prepared solid acid catalyst has good catalytic effect on esterification and transesterification of the kitchen waste oil, the yield of fatty acid methyl ester is higher than 90%, the solid acid catalyst is easy to separate from products, the solid acid catalyst can be recycled after simple treatment, no pollution is caused, and the production cost of biodiesel prepared from the kitchen waste oil is greatly reduced.

Description

Solid acid catalyst, preparation method thereof and application thereof in esterification transesterification
Technical Field
The invention relates to a solid acid catalyst, in particular to a solid acid catalyst for catalyzing esterification or transesterification of kitchen waste oil, and a preparation method and application thereof, and belongs to the technical field of solid acid catalyst preparation.
Background
At present, catalysts used for transesterification are mainly base catalysts, such as sodium hydroxide, potassium hydroxide, sodium carbonate and the like, and the catalysts have the advantages of mild reaction conditions and high reaction rate, but the base-catalyzed transesterification is very sensitive to the content of water and free fatty acid in raw materials, and the waste cooking oil often contains a large amount of free fatty acid and water, so that the base-catalyzed transesterification is not suitable for catalyzing transesterification of high acid value grease such as kitchen waste oil and the like. Acid catalysis is therefore a more suitable method of catalyzing waste kitchen oil.
Compared with alkali catalysis, the acid catalysis has the advantages that the requirement on raw materials is not high, and good effect can be achieved for the raw materials of high acid value grease such as restaurant waste oil, because free fatty acid in the high acid value grease can be subjected to esterification reaction with methanol to generate fatty acid methyl ester under the acidic condition. The traditional acid catalysis adopts liquid acid such as sulfuric acid, hydrochloric acid, sulfonic acid and the like, and has high catalysis efficiency, but is difficult to separate from a reaction mixture after reaction, and a large amount of acid wastewater can be generated in the separation process to pollute the environment. Thus, research into highly active, easily separable solid acid catalysts is a current research hotspot.
The solid acid used in the preparation of the biodiesel at present mainly comprises heteropolyacid, solid super acid and other types.
(1) Heteropoly acid: heteropoly acids are a class of compounds formed from a variety of transition metals linked by oxygen atoms. Shu Qing et al (journal of Fuel chemistry 2017,45 (08): 939-949) in the form of a dodecaphosphotungstic heteropolyacid (H) 3 PW 12 O 40 ) A series of heteropolyacid catalysts are prepared for a matrix, and are used for esterification reaction of oleic acid and methanol to prepare biodiesel, and the heteropolyacid B-LaPW prepared by a sol-gel method 12 O 40 Si has the best catalytic effect. The mass ratio of oleic acid to methanol is 1:8, and the catalyst is usedAfter the reaction is carried out for 1 hour at the temperature of 65 ℃ and the amount of 2 percent, the oleic acid conversion rate reaches 93 percent, and after the catalyst is recycled for 6 times, the oleic acid conversion rate of 86.4 percent can be obtained. The heteropolyacid has good catalytic activity, but has the defects of small specific surface area, difficult recovery and the like, and limits the application of the heteropolyacid in biodiesel production.
(2) Solid superacid: the solid super acid is Hammett function H 0 The acidity of the acid which is < -11.93 > and the solid super acid can reach over ten thousand times of that of 100 percent sulfuric acid. The solid superacids mainly comprise sulfated metal oxides (SO 4 2- /M x O y ) Tungstic acid metal oxide (WO 3 /M x O y ) Phosphorylated metal oxide (P) 2 O 3 /M x O y ) Etc. Ltsupez et al (Applied Catalysis A: general,2005, 295:97-105) studied TiO 2 /SO 4 2- And ZrO(s) 2 /SO 4 2- As the activity of the solid strong acid catalyst in the transesterification reaction of the cotton seed oil, both catalysts show higher activity. Specific surface area of sulfated titanium oxide was 99.5m 2 Per gram, 91.5m higher than sulfated zirconia 2 /g, thus higher yields of fatty acid methyl esters are obtained. Finally, under the conditions of 2 weight percent of catalyst adding amount and 12:1 alcohol/oil mass ratio, reacting for 8 hours, and then, obtaining TiO 2 /SO 4 2- And ZrO(s) 2 /SO 4 2- The methyl ester yields in the presence were 90% and 85%, respectively. Solid superacids, particularly sulfated metal oxide solid acids, are currently the most used solid acid catalysts in biodiesel production. However, the sulfated metal oxide has only Lewis acid centers, and the acid centers are easy to lose and difficult to regenerate. In summary, it is of great significance to find a solid acid catalyst which is simple in catalyst recovery and regeneration, high in activity, low in pollution and suitable for high acid value oil raw materials such as kitchen waste oil.
Disclosure of Invention
Aiming at the defects of difficult recovery and regeneration, insufficient activity, environmental pollution and the like of the conventional solid acid catalyst in the esterification and transesterification process of kitchen waste oil, the first aim of the invention is to provide the solid acid catalyst which has large specific surface area, more active sites, lewis and Bronsted acid active centers, less loss of the acid active centers and more stable catalytic performance.
The second aim of the invention is to provide a method for preparing the solid acid catalyst, which has low raw material cost, simple preparation process and mild condition.
The third object of the present invention is to provide an application of a solid acid catalyst in catalytic esterification or transesterification, wherein the solid acid catalyst has the advantages of better catalytic activity, more stable performance, easy recovery and regeneration, repeated use and the like, and is particularly suitable for transesterification of waste oil containing fatty acid, such as kitchen waste oil and the like.
In order to achieve the technical aim, the invention provides a preparation method of a solid acid catalyst, which comprises the steps of carrying out liquid phase deposition on a graphene oxide suspension in which aluminum salt is dissolved to obtain aluminum oxide modified graphene oxide; and mixing the alumina modified graphene oxide with concentrated sulfuric acid for reaction to obtain the catalyst.
According to the technical scheme, graphene oxide is used as a carrier of solid acid, the surface of the graphene oxide is provided with rich hydrophilic groups such as hydroxyl groups and carboxyl groups, the graphene oxide is better in dispersibility in water due to the hydrophilic groups, and subsequent aluminum ions are favorably adsorbed on the surface of the graphene oxide through coordination, so that the aluminum ions can be uniformly dispersed and loaded nano aluminum oxide particles on the surface of the graphene oxide in situ in the liquid phase deposition process, and exposure of more catalytic active sites is facilitated. And the solid acid using the graphene oxide as a carrier is beneficial to the subsequent recovery of the solid acid catalyst, and the recovery can be realized through simple filtration and separation. Particularly, after the graphene oxide loaded alumina is acidified by concentrated sulfuric acid, lewis and Bronsted acid active centers are generated simultaneously, the number of the acid active centers is more, the acid active centers are not easy to run off, and the problems that the acid active centers of the common sulfated metal oxide catalyst are single and are easy to run off are solved.
As a preferable scheme, the mass ratio of the graphene oxide to the aluminum oxide in the aluminum oxide modified graphene oxide is controlled to be 2:1-5:1 by using the graphene oxide and aluminum salt. The ratio of the graphene oxide to the aluminum oxide mainly shows the ratio of Lewis and Bronsted acid active centers, the synergistic effect of the two acid active centers can be shown in the preferred ratio range, the catalyst activity is best, the yield of fatty acid methyl ester is higher, and can be kept about 90 percent, and when the ratio of the graphene oxide is too low and too low, the catalytic activity of the catalyst is obviously deteriorated, and the yield of fatty acid methyl ester is obviously lower. In the most preferred scheme, the catalytic effect is obviously reduced when the mass ratio of the graphene oxide to the aluminum oxide in the aluminum oxide modified graphene oxide is controlled to be 2.5-3.5:1, and most preferred is 3:1, for example, the ratio is 2:1 and 4:1.
As a more preferable scheme, the temperature of the liquid phase deposition is 60-100 ℃ and the time is 1-3 hours. The most preferred liquid deposition conditions are: the temperature was 80℃and the time was 2 hours. The nanometer alumina particles can be generated in situ and are dispersed and loaded on the surface of the graphene oxide under the preferable reaction condition.
As a preferable scheme, the reaction temperature of the alumina modified graphene oxide and the concentrated sulfuric acid is 80-120 ℃, the reaction time is 8-15 hours, and the liquid-solid ratio of the reaction is 80-120 mg/mL. The most preferable reaction condition is that the reaction temperature of the alumina modified graphene oxide and the concentrated sulfuric acid is 100 ℃, the reaction time is 12 hours, and the liquid-solid ratio of the reaction is 100mg/mL.
As a preferred embodiment, the aluminum salt is a readily water-soluble aluminum salt commonly known in the art, such as aluminum nitrate.
As a preferred embodiment, the concentration of graphene oxide in the graphene oxide suspension is 1mg/mL. Too high a concentration results in poor stability of the graphene oxide suspension.
The graphene oxide suspension of the present invention may be prepared from graphene oxide conventional in the art, or synthesized with reference to the following method: mixing 3g of graphite powder with 9:1 concentrated sulfuric acid and phosphoric acid, stirring for 1 hour in an ice bath, then adding 18g of potassium permanganate, heating the reaction system to 50 ℃, stirring at constant temperature for 12 hours, pouring the mixture into a beaker filled with crushed ice, dripping 30% hydrogen peroxide solution until the color of the solution changes from dark brown to bright yellow, centrifuging with 30% dilute hydrochloric acid and clear water, washing for multiple times until the pH of supernatant reaches more than 5 after the mixture is centrifuged. And diluting the centrifuged precipitate to 1 liter by adding water, and carrying out ultrasonic treatment for 2 hours to obtain graphene oxide suspension.
The preparation steps of the solid acid catalyst of the invention are as follows:
(1) Weighing a certain amount of aluminum nitrate nonahydrate, adding the aluminum nitrate nonahydrate into the graphene oxide suspension, uniformly stirring, adjusting the pH value of the mixture to be neutral by using a sodium hydroxide solution, and stirring at the constant temperature of 80 ℃ for 2 hours. Taking out the mixture, cooling, standing and aging for 10 hours, filtering, drying, washing, and drying at 100 ℃ to obtain an intermediate product of alumina modified graphene oxide, wherein the reaction is shown as the following formula:
(2) Placing the intermediate product in a beaker, adding concentrated sulfuric acid, performing ultrasonic dispersion for 30 minutes, placing the mixture in a 100 ℃ oven for reaction for 12 hours, and filtering, washing and drying the mixed system to obtain the solid acid catalyst, wherein the solid acid catalyst has the following reaction formula:
the invention also provides a solid acid catalyst, which is obtained by the preparation method.
The invention also provides application of the solid acid catalyst in catalyzing esterification and/or transesterification.
As a preferred embodiment, the solid acid catalyst is used to catalyze the esterification and/or transesterification of waste kitchen oil with formic acid.
As a more preferred scheme, the condition of esterification and/or transesterification of waste kitchen oil with formic acid: the reaction temperature is 60-90 ℃, the reaction time is 4-6 h, the molar ratio of methanol to the kitchen waste oil is 9:1-12:1, and the mass of the solid acid catalyst is 3-6% of the mass of the kitchen waste oil. Most preferred is a process wherein the waste kitchen oil is esterified and/or transesterified with formic acid: the reaction temperature is 60 ℃, the reaction time is 5 hours, the molar ratio of methanol to the kitchen waste oil is 9:1, and the mass of the solid acid catalyst is 3% of the mass of the kitchen waste oil. The catalyst already shows a higher catalytic activity at a temperature of 60 c, whereas further increases in temperature are not significant.
The solid acid catalyst provided by the invention has acidic active centers such as sulfonic acid groups, carboxyl groups and sulfated alumina, can catalyze esterification reaction and transesterification reaction simultaneously, and has a good catalytic effect on high acid value grease such as kitchen waste oil.
The solid acid catalyst regeneration process is simple, only concentrated sulfuric acid is needed for acidification again, and the catalytic activity of the regenerated catalyst is kept above 93%, so that the method has great significance for recycling the catalyst.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
the solid acid catalyst disclosed by the invention takes graphene oxide as a carrier, has a large specific surface area, and generates sulfated alumina and sulfonate in situ, so that uniform dispersion and full exposure of acid active centers are realized, higher esterification or transesterification catalytic activity is shown, the solid acid catalyst simultaneously has Lewis and Bronsted two acid active centers, has an obvious synergistic effect when the two active centers reach a proper proportion, shows an optimal catalytic effect, and shows a decreasing trend in catalytic activity of a catalytic system when the proportion of sulfated alumina is too high or the proportion of sulfated graphene oxide is too high, and the acid active centers in the catalytic system are not easy to run off, so that the catalytic performance is more stable. Compared with the traditional modified sulfated metal oxide catalyst, the catalyst has better modification effect and higher catalytic activity, and is more suitable for being used as a catalyst for esterification and transesterification of kitchen waste oil.
The preparation process of the solid acid catalyst adopts conventional cheap raw materials, has low cost, simple preparation process and mild conditions, and is beneficial to large-scale production and application.
The solid acid catalyst of the invention has the advantages of better catalytic activity, more stable performance, easy recovery and regeneration, repeated use and the like in the application process of catalytic esterification or transesterification, and is particularly suitable for the transesterification process of waste oil containing fatty acid such as kitchen waste oil and the like.
The solid acid catalyst disclosed by the invention adopts the graphene oxide with larger specific surface area as the carrier, is favorable for the diffusion of reaction raw materials and products in the catalytic reaction process of the catalyst, enhances the mass transfer effect of reactants, can improve the catalytic reaction efficiency and shortens the catalytic reaction time. The solid acid catalyst is applied to the esterification transesterification reaction of the kitchen waste oil collected by restaurants and the methanol, the catalyst has shorter catalytic reaction time and higher catalytic activity than the traditional solid acid catalyst, the higher fatty acid methyl ester yield is obtained, the catalyst can be recycled by only filtering after the reaction, and the catalyst can be recycled after simple regeneration, so that the catalyst has no pollution and greatly reduces the cost of the esterification transesterification reaction of the kitchen waste oil.
Detailed Description
The present invention is further illustrated with respect to the following examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting the practice of the invention.
Example 1
Taking a certain amount of graphene oxide suspension, and weighing a certain amount of Al after ultrasonic treatment 2 (SO 4 ) 3 ·9H 2 O is added into the GO suspension, the mass ratio of graphene oxide to aluminum oxide in the product is controlled to be 2:1, after uniform stirring, the pH value of the mixture is regulated to about 7, and the mixture is stirred for 2 hours at the constant temperature of 80 ℃. Taking out the mixture, cooling, standing and aging for 10 hours, filtering and drying to obtain the alumina graphene oxide nanocomposite material, namely GA 21 。
The GO-Al is prepared 2 O 3 Adding concentrated sulfuric acid into the nanocomposite in the amount of 100mg/mL for excessive impregnation, stirring uniformly, performing ultrasonic treatment for 30 minutes, reacting at 100 ℃ for 12 hours, and simultaneously completing Al 2 O 3 Is filtered, washed and driedThe solid acid catalyst is obtained and is marked as GAS 21 。
Example 2
Taking a certain amount of graphene oxide suspension, and weighing a certain amount of Al after ultrasonic treatment 2 (SO 4 ) 3 ·9H 2 O is added into the GO suspension, the mass ratio of graphene oxide to aluminum oxide in the product is controlled to be 3:1, after uniform stirring, the pH value of the mixture is regulated to about 7, and the mixture is stirred for 2 hours at the constant temperature of 80 ℃. Taking out the mixture, cooling, standing and aging for 10 hours, filtering and drying to obtain the alumina graphene oxide nanocomposite material, namely GA 31 。
The GO-Al is prepared 2 O 3 Adding concentrated sulfuric acid into the nanocomposite in the amount of 100mg/mL for excessive impregnation, stirring uniformly, performing ultrasonic treatment for 30 minutes, reacting at 100 ℃ for 12 hours, and simultaneously completing Al 2 O 3 Is filtered, washed and dried to obtain solid acid catalyst, which is named GAS 31 。
Example 3
Taking a certain amount of graphene oxide suspension, and weighing a certain amount of Al after ultrasonic treatment 2 (SO 4 ) 3 ·9H 2 O is added into the GO suspension, the mass ratio of graphene oxide to aluminum oxide in the product is controlled to be 4:1, after uniform stirring, the pH value of the mixture is regulated to about 7, and the mixture is stirred for 2 hours at the constant temperature of 80 ℃. Taking out the mixture, cooling, standing and aging for 10 hours, filtering and drying to obtain the alumina graphene oxide nanocomposite material, namely GA 41 。
The GO-Al is prepared 2 O 3 Adding concentrated sulfuric acid into the nanocomposite in the amount of 100mg/mL for excessive impregnation, stirring uniformly, performing ultrasonic treatment for 30 minutes, reacting at 100 ℃ for 12 hours, and simultaneously completing Al 2 O 3 Is filtered, washed and dried to obtain solid acid catalyst, which is named GAS 41 。
Example 4
The solid acid catalysts prepared in examples 1 to 3 were used for esterification transesterification of kitchen waste oil and methanol, respectively, and the reaction conditions were:
the reaction temperature is 60 ℃, the molar ratio of methanol to the kitchen waste oil is 9:1, the adding amount of the catalyst is 3% of the mass of the kitchen waste oil, and the reaction time is 5 hours.
The reaction product fatty acid methyl ester is analyzed by gas chromatography, the chromatographic condition is a Wax capillary chromatographic column (30 m multiplied by 0.25mm multiplied by 0.25 mu m), the temperature of a sample inlet is 250 ℃, the temperature of a FID detector is 280 ℃, 1mg/mL of methyl undecanoate solution is used as an internal standard solution, the sample injection amount of a sample is 1 mu L, the sample is kept at an initial temperature of 100 ℃ for 1min, then the temperature is raised to 200 ℃ at a speed of 20 ℃/min, the temperature is kept for 3min, the temperature is raised to 220 ℃ at a speed of 10 ℃/min, the temperature is kept for 3min, and finally the temperature is raised to 240 ℃ at a speed of 10 ℃/min, and the temperature is kept for 3min. The yield of fatty acid methyl esters was determined by chromatographic analysis and the specific results are shown in table 1.
TABLE 1 catalytic Activity of solid acid catalysts
Catalyst Fatty acid methyl ester yield (%)
GAS 21 83.57％
GAS 31 91.23％
GAS 41 89.05％
As can be seen from Table 1, the catalyst of the present invention has high activity when applied to the esterification transesterification of kitchen waste oil and methanol.
The solid acid catalyst in the reaction product is recovered by adopting a filtering method, is repeatedly used for 3 times after being immersed and regenerated by concentrated sulfuric acid, and the secondary use effect of the catalyst is shown in table 2.
Catalyst Fatty acid methyl ester yield (%)
GAS 21 77.88％
GAS 31 86.25％
GAS 41 82.63％
As can be seen from Table 2, the catalyst has a good regeneration effect after the catalyst is regenerated by sulfuric acid impregnation and reused for 3 times, and the yield of fatty acid methyl ester is only slightly reduced.
With the above-described ideal examples according to the present invention as a teaching, the related workers can make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.

Claims (4)

1. The application of the solid acid catalyst is characterized in that: the catalyst is applied to catalyzing esterification and/or transesterification of the kitchen waste oil and methanol;
the preparation method of the solid acid catalyst comprises the following steps: carrying out liquid phase deposition reaction on the graphene oxide suspension dissolved with aluminum salt to obtain alumina modified graphene oxide; mixing the alumina modified graphene oxide with concentrated sulfuric acid for reaction to obtain the catalyst; the mass ratio of graphene oxide to aluminum oxide in the aluminum oxide modified graphene oxide is controlled to be 2.5: 1-3.5: 1.
2. the use of a solid acid catalyst according to claim 1, characterized in that: the temperature of the liquid phase deposition is 60-100 ℃ and the time is 1-3 h.
3. The use of a solid acid catalyst according to claim 1, characterized in that: the reaction temperature of the alumina modified graphene oxide and the concentrated sulfuric acid is 80-120 ℃, the reaction time is 8-15 h, and the reaction liquid-solid ratio is 80-120 mg/mL.
4. The application of the solid acid catalyst according to any one of claims 1 to 3, which is characterized in that: the esterification and/or transesterification conditions of the kitchen waste oil and methanol: the reaction temperature is 60-90 ℃, the reaction time is 4-6 h, and the molar ratio of methanol to kitchen waste oil is 9: 1-12: 1, wherein the mass of the solid acid catalyst is 3-6% of the mass of the kitchen waste oil.
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Effect of Metal Oxides on the Catalytic Activities of Sulfonated Graphene Oxide for the Esterification of Oleic Acid and Conversion of Waste Cooking Oil to Biodiesel;Reena D. Souza et al.;《Catalysis Letters》;20180703;第148卷;第2849-2850页第2.3、2.8、2.9节 *
氧化铝-硫酸固体酸催化剂催化油酸与甲醇酯化反应及其动力学研究;陈建军等;《中国油脂》;20141231;第39卷(第9期);第49页第1.2.1、1.2.3节 *

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