CN112403464B - Modified gasification slag biodiesel catalyst and preparation method and application thereof - Google Patents
Modified gasification slag biodiesel catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a modified gasified slag biodiesel catalyst and a preparation method and application thereof, wherein the modified gasified slag is subjected to modification treatment by copper nitrate, sodium hydroxide and irradiation treatment, so that active groups of the modified gasified slag are effectively activated, and the modified gasified slag is further loaded with copper oxide and other active components, so that the catalytic activity is remarkably improved; the catalyst has the advantages of low preparation cost, easy operation, low energy consumption, simple process, environmental protection, no peculiar smell, high activity, good reusability, simple separation and purification procedures, and capability of effectively separating and purifying the catalyst through simple operations of filtering and washing.
Description
Technical Field
The invention belongs to the technical field of biodiesel, and relates to a modified gasified slag biodiesel catalyst, a preparation method and application thereof.
Background
With the increasing exhaustion of fossil fuels and the increasing environmental pollution, there is an urgent need for humans to find new alternative clean energy sources. The biodiesel as a renewable 'green energy' has the advantages of no sulfur, cleanness, no pollution, safe use, biodegradability and the like, and has attracted wide attention. At present, the preparation method of biodiesel mainly adopts a chemical method, namely, a proper catalyst is selected to catalyze the transesterification of alcohol oil so as to prepare biodiesel. The selection of the catalyst is critical, which can directly influence the reaction rate and the product quality, and more catalysts are used nowadays, such as concentrated sulfuric acid, sodium hydroxide and the like, but a large number of experiments show that: the homogeneous catalyst has the defects of multiple side reactions, complicated subsequent product separation and purification procedures, poor controllability, difficult catalyst recovery, environmental pollution, serious corrosion of production equipment and the like. Therefore, there is a need to find an efficient, clean catalyst to replace the traditional catalyst.
The present scholars have been working on solving the above problems, huang Zhenxu et al, volume 52, 6, phase P83-86, na 2 SiO 3 /ZrO 2 In the research of preparing biodiesel by catalyzing soybean oil with solid alkali, sodium silicate/zirconium dioxide serving as a solid alkali catalyst is prepared by an impregnation method, and the biodiesel is prepared by catalyzing the soybean oil with the sodium silicate/zirconium dioxide, the test result shows that when the roasting temperature of the catalyst is 600 ℃, the roasting time of the catalyst is 3h, the mass ratio of silicon to zirconium substances is 4, the mass ratio of alcohol oil substances is 7, and the catalyst consumption (the catalyst accounts for the mass of the soybean oil) is 3%, the yield of the biodiesel can reach 92.5%. Cheng Jun and the like are used for preparing a bifunctional catalyst by loading metallic nickel on a mesoporous Y molecular sieve in P224-228 'nickel-based mesoporous Y catalytic microalgae biodiesel preparation aviation fuel' of solar school report volume 41 and period 5, and catalyzing microalgae biodiesel to be converted into aviation fuel in a fixed bed continuous flow reactor, and test results show that when the reaction temperature is 280 ℃ and the algae oil flow rate is 0.02mL/min, the aviation fuel selectivity is enhanced to 90.19%, and the alkane content in the aviation fuel reaches the highest value 86.43%. Cheng Zhifa et al, in the "research on NiFe bimetallic catalyst for methyl laurate hydrogenation" at 7 th stage P860-866 of the journal of Fuel chemistry ", the NF420 catalyst prepared by reduction at 420 ℃ intensifies the hydrogenation activity and the product selectivity of methyl laurate, and the experimental result shows that the catalyst has the hydrogenation conversion rate of methyl laurate and the selectivity of alkane compound as high as 93.3% and 90.0% respectively at the reaction temperature of 380 ℃ and the reaction pressure of 2.0 MPa.
Compared with a homogeneous catalyst, the catalyst prepared by the research has the advantages that the subsequent separation process is simpler, but the raw material cost of the catalyst is higher, the recycling property of the catalyst is poorer, and the catalytic effect is still to be further improved.
The gasified slag, namely the coal-gasification slag and coal-based solid waste are accumulated on the waste land in a large quantity, so that a large quantity of land is occupied, and meanwhile, the surrounding environments such as soil, water body, atmosphere and the like are seriously polluted. If the modified biodiesel can be subjected to proper modification treatment and used for strengthening transesterification reaction to prepare biodiesel, the modified biodiesel can realize high-efficiency conversion of clean energy and can effectively inhibit gasification slag from polluting the environment.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the modified gasification slag biodiesel catalyst and the preparation method and application thereof, and overcomes the defects of high preparation energy cost, poor recycling property, complicated separation and purification procedures and the like of the existing biodiesel catalyst.
In order to achieve the above purpose, the invention provides a preparation method of a modified gasification slag biodiesel catalyst, which comprises the following steps:
s1, primary modification of gasification slag: roasting gasification slag, cooling after roasting, immersing in a copper nitrate aqueous solution after cooling, carrying out first gamma ray irradiation to obtain a first precursor, cooling the first precursor, carrying out first standing, heating after the first standing is finished, carrying out second standing, carrying out second gamma ray irradiation to obtain a solid-liquid mixture A, carrying out solid-liquid separation on the solid-liquid mixture A to obtain gasification slag particles, and washing, drying, grinding and sieving the obtained gasification slag particles to obtain the first-stage modified gasification slag.
S2, carrying out secondary modification on gasification slag: and (2) fully mixing an alkaline water solution and the first-stage modified gasified slag obtained in the step (S1), then carrying out gamma ray irradiation for the third time to obtain a second precursor, cooling the second precursor, then carrying out standing for the third time, then carrying out gamma ray irradiation for the fourth time to obtain a solid-liquid mixture B, carrying out solid-liquid separation on the solid-liquid mixture B to obtain gasified slag granules, and washing, drying, grinding and sieving the obtained gasified slag granules to obtain the modified gasified slag catalyst.
Further, in the step S1, the roasting condition is that roasting is carried out for 1-2 hours at 250-300 ℃; the solid-liquid mass ratio of the gasified slag after roasting to the copper nitrate aqueous solution is 1 (3-7), and the mass concentration of the copper nitrate aqueous solution is 3% -7% (w/v); cooling the first precursor to room temperature, and then carrying out first standing for 3-6 hours; and after the first standing is finished, heating to 70-100 ℃, and carrying out second standing, wherein the standing time is 2-4 h.
Further, in the step S1, the first gamma ray irradiation condition is: irradiating with gamma rays of 150kGy-300kGy for 3min-8min at 50-70 ℃; the second gamma ray irradiation conditions are as follows: irradiating with gamma rays of 13kGy-17kGy at 35-50deg.C for 5-10 min.
Further, in the step S1, the gasified slag particles are rinsed with deionized water until floating impurities on the gasified slag particles are thoroughly removed, and then the gasified slag particles are dried and ground and sieved by a sieve of 50-100 meshes, thus obtaining the first-stage modified gasified slag.
Further, in the step S2, the aqueous alkali solution is a sodium hydroxide aqueous solution with a mass concentration of 1% -7% (w/v), and a mass ratio of the primary modified gasified slag to the sodium hydroxide aqueous solution is 1: (1-5); and cooling the second precursor to room temperature for third standing, wherein the third standing time is 0.5-2 h.
Further, in the step S2, the condition of the third gamma ray irradiation is that the gamma ray of 15kGy-33kGy is irradiated for 18min-30min at room temperature; the condition of the fourth gamma ray irradiation is that the gamma ray of 100kGy-180kGy is irradiated for 0.5min-5min at 60-86 ℃.
Further, in the step S2, the gasified slag granules are rinsed with deionized water until attachments on the surfaces of the gasified slag granules are thoroughly removed, and then the gasified slag granules are dried and ground, and the gasified slag granules are sieved by a sieve of 50-100 meshes, so that the modified gasified slag catalyst is obtained.
The invention also provides a modified gasification slag catalyst prepared by the preparation method of the modified gasification slag biodiesel catalyst.
Further, the modified gasification slag catalyst is added into an alcohol-oil transesterification reaction system, the dosage of the modified gasification slag catalyst accounts for 3.5-7.8% of the mass ratio of oil, the reaction temperature is 160-230 ℃, and the catalyst and the product are recovered after the reaction is completed.
Further, the product is decompressed to remove low molecular alcohol, the product from which the low molecular alcohol is removed is subjected to solid-liquid separation, and the solid obtained by filtration separation is a modified gasified slag catalyst which can be reused after being washed by deionized water; and layering the liquid obtained by filtering and separating through a separating funnel, wherein the upper layer is biodiesel and the lower layer is byproduct crude glycerol.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention provides a preparation method of a modified gasified slag biodiesel catalyst, which is characterized in that the modified gasified slag is subjected to modification treatment by copper nitrate, sodium hydroxide and irradiation treatment, so that active groups of the modified gasified slag are effectively activated, and the modified gasified slag is further loaded with copper oxide and other active components, so that the catalytic activity is obviously improved; the catalyst has the advantages of low preparation cost, easy operation, low energy consumption, simple process, environmental protection, no peculiar smell, high activity, good reusability, simple separation and purification procedures, and capability of effectively separating and purifying the catalyst through simple operations of filtering and washing.
In the invention, gasified slag is soaked in copper nitrate solution, so that active groups are loaded on the gasified slag; compared with the traditional high-temperature roasting modification, the method has the advantages that the roasting time and the roasting temperature are obviously reduced, the energy consumption is effectively reduced, and meanwhile, the irradiation strengthens the load of active groups of the gasified slag, activates the active groups in the soaked copper nitrate solution and further improves the pore structure of the gasified slag; in the invention, sodium hydroxide is adopted to secondarily modify gasified slag, active groups are secondarily loaded on the gasified slag, and meanwhile gamma ray irradiation is carried out, so that the active group loading and pore structure of the gasified slag are strengthened by the synergistic effect generated by alkali solution treatment and irradiation, and the catalytic activity of the gasified slag is further improved.
Furthermore, the invention realizes the resource utilization of the solid waste gas gasification slag, relieves the environmental pollution pressure of the gasification slag, and effectively solves the treatment problem of the gasification slag; the catalyst provided by the invention has obvious effect in the transesterification reaction process, improves the conversion rate of biodiesel, realizes the recycling harmless utilization of gasified slag, and effectively solves the treatment problem of gasified slag.
Detailed Description
The invention is further described below in connection with the following detailed description.
Example 1
1) Primary modification of gasification slag: taking a certain amount of gasified slag to remove surface impurities, roasting at 250 ℃ for 1h, cooling, immersing in a copper nitrate aqueous solution (solid-liquid mass ratio is 1:3), irradiating for 3min at 50 ℃ by using 150kGy gamma rays, cooling the solid-liquid mixture to room temperature, standing for 3h, and standing for 2h at 70 ℃; then irradiated with gamma rays of 13kGy at 35℃for 5min. Separating the irradiated solid-liquid mixture, flushing the gasified slag with deionized water until floating impurities are thoroughly removed, drying and grinding gasified slag particles, and sieving the gasified slag particles with a 50-mesh sieve;
2) Secondary modification of gasification slag: fully mixing the gasified slag obtained in the step 1 with sodium hydroxide aqueous solution according to the mass ratio of 1:1, irradiating with gamma rays of 15kGy at room temperature for 18min, and then cooling the solid-liquid mixture to room temperature and standing for 0.5h; then irradiated with gamma rays of 100kGy for 0.5min at 60 ℃. Separating the solid-liquid mixture, repeatedly flushing the gasification slag with deionized water until the attachments on the surface of the gasification slag are thoroughly removed, then drying and grinding gasification slag granules, and sieving the granules with a 50-mesh sieve to obtain a modified gasification slag catalyst;
3) Adding a modified gasified slag catalyst into an alcohol-oil transesterification reaction system, wherein the oil is illegal cooking oil, the alcohol is methanol, the catalyst consumption (the mass ratio of the catalyst to the oil) is 3.5%, and after the reaction temperature is 160 ℃, the catalyst and the product are recovered after the reaction is completed. Removing low molecular alcohol from the product by decompression, filtering and separating the catalyst, and cleaning the catalyst with deionized water for continuous utilization; separating biodiesel and byproduct glycerol after layering the liquid through a separating funnel, wherein the biodiesel at the upper layer and the byproduct crude glycerol at the lower layer are subjected to performance comparison analysis.
And (3) taking out the catalyst, repeating the esterification experiment described in the step (3) for 10 times, and the recycling effect of the catalyst is shown in the following table 1-1.
TABLE 1-1 modified gasification slag catalyst recycling effect
As can be seen from the data in Table 1-1, the conversion rate of biodiesel can reach 98.7% at most by using the modified gasification slag catalyst for transesterification in the above-mentioned example 1; and after the modified gasification slag catalyst is recycled for 10 times, the conversion rate of biodiesel is still more than 80%, so that the catalytic effect of the modified gasification slag catalyst is very good.
The obtained biodiesel was subjected to product performance detection and comparison analysis of the main physicochemical parameters, and the results are shown in tables 1-2 below.
TABLE 1-2 Main physicochemical Properties of self-made biodiesel
From the data in tables 1-2, all physicochemical properties of the obtained biodiesel meet European Union EN14214 standard.
Example 2
1) Primary modification of gasification slag: taking a certain amount of gasified slag to remove surface impurities, roasting at 260 ℃ for 1.2 hours, cooling, immersing in a copper nitrate aqueous solution (solid-liquid ratio is 1:4), irradiating for 4 minutes at 55 ℃ by using gamma rays of 180kGy, cooling the solid-liquid mixture to room temperature, standing for 3.5 hours, and standing at 80 ℃ for 2.5 hours; then irradiated with gamma rays of 14kGy for 6min at 37 ℃. Separating the irradiated solid-liquid mixture, flushing the gasified slag with deionized water until floating impurities are thoroughly removed, drying and grinding gasified slag particles, and sieving the gasified slag particles with a 60-mesh sieve;
2) Secondary modification of gasification slag: fully mixing the gasified slag obtained in the step 1 with sodium hydroxide aqueous solution according to the mass ratio of 1:2, irradiating with gamma rays of 18kGy at room temperature for 22min, and then cooling the solid-liquid mixture to room temperature and standing for 0.8h; then irradiated with gamma rays of 110kGy for 1min at 65 ℃. Separating the solid-liquid mixture, repeatedly flushing the gasification slag with deionized water until the attachments on the surface of the gasification slag are thoroughly removed, then drying and grinding gasification slag granules, and sieving the granules with a 60-mesh sieve to obtain a modified gasification slag catalyst;
3) Adding the modified gasified slag catalyst into an alcohol-oil transesterification reaction system, wherein the catalyst dosage (the catalyst accounts for the mass ratio of oil) is 4%, and recovering the catalyst and the product after the reaction is completed at 170 ℃. Removing low molecular alcohol from the product by decompression, filtering and separating the catalyst, and cleaning the catalyst with deionized water for continuous utilization; separating biodiesel and byproduct glycerol after layering the liquid through a separating funnel, wherein the biodiesel at the upper layer and the byproduct crude glycerol at the lower layer are subjected to performance comparison analysis.
The catalyst was removed and the esterification experiment described in (3) was repeated 10 times, with the catalyst reuse effect shown in Table 2-1 below.
TABLE 2-1 modified gasification slag catalyst recycle conversion effect
As can be seen from the data in Table 2-1, the modified gasification slag catalyst is used for transesterification in the above example 2, and the conversion rate of biodiesel can reach 98.9% at the highest; and after the modified gasification slag catalyst is recycled for 10 times, the conversion rate of biodiesel is still more than 80%, so that the catalytic effect of the modified gasification slag catalyst is very good.
The obtained biodiesel was subjected to product performance detection and comparison analysis of the main physicochemical parameters, and the results are shown in tables 2-2 below.
TABLE 2-2 Main physicochemical Properties of self-made biodiesel
From the data in Table 2-2, it is clear that each physicochemical characteristic of the obtained biodiesel meets European Union EN14214 standard.
Example 3
1) Primary modification of gasification slag: taking a certain amount of gasified slag to remove surface impurities, roasting at 270 ℃ for 1.4 hours, cooling, immersing in a copper nitrate aqueous solution (solid-liquid ratio is 1:5), irradiating at 60 ℃ for 5 minutes by using gamma rays of 210kGy, cooling the solid-liquid mixture to room temperature, standing for 4 hours, and standing at 80 ℃ for 3 hours; then irradiated with gamma rays of 15kGy at 40℃for 7min. Separating the irradiated solid-liquid mixture, flushing the gasified slag with deionized water until floating impurities are thoroughly removed, drying and grinding gasified slag particles, and sieving the gasified slag particles with a 70-mesh sieve;
2) Secondary modification of gasification slag: fully mixing the gasified slag obtained in the step 1 with sodium hydroxide aqueous solution according to the mass ratio of 1:3, irradiating with gamma rays of 22kGy for 24min at room temperature, and then cooling the solid-liquid mixture to room temperature and standing for 1h; then irradiated with 140kGy of gamma rays at 75℃for 2min. Separating the solid-liquid mixture, repeatedly flushing the gasification slag with deionized water until the attachments on the surface of the gasification slag are thoroughly removed, then drying and grinding gasification slag granules, and sieving the granules with a 70-mesh sieve to obtain a modified gasification slag catalyst;
3) Adding the modified gasified slag catalyst into an alcohol-oil transesterification reaction system, wherein the catalyst dosage (the catalyst accounts for the mass ratio of oil) is 5%, and recovering the catalyst and the product after the reaction is completed at the reaction temperature of 190 ℃. Removing low molecular alcohol from the product by decompression, filtering and separating the catalyst, and cleaning the catalyst with deionized water for continuous utilization; separating biodiesel and byproduct glycerol after layering the liquid through a separating funnel, wherein the biodiesel at the upper layer and the byproduct crude glycerol at the lower layer are subjected to performance comparison analysis.
The catalyst was removed and the esterification experiment described in (3) was repeated 10 times, the catalyst recycling effect being shown in Table 3-1 below.
TABLE 3-1 modified gasification slag catalyst recycle conversion effect
As can be seen from the data in Table 3-1, the modified gasification slag catalyst is used for transesterification in the above example 3, and the conversion rate of biodiesel can reach 99.1% at most; and after the modified gasification slag catalyst is recycled for 10 times, the conversion rate of biodiesel is still more than 80%, so that the catalytic effect of the modified gasification slag catalyst is very good.
The obtained biodiesel was subjected to product performance detection and comparison analysis of the main physicochemical parameters, and the results are shown in tables 3-2 below.
Table 3-2 main physicochemical properties of homemade biodiesel.
From the data in Table 3-2, it is clear that each physicochemical characteristic of the obtained biodiesel meets European Union EN14214 standard.
Example 4
1) Primary modification of gasification slag: taking a certain amount of gasified slag to remove surface impurities, roasting at 290 ℃ for 1.8 hours, cooling, immersing in a copper nitrate aqueous solution (solid-liquid ratio is 1:6), radiating for 7 minutes at 65 ℃ by using 270kGy gamma rays, cooling the solid-liquid mixture to room temperature, standing for 5.5 hours, and standing for 3.5 hours at 90 ℃; then irradiated with gamma rays of 16kGy for 9min at 45 ℃. Separating the irradiated solid-liquid mixture, flushing the gasified slag with deionized water until floating impurities are thoroughly removed, drying and grinding gasified slag particles, and sieving the gasified slag particles with a 90-mesh sieve;
2) Secondary modification of gasification slag: fully mixing the gasified slag obtained in the step 1 with sodium hydroxide aqueous solution according to the mass ratio of 1:4, irradiating for 27min by using gamma rays of 30kGy at room temperature, and then cooling the solid-liquid mixture to room temperature and standing for 1.7h; then irradiated with gamma rays of 160kGy for 4min at 80 ℃. Separating the solid-liquid mixture, repeatedly flushing the gasification slag with deionized water until the attachments on the surface of the gasification slag are thoroughly removed, then drying and grinding gasification slag granules, and sieving the granules with a 90-mesh sieve to obtain a modified gasification slag catalyst;
3) Adding the modified gasified slag catalyst into an alcohol-oil transesterification reaction system, wherein the catalyst dosage (the catalyst accounts for 7% of the mass of oil), and recovering the catalyst and the product after the reaction is completed at the reaction temperature of 210 ℃. Removing low molecular alcohol from the product by decompression, filtering and separating the catalyst, and cleaning the catalyst with deionized water for continuous utilization; separating biodiesel and byproduct glycerol after layering the liquid through a separating funnel, wherein the biodiesel at the upper layer and the byproduct crude glycerol at the lower layer are subjected to performance comparison analysis.
The catalyst was removed and the esterification experiment described in (3) was repeated 10 times, the catalyst recycling effect being shown in Table 4-1 below.
TABLE 4-1 modified gasification slag catalyst recycle conversion effect
As can be seen from the data in Table 4-1, the modified gasification slag catalyst is used for transesterification in the above example 4, and the conversion rate of biodiesel can reach 99.5% at the highest; and after the modified gasification slag catalyst is recycled for 10 times, the conversion rate of biodiesel is still more than 80%, so that the catalytic effect of the modified gasification slag catalyst is very good.
The obtained biodiesel was subjected to product performance detection and comparison analysis of the main physicochemical parameters, and the results are shown in tables 3-2 below.
Table 4-2 main physicochemical properties of homemade biodiesel.
From the data in Table 4-2, it is clear that each physicochemical characteristic of the obtained biodiesel meets European Union EN14214 standard.
Example 5
1) Primary modification of gasification slag: taking a certain amount of gasified slag to remove surface impurities, roasting at 300 ℃ for 2 hours, cooling, immersing in a copper nitrate aqueous solution (solid-liquid ratio is 1:7), irradiating for 8 minutes at 70 ℃ by using gamma rays of 300kGy, cooling the solid-liquid mixture to room temperature, standing for 6 hours, and standing for 4 hours at 100 ℃; then irradiated with gamma rays of 17kGy for 10min at 50 ℃. Separating the irradiated solid-liquid mixture, flushing the gasified slag with deionized water until floating impurities are thoroughly removed, drying and grinding gasified slag particles, and sieving the gasified slag particles with a 100-mesh sieve;
2) Secondary modification of gasification slag: fully mixing the gasified slag obtained in the step 1 with sodium hydroxide aqueous solution according to the mass ratio of 1:5, irradiating for 30min with gamma rays of 33kGy at room temperature, and then cooling the solid-liquid mixture to room temperature and standing for 2h; then irradiated with 180kGy gamma rays at 86℃for 5min. Separating the solid-liquid mixture, repeatedly flushing the gasification slag with deionized water until the attachments on the surface of the gasification slag are thoroughly removed, then drying and grinding gasification slag granules, and sieving the granules with a 100-mesh sieve to obtain a modified gasification slag catalyst;
3) Adding the modified gasified slag catalyst into an alcohol-oil transesterification reaction system, wherein the catalyst dosage (the catalyst accounts for 7.8% of the mass of oil), and recovering the catalyst and the product after the reaction is completed at the reaction temperature of 230 ℃. Removing low molecular alcohol from the product by decompression, filtering and separating the catalyst, and cleaning the catalyst with deionized water for continuous utilization; separating biodiesel and byproduct glycerol after layering the liquid through a separating funnel, wherein the biodiesel at the upper layer and the byproduct crude glycerol at the lower layer are subjected to performance comparison analysis.
The catalyst was removed and the esterification experiment described in (3) was repeated 10 times, the catalyst recycling effect being shown in Table 5-1 below.
TABLE 5-1 modified gasification slag catalyst recycle conversion effect
As can be seen from the data in Table 5-1, the modified gasification slag catalyst is used for transesterification in the above example 5, and the conversion rate of biodiesel can reach 99.3% at the highest; and after the modified gasification slag catalyst is recycled for 10 times, the conversion rate of biodiesel is still more than 80%, so that the catalytic effect of the modified gasification slag catalyst is very good.
The obtained biodiesel was subjected to product performance detection and comparison analysis of the main physicochemical parameters, and the results are shown in Table 5-2 below.
Table 5-2 main physicochemical properties of homemade biodiesel.
From the data in Table 5-2, it is clear that each physicochemical characteristic of the obtained biodiesel meets European Union EN14214 standard.
The catalyst prepared by the method not only solves the treatment problem of gasified slag, but also improves the conversion rate of biodiesel and reduces the conversion cost of biodiesel, and the obtained catalyst has high catalytic activity, no peculiar smell and repeated use for many times; the main performance index of the biodiesel preparation meets the European Union EN14214 standard.
The above description and the content are only basic illustrations under the concept of the present invention, and any equivalent transformation made according to the technical solution of the present invention shall fall within the protection scope of the present invention.
Claims (6)
1. The preparation method of the modified gasification slag biodiesel catalyst is characterized by comprising the following steps:
s1, primary modification of gasification slag: roasting gasification slag, cooling after roasting, immersing the gasified slag in a copper nitrate aqueous solution after cooling, carrying out first gamma ray irradiation to obtain a first precursor, cooling the first precursor, carrying out first standing, heating after the first standing is finished, carrying out second standing, then carrying out second gamma ray irradiation to obtain a solid-liquid mixture A, carrying out solid-liquid separation on the solid-liquid mixture A to obtain gasification slag particles, and washing, drying, grinding and sieving the obtained gasification slag particles to obtain first-stage modified gasification slag;
s2, carrying out secondary modification on gasification slag: fully mixing an alkaline water solution and the first-stage modified gasified slag, performing gamma ray irradiation for the third time to obtain a second precursor, cooling the second precursor, performing standing for the third time, performing gamma ray irradiation for the fourth time to obtain a solid-liquid mixture B, performing solid-liquid separation on the solid-liquid mixture B to obtain gasified slag granules, and washing, drying, grinding and sieving the obtained gasified slag granules to obtain a modified gasified slag catalyst;
in the step S1, the roasting condition is that roasting is carried out for 1-h-2 hours at the temperature of 250-300 ℃; the solid-liquid mass ratio of the gasified slag after roasting to the copper nitrate aqueous solution is 1 (3-7), and the mass concentration of the copper nitrate aqueous solution is 3% -7%; cooling the first precursor to room temperature, and then carrying out first standing for 3h-6h; heating to 70-100 ℃ after the first standing is finished, and carrying out second standing, wherein the standing time is 2h-4 h;
in the step S1, the first gamma ray irradiation conditions are as follows: irradiating with gamma rays of 150kGy-300kGy for 3min-8min at 50-70 ℃; the second gamma ray irradiation conditions are as follows: irradiating with gamma rays of 13kGy-17kGy at 35-50deg.C for 5-10 min;
in the step S2, the aqueous alkali solution is a sodium hydroxide aqueous solution with a mass concentration of 1% -7%, and the mass ratio of the primary modified gasified slag to the sodium hydroxide aqueous solution is 1: (1-5); cooling the second precursor to room temperature for third standing, wherein the third standing time is 0.5-h-2 h;
in the step S2, the condition of the third gamma ray irradiation is that the gamma ray of 15kGy-33kGy is irradiated for 18min-30min at room temperature; the condition of the fourth gamma ray irradiation is that the gamma ray of 100kGy-180kGy is irradiated for 0.5min-5min at 60-86 ℃.
2. The method for preparing the modified gasified slag biodiesel catalyst according to claim 1, wherein in the step S1, the gasified slag particles are washed by deionized water until floating impurities on the gasified slag particles are thoroughly removed, and then the gasified slag particles are dried and ground and pass through a sieve of 50-100 meshes, so that the first-stage modified gasified slag is obtained.
3. The method for preparing the modified gasified slag biodiesel catalyst according to claim 1, wherein in the step S2, the gasified slag granules are washed by deionized water until attachments on the surfaces of the gasified slag granules are thoroughly removed, and then the gasified slag granules are dried and ground, and the dried gasified slag granules are sieved by a sieve of 50-100 meshes, so that the modified gasified slag catalyst is obtained.
4. A modified gasification slag catalyst produced by the production method of a modified gasification slag biodiesel catalyst according to any one of claims 1 to 3.
5. The method for using modified gasified slag catalyst according to claim 4, wherein the modified gasified slag catalyst is added into an alcohol-oil transesterification reaction system, the amount of the modified gasified slag catalyst is 3.5% -7.8% of the mass ratio of oil, the reaction temperature is 160 ℃ -230 ℃, and the catalyst and the product are recovered after the reaction is completed.
6. The method for using a modified gasified slag catalyst according to claim 5, wherein the product is decompressed to remove low molecular alcohol, the product from which the low molecular alcohol is removed is subjected to solid-liquid separation, the solid obtained by filtration separation is the modified gasified slag catalyst, and the modified gasified slag catalyst can be reused after being washed by deionized water; and layering the liquid obtained by filtering and separating through a separating funnel, wherein the upper layer is biodiesel and the lower layer is byproduct crude glycerol.
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