CN112403464A - Modified gasified slag biodiesel catalyst and preparation method and application thereof - Google Patents
Modified gasified 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 gasified slag is modified by copper nitrate, sodium hydroxide and irradiation treatment, so that the active groups of the gasified slag are effectively activated, and the modified gasified slag is further loaded with active components such as copper oxide and the like, 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 and high activity, can effectively strengthen the ester exchange reaction of alcohol oil in the ester exchange reaction process, has good reusability and simple separation and purification procedures, and can effectively separate and purify the catalyst through simple operation of filtering and washing.
Description
Technical Field
The invention belongs to the technical field of biodiesel, and relates to a modified gasification slag biodiesel catalyst, and a preparation method and application thereof.
Background
With the gradual depletion of fossil fuels and the increasing increase of environmental pollution, people are urgently required to find new alternative clean energy sources. As a renewable 'green energy source', biodiesel has the advantages of no sulfur, cleanness, no pollution, safe use, biodegradability and the like, and has attracted extensive attention of people. At present, the preparation method of the biodiesel mainly adopts a chemical method, namely, a proper catalyst is selected to catalyze the alcohol-oil transesterification reaction so as to prepare the biodiesel. Among them, the selection of the catalyst is key, which can directly affect the reaction rate and the product quality, and the most applied catalysts nowadays are concentrated sulfuric acid, sodium hydroxide, etc., but a lot of experiments show that: the homogeneous catalyst generally has the defects of more side reactions, complex subsequent product separation and purification procedures, poor controllability, difficult recovery of the catalyst, environmental pollution, serious corrosion of production equipment and the like. Therefore, there is a need to find an efficient, clean catalyst to replace traditional catalysts.
To solve the above problems, Huang Sha Xue et al, inorganic salt industry vol.52, No. 6, P83-86, "Na2SiO3/ZrO2In the research of preparing biodiesel by catalyzing soybean oil with solid base, the solid base catalyst sodium silicate/zirconium dioxide is prepared by an impregnation method, and the biodiesel is prepared by catalyzing the soybean oil with the solid base catalyst sodium silicate/zirconium dioxide, and the test result shows that when the roasting temperature of the catalyst is 600 ℃, the roasting time of the catalyst is 3 hours, the mass ratio of silicon to zirconium substances is 4, the mass ratio of alcohol oil substances is 7, and the dosage of the catalyst (the mass of the catalyst in the soybean oil) is 3%, the yield of the biodiesel can reach 92.5%. Chengjun et al in "solar journal of 41 vol. No. 5 No. P224-228" preparation of aviation fuel oil from microalgae biodiesel by nickel-based mesoporous Y catalysisThe dual-function catalyst is prepared by loading metal nickel on the porous Y molecular sieve, the microalgae biodiesel is catalyzed and converted into aviation fuel oil in the fixed bed continuous flow reactor, and the test result shows that when the reaction temperature is 280 ℃ and the flow rate of the algae oil is 0.02mL/min, the aviation fuel oil selectivity is enhanced to 90.19%, and the alkane content in the aviation fuel oil reaches the highest value of 86.43%. "the research of using NiFe bimetallic catalyst in methyl laurate hydrogenation" in No. 7P 860-866 of volume 48 of "journal of Fuel chemistry" of proceedings et al, the research of using NiFe bimetallic catalyst in methyl laurate hydrogenation "strengthens the hydrogenation activity and product selectivity of methyl laurate by NF420 catalyst prepared by reduction at 420 ℃, and the test result shows that when the reaction temperature of the catalyst is 380 ℃ and the reaction pressure is 2.0MPa, the hydrogenation conversion rate of methyl laurate and the selectivity of alkane compounds are respectively as high as 93.3% and 90.0%.
The catalysts prepared by the research have better effects, compared with homogeneous catalysts, the subsequent separation process is simpler, but the raw material cost of the catalysts is higher, the reusability of the catalysts is poorer, and the catalytic effect is to be further improved.
The gasified slag, namely the gasified slag-coal-based solid waste, is accumulated on the waste land in large quantity, not only occupies a large amount of land, but also causes serious pollution to the surrounding environments such as soil, water, atmosphere and the like. If the modified biodiesel can be modified properly and used for preparing biodiesel by enhancing ester exchange reaction, the high-efficiency conversion of clean energy can be realized, and the environment pollution caused by gasified slag can be effectively prevented.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a modified gasified residue biodiesel catalyst, a preparation method and application thereof, and overcomes the defects of high preparation energy cost, poor reusability, complicated separation and purification procedures and the like of the conventional biodiesel catalyst.
In order to realize the aim, the invention provides the following technical scheme that the preparation method of the modified gasified slag biodiesel catalyst comprises the following steps:
s1, primary modification of gasified slag: roasting the gasified slag, cooling after roasting, soaking in a copper nitrate aqueous solution after cooling, performing first gamma ray irradiation to obtain a first precursor, cooling the first precursor, standing for the first time, heating after the first standing is finished, standing for the second time, performing second gamma ray irradiation to obtain a solid-liquid mixture A, performing solid-liquid separation on the solid-liquid mixture A to obtain gasified slag particles, and washing, drying, grinding and sieving the obtained gasified slag particles to obtain the primary modified gasified slag.
S2, secondary modification of gasified slag: and (4) fully mixing an alkaline aqueous solution with the first-stage modified gasification slag obtained in the step S1, performing gamma ray irradiation for the third time to obtain a second precursor, cooling the second precursor, 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 gasification slag aggregates, and washing, drying, grinding and sieving the obtained gasification slag aggregates to obtain the modified gasification slag catalyst.
Further, in the step S1, the roasting condition is roasting at 250-300 ℃ for 1-2 h; the solid-liquid mass ratio of the roasted gasification slag 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 h; and after the first standing is finished, heating to 70-100 ℃, and standing for the second time, wherein the standing time is 2-4 h.
Further, in step S1, the first gamma ray irradiation conditions are: irradiating by using a gamma ray of 150kGy-300kGy at the temperature of 50-70 ℃ for 3-8 min; the second gamma ray irradiation conditions are as follows: irradiating with gamma ray of 13-17 kGy at 35-50 deg.c for 5-10 min.
Further, in the step S1, the gasified slag particles are washed with deionized water until the floating impurities on the gasified slag particles are completely removed, and then the gasified slag particles are dried and ground, and pass through a 50-100 mesh sieve, so as to obtain the first-grade modified gasified slag.
Further, in the step S2, the aqueous alkali solution is an aqueous sodium hydroxide solution with a mass concentration of 1% to 7% (w/v), and the mass ratio of the first-stage modified gasified slag to the aqueous sodium hydroxide solution is 1: (1-5); and cooling the second precursor to room temperature, and standing for the third time, wherein the standing time for the third time is 0.5-2 h.
Further, in the step S2, the third gamma ray irradiation condition is that the gamma ray irradiation with 15kGy to 33kGy is performed at room temperature for 18min to 30 min; the condition of the fourth gamma ray irradiation is that the gamma ray irradiation of 100kGy-180kGy is carried out for 0.5min-5min at the temperature of 60 ℃ to 86 ℃.
Further, in the step S2, the gasification slag granules are washed with deionized water until the attachments on the surfaces of the gasification slag granules are completely removed, and then the gasification slag granules are dried and ground, and are sieved by a 50-100 mesh sieve, so as to obtain the modified gasification slag catalyst.
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 amount of the modified gasification slag catalyst accounts for 3.5-7.8% of the mass ratio of the oil, the reaction temperature is 160-230 ℃, and the catalyst and the product are recovered after the reaction is finished.
Further, the product is subjected to reduced pressure 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 filtering and separation is a modified gasification slag catalyst which can be reused after being washed by deionized water; the liquid obtained by filtration and separation is layered by a separating funnel, the upper layer is the biodiesel, and the lower layer is the byproduct crude glycerin.
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, wherein the gasified slag is subjected to modification treatment through copper nitrate, sodium hydroxide and irradiation treatment, so that the active groups of the gasified slag are effectively activated, and the modified gasified slag is further loaded with active ingredients such as copper oxide and the like, 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 and high activity, can effectively strengthen the ester exchange reaction of alcohol oil in the ester exchange reaction process, has good reusability and simple separation and purification procedures, and can effectively separate and purify the catalyst through simple operation of filtering and washing.
In the invention, the gasified slag is soaked in a copper nitrate solution, so that the gasified slag is loaded with active groups; the method has the advantages that the gasification slag is roasted, so that the pore structure of the gasification slag can be increased, and compared with the traditional high-temperature roasting modification, the method has the advantages that the roasting time and the roasting temperature are obviously reduced and the energy consumption is effectively reduced by effectively irradiating at a proper temperature, meanwhile, the irradiation treatment strengthens the load of the active groups of the gasification slag, activates the active groups in the soaked copper nitrate solution and further improves the pore structure of the gasification slag; according to the method, sodium hydroxide is adopted to carry out secondary modification on the gasified slag, the gasified slag carries active groups for the second time, and meanwhile gamma ray irradiation, alkali solution treatment and irradiation are carried out to generate a synergistic effect to strengthen the active group load and the pore structure of the gasified slag, so that the catalytic activity of the gasified slag is further improved.
Furthermore, the invention realizes the resource utilization of the solid waste gasification slag, relieves the environmental pollution pressure of the gasification slag and effectively solves the problem of treatment and disposal of the gasification slag; the catalyst provided by the invention has obvious effect when being applied to an ester exchange reaction process, improves the conversion rate of biodiesel, realizes the resource harmless utilization of gasified slag, and effectively solves the problem of treatment of the gasified slag.
Detailed Description
The present invention will be further described with reference to the following embodiments.
Example 1
1) First-stage modification of gasified slag: removing surface impurities from a certain amount of gasification slag, roasting at 250 ℃ for 1h, cooling, soaking in a copper nitrate aqueous solution (solid-liquid mass ratio is 1:3), irradiating with 150kGy gamma ray at 50 ℃ for 3min, cooling the solid-liquid mixture to room temperature, standing for 3h, and standing at 70 ℃ for 2 h; then irradiated with 13kGy of gamma rays for 5min at 35 ℃. Separating the solid-liquid mixture after irradiation, washing the gasified slag with deionized water until the floating impurities are thoroughly removed, drying and grinding the gasified slag particles, and sieving the particles with a 50-mesh sieve;
2) secondary modification of gasified slag: fully mixing the gasified slag obtained in the step 1 with an aqueous solution of sodium hydroxide according to the mass ratio of 1:1, irradiating for 18min by using gamma rays with the intensity of 15kGy at room temperature, and then cooling the solid-liquid mixture to room temperature and standing for 0.5 h; then irradiated with 100kGy of gamma rays at 60 ℃ for 0.5 min. Separating a solid-liquid mixture, repeatedly washing the gasification slag by using deionized water until attachments on the surface of the gasification slag are completely removed, drying and grinding the gasification slag granules, and sieving the granules by using a 50-mesh sieve to obtain a modified gasification slag catalyst;
3) adding the modified gasification residue catalyst into an alcohol-oil transesterification reaction system, wherein oil is selectively selected from waste oil, the alcohol is methanol, the catalyst dosage (the mass ratio of the catalyst to the oil) is 3.5%, and after the reaction temperature is 160 ℃, recovering the catalyst and products after the reaction is finished. The low molecular alcohol of the product is removed by decompression, the catalyst is filtered and separated, and the catalyst can be continuously utilized after being washed by deionized water; and (3) layering the liquid by a separating funnel, separating the biodiesel and the byproduct glycerol, wherein the upper layer of the biodiesel and the lower layer of the byproduct crude glycerol are subjected to performance comparison analysis on the biodiesel.
And (4) taking out the catalyst, and repeating the esterification experiment in the step (3) for 10 times, wherein the recycling effect of the catalyst is shown in the following table 1-1.
TABLE 1-1 Recycling Effect of modified gasification slag catalyst
As can be seen from the data in Table 1-1, the conversion rate of the biodiesel can reach 98.7% at most when the ester exchange reaction is carried out by using the modified gasification slag catalyst in the example 1; and after the modified gasification slag catalyst is repeatedly used for 10 times, the conversion rate of the biodiesel is still over 80 percent, and the catalytic effect of the modified gasification slag catalyst is very good.
The product performance of the obtained biodiesel is detected, and the main physicochemical parameters are compared and analyzed, and the results are shown in tables 1-2 below.
TABLE 1-2 Main physicochemical characteristics of self-made biodiesel
As can be seen from the data in tables 1-2, the physicochemical properties of the obtained biodiesel all meet the European Union EN14214 standard.
Example 2
1) First-stage modification of gasified slag: removing surface impurities from a certain amount of gasified slag, roasting at 260 ℃ for 1.2h, cooling, soaking in copper nitrate aqueous solution (solid-to-liquid ratio is 1:4), irradiating with 180kGy gamma ray at 55 ℃ for 4min, cooling the solid-liquid mixture to room temperature, standing for 3.5h, and standing at 80 ℃ for 2.5 h; then irradiated with 14kGy of gamma radiation at 37 ℃ for 6 min. Separating the solid-liquid mixture after irradiation, washing the gasified slag with deionized water until the floating impurities are thoroughly removed, drying and grinding the gasified slag particles, and sieving the particles with a 60-mesh sieve;
2) secondary modification of gasified slag: fully mixing the gasified slag obtained in the step 1 with an aqueous solution of sodium hydroxide according to a mass ratio of 1:2, irradiating for 22min by using gamma rays of 18kGy at room temperature, and then cooling the solid-liquid mixture to room temperature and standing for 0.8 h; then irradiated with 110kGy gamma rays for 1min at 65 ℃. Separating a solid-liquid mixture, repeatedly washing the gasification slag by using deionized water until attachments on the surface of the gasification slag are completely removed, drying and grinding the gasification slag granules, and sieving the granules by using a 60-mesh sieve to obtain a modified gasification slag catalyst;
3) adding the modified gasification residue catalyst into an alcohol-oil transesterification reaction system, wherein the catalyst dosage (the mass ratio of the catalyst to the oil) is 4%, and after the reaction temperature is 170 ℃, recovering the catalyst and the product after the reaction is finished. The low molecular alcohol of the product is removed by decompression, the catalyst is filtered and separated, and the catalyst can be continuously utilized after being washed by deionized water; and (3) layering the liquid by a separating funnel, separating the biodiesel and the byproduct glycerol, wherein the upper layer of the biodiesel and the lower layer of the byproduct crude glycerol are subjected to performance comparison analysis on the biodiesel.
The catalyst was taken out and the esterification experiment described in (3) was repeated 10 times, and the catalyst recycling effect is shown in table 2-1 below.
TABLE 2-1 modified gasification slag catalyst recycle to Effect
As can be seen from the data in the table 2-1, the highest conversion rate of the biodiesel can reach 98.9% when the ester exchange reaction is carried out by using the modified gasified residue catalyst in the example 2; and after the modified gasification slag catalyst is repeatedly used for 10 times, the conversion rate of the biodiesel is still over 80 percent, and the catalytic effect of the modified gasification slag catalyst is very good.
The product performance of the obtained biodiesel is detected, and the main physicochemical parameters are compared and analyzed, and the results are shown in the following tables 2-2.
TABLE 2-2 Main physicochemical characteristics of the homemade biodiesel
As can be seen from the data in Table 2-2, the physicochemical properties of the obtained biodiesel all meet the EU EN14214 standard.
Example 3
1) First-stage modification of gasified slag: removing surface impurities from a certain amount of gasified slag, roasting at 270 ℃ for 1.4h, cooling, soaking in copper nitrate aqueous solution (solid-to-liquid ratio is 1:5), irradiating with 210kGy gamma ray at 60 ℃ for 5min, cooling the solid-liquid mixture to room temperature, standing for 4h, and standing at 80 ℃ for 3 h; then irradiated with 15kGy of gamma rays at 40 ℃ for 7 min. Separating the solid-liquid mixture after irradiation, washing the gasified slag with deionized water until the floating impurities are thoroughly removed, drying and grinding the gasified slag particles, and sieving the particles with a 70-mesh sieve;
2) secondary modification of gasified slag: fully mixing the gasified slag obtained in the step 1 with an aqueous solution of sodium hydroxide according to a mass ratio of 1:3, irradiating for 24min by using 22kGy gamma rays at room temperature, and then cooling the solid-liquid mixture to room temperature and standing for 1 h; then irradiated with 140kGy of gamma rays for 2min at 75 ℃. Separating a solid-liquid mixture, repeatedly washing the gasification slag by using deionized water until attachments on the surface of the gasification slag are completely removed, drying and grinding the gasification slag granules, and sieving the granules by using a 70-mesh sieve to obtain a modified gasification slag catalyst;
3) adding the modified gasification residue catalyst into an alcohol-oil transesterification reaction system, wherein the catalyst dosage (the mass ratio of the catalyst to the oil) is 5%, and after the reaction temperature is 190 ℃, recovering the catalyst and the product after the reaction is finished. The low molecular alcohol of the product is removed by decompression, the catalyst is filtered and separated, and the catalyst can be continuously utilized after being washed by deionized water; and (3) layering the liquid by a separating funnel, separating the biodiesel and the byproduct glycerol, wherein the upper layer of the biodiesel and the lower layer of the byproduct crude glycerol are subjected to performance comparison analysis on the biodiesel.
The catalyst was taken out, and the esterification experiment described in (3) was repeated 10 times, and the catalyst recycling effect is shown in table 3-1 below.
TABLE 3-1 modified gasification slag catalyst recycle to Effect
As can be seen from the data in Table 3-1, the conversion rate of the biodiesel can reach 99.1% to the maximum in the ester exchange reaction by using the modified gasified residue catalyst in the above example 3; and after the modified gasification slag catalyst is repeatedly used for 10 times, the conversion rate of the biodiesel is still over 80 percent, and the catalytic effect of the modified gasification slag catalyst is very good.
The product performance of the obtained biodiesel is detected, and the main physicochemical parameters are compared and analyzed, and the result is shown in the following table 3-2.
Table 3-2 main physicochemical properties of homemade biodiesel.
As can be seen from the data in Table 3-2, the physicochemical properties of the obtained biodiesel all meet the EU EN14214 standard.
Example 4
1) First-stage modification of gasified slag: removing surface impurities from a certain amount of gasified slag, roasting at 290 ℃ for 1.8h, cooling, soaking in copper nitrate aqueous solution (solid-to-liquid ratio is 1:6), irradiating with 270kGy gamma ray at 65 ℃ for 7min, cooling the solid-liquid mixture to room temperature, standing for 5.5h, and standing at 90 ℃ for 3.5 h; then irradiated with 16kGy of gamma radiation at 45 ℃ for 9 min. Separating the solid-liquid mixture after irradiation, washing the gasified slag with deionized water until the floating impurities are thoroughly removed, drying and grinding the gasified slag particles, and sieving the particles with a 90-mesh sieve;
2) secondary modification of gasified slag: fully mixing the gasified slag obtained in the step 1 with an aqueous solution of sodium hydroxide according to a 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 1.7 h; then irradiated with 160kGy gamma-ray at 80 ℃ for 4 min. Separating a solid-liquid mixture, repeatedly washing the gasification slag by using deionized water until attachments on the surface of the gasification slag are completely removed, drying and grinding the gasification slag granules, and sieving the granules by using a 90-mesh sieve to obtain a modified gasification slag catalyst;
3) adding the modified gasification residue catalyst into an alcohol-oil transesterification reaction system, wherein the catalyst dosage (the mass ratio of the catalyst to the oil) is 7%, and after the reaction temperature is 210 ℃, recovering the catalyst and the product after the reaction is finished. The low molecular alcohol of the product is removed by decompression, the catalyst is filtered and separated, and the catalyst can be continuously utilized after being washed by deionized water; and (3) layering the liquid by a separating funnel, separating the biodiesel and the byproduct glycerol, wherein the upper layer of the biodiesel and the lower layer of the byproduct crude glycerol are subjected to performance comparison analysis on the biodiesel.
The catalyst was taken out, and the esterification experiment described in (3) was repeated 10 times, and the catalyst recycling effect is shown in table 4-1 below.
TABLE 4-1 modified gasification slag catalyst recycle to Effect
As can be seen from the data in Table 4-1, the conversion rate of the biodiesel can reach 99.5% at most when the ester exchange reaction is carried out by using the modified gasification slag catalyst in the above example 4; and after the modified gasification slag catalyst is repeatedly used for 10 times, the conversion rate of the biodiesel is still over 80 percent, and the catalytic effect of the modified gasification slag catalyst is very good.
The product performance of the obtained biodiesel is detected, and the main physicochemical parameters are compared and analyzed, and the result is shown in the following table 3-2.
Table 4-2 main physicochemical properties of homemade biodiesel.
As can be seen from the data in Table 4-2, the physicochemical properties of the obtained biodiesel all meet the EU EN14214 standard.
Example 5
1) First-stage modification of gasified slag: removing surface impurities from a certain amount of gasified slag, roasting at 300 ℃ for 2h, cooling, soaking in copper nitrate aqueous solution (solid-to-liquid ratio is 1:7), irradiating with 300kGy gamma ray at 70 ℃ for 8min, cooling the solid-liquid mixture to room temperature, standing for 6h, and standing at 100 ℃ for 4 h; then irradiated with 17kGy of gamma radiation for 10min at 50 ℃. Separating the solid-liquid mixture after irradiation, washing the gasified slag with deionized water until the floating impurities are thoroughly removed, drying and grinding the gasified slag particles, and sieving the particles with a 100-mesh sieve;
2) secondary modification of gasified slag: fully mixing the gasified slag obtained in the step 1 with an aqueous solution of sodium hydroxide according to a mass ratio of 1:5, irradiating for 30min by using 33kGy gamma rays at room temperature, and then cooling the solid-liquid mixture to room temperature and standing for 2 h; then irradiated with 180kGy gamma rays for 5min at 86 ℃. Separating a solid-liquid mixture, repeatedly washing the gasification slag by using deionized water until attachments on the surface of the gasification slag are completely removed, drying and grinding the gasification slag granules, and sieving the granules by using a 100-mesh sieve to obtain a modified gasification slag catalyst;
3) adding the modified gasification residue catalyst into an alcohol-oil transesterification reaction system, wherein the catalyst dosage (the mass ratio of the catalyst to the oil) is 7.8%, and after the reaction temperature is 230 ℃, recovering the catalyst and the product after the reaction is finished. The low molecular alcohol of the product is removed by decompression, the catalyst is filtered and separated, and the catalyst can be continuously utilized after being washed by deionized water; and (3) layering the liquid by a separating funnel, separating the biodiesel and the byproduct glycerol, wherein the upper layer of the biodiesel and the lower layer of the byproduct crude glycerol are subjected to performance comparison analysis on the biodiesel.
The catalyst was taken out and the esterification experiment described in (3) was repeated 10 times, and the catalyst recycling effect is shown in table 5-1 below.
TABLE 5-1 modified gasification slag catalyst recycle to Effect
As can be seen from the data in Table 5-1, the conversion rate of the biodiesel can reach 99.3% at most when the ester exchange reaction is carried out by using the modified gasification slag catalyst in the example 5; and after the modified gasification slag catalyst is repeatedly used for 10 times, the conversion rate of the biodiesel is still over 80 percent, and the catalytic effect of the modified gasification slag catalyst is very good.
The product performance of the obtained biodiesel is detected, and the main physicochemical parameters are compared and analyzed, and the result is shown in the following table 5-2.
Table 5-2 main physicochemical properties of homemade biodiesel.
As can be seen from the data in Table 5-2, the physicochemical properties of the obtained biodiesel all meet the EU EN14214 standard.
The catalyst prepared by the method solves the problem of treatment and disposal of the gasification slag, improves the conversion rate of the biodiesel, reduces the conversion cost of the biodiesel, and has high catalytic activity, no peculiar smell and repeated use; the main performance index of the prepared biodiesel meets the European Union EN14214 standard.
The above description is only a basic description of the present invention, and any equivalent changes made according to the technical solution of the present invention should fall within the protection scope of the present invention.
Claims (10)
1. The preparation method of the modified gasification slag biodiesel catalyst is characterized by comprising the following steps:
s1, primary modification of gasified slag: roasting the gasified slag, cooling the roasted slag, immersing the cooled slag in a copper nitrate aqueous solution, performing first gamma ray irradiation to obtain a first precursor, cooling the first precursor, standing the first precursor for the first time, heating the cooled first precursor after the first standing is finished, standing the cooled first precursor for the second time, performing second gamma ray irradiation to obtain a solid-liquid mixture A, performing solid-liquid separation on the solid-liquid mixture A to obtain gasified slag particles, and washing, drying, grinding and sieving the obtained gasified slag particles to obtain first-stage modified gasified slag;
s2, secondary modification of gasified slag: fully mixing an alkaline water solution and the first-stage modified gasification slag, performing gamma ray irradiation for the third time to obtain a second precursor, cooling the second precursor, 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 gasification slag aggregates, and washing, drying, grinding and sieving the obtained gasification slag aggregates to obtain the modified gasification slag catalyst.
2. The preparation method of the modified gasification slag biodiesel catalyst according to claim 1, wherein in the step S1, the roasting condition is roasting at 250-300 ℃ for 1-2 h; the solid-liquid mass ratio of the roasted gasification slag 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 3-6 h; and after the first standing is finished, heating to 70-100 ℃, and standing for the second time, wherein the standing time is 2-4 h.
3. The method for preparing the modified gasification slag biodiesel catalyst according to claim 1, wherein in the step S1, the first gamma ray irradiation conditions are as follows: irradiating by using a gamma ray of 150kGy-300kGy at the temperature of 50-70 ℃ for 3-8 min; the second gamma ray irradiation conditions are as follows: irradiating with gamma ray of 13-17 kGy at 35-50 deg.c for 5-10 min.
4. The preparation method of 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 the floating impurities on the gasified slag particles are completely removed, and then the gasified slag particles are dried and ground, and are sieved by a 50-100 mesh sieve, so that the first-grade modified gasified slag is obtained.
5. The method for preparing the modified gasification slag biodiesel catalyst according to claim 1, wherein in the step S2, the aqueous alkali solution is an aqueous sodium hydroxide solution with a mass concentration of 1-7%, and the mass ratio of the first-stage modified gasification slag to the aqueous sodium hydroxide solution is 1: (1-5); and cooling the second precursor to room temperature, and standing for the third time, wherein the standing time for the third time is 0.5-2 h.
6. The method for preparing the modified gasification slag biodiesel catalyst according to claim 1, wherein in the step S2, the condition of the third gamma ray irradiation is that the gamma ray irradiation with 15kGy-33kGy is carried out for 18min-30min at room temperature; the condition of the fourth gamma ray irradiation is that the gamma ray irradiation of 100kGy-180kGy is carried out for 0.5min-5min at the temperature of 60 ℃ to 86 ℃.
7. The preparation method of the modified gasification slag biodiesel catalyst according to claim 1, wherein in the step S2, the gasification slag granules are washed with deionized water until the attachments on the surfaces of the gasification slag granules are completely removed, and then the gasification slag granules are dried and ground, and are sieved by a 50-100 mesh sieve, so that the modified gasification slag catalyst is obtained.
8. The modified gasification slag catalyst prepared by the preparation method of the modified gasification slag biodiesel catalyst according to any one of claims 1 to 7.
9. The use method of the modified gasified residue catalyst according to claim 8, wherein the modified gasified residue catalyst is added into an alcohol-oil transesterification reaction system, the use amount of the modified gasified residue 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.
10. The use method of the modified gasification slag catalyst according to claim 9, wherein the product is subjected to reduced pressure 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 the modified gasification slag catalyst, and the modified gasification slag catalyst can be reused after being washed with deionized water; the liquid obtained by filtration and separation is layered by a separating funnel, the upper layer is the biodiesel, and the lower layer is the byproduct crude glycerin.
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