CN110064413B - SO loaded with metal molybdenum42-/TiO2Solid catalyst and application thereof - Google Patents

SO loaded with metal molybdenum42-/TiO2Solid catalyst and application thereof Download PDF

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CN110064413B
CN110064413B CN201910354333.7A CN201910354333A CN110064413B CN 110064413 B CN110064413 B CN 110064413B CN 201910354333 A CN201910354333 A CN 201910354333A CN 110064413 B CN110064413 B CN 110064413B
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biodiesel
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CN110064413A (en
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吴国强
陈超
蔡雷
洪艳平
王文君
蒋艳
黎冬明
李亮
颜贤仔
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Jiangxi Agricultural University
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract

The invention provides SO loaded with metal molybdenum4 2‑/TiO2Solid catalyst and its application in catalyzing the transesterification of barbadosnut seed oil to produce biodiesel oil, the invention is in solid super acid (SO)4 2‑/TiO2) The molybdenum is supported on solid super acid (SO) by an isovolumetric impregnation method4 2‑/TiO2) The method forms a bifunctional catalyst with metal and acid catalysis, introduces new metal molybdenum sites, and leads SO4 2‑/TiO2The solid super acid is changed from simple acid catalysis transesterification into dual-function catalysis transesterification, and is applied to catalysis of the barbadosnut seed oil transesterification, so that the yield of the biodiesel can be remarkably improved; meanwhile, the existence of metal molybdenum changes the pure SO4 2‑/TiO2The solid superacid has a catalytic site concept, so that the solid superacid can keep good stability in the transesterification process and has wider industrial application value.

Description

SO loaded with metal molybdenum42-/TiO2Solid catalyst and application thereof
Technical Field
The invention relates to a catalyst and application thereof in energy development, in particular to SO loaded with metal molybdenum4 2-/TiO2Solid catalyst and its application.
Background
With the gradual decrease of fossil energy, the research on biological energy is particularly important, and the biological diesel oil is widely concerned as a sustainable development energy. Besides technical difficulties in the production process of biodiesel, the source of raw oil is one of the bottlenecks in inhibiting the development of biodiesel. With the continuous expansion of the production and use scale of biodiesel, the edible oil plants such as soybean, rapeseed, sunflower seed, corn and the like are not allowed to be used as raw materials for producing the biodiesel. Therefore, Jatropha curcas, a non-edible oil plant, has received much attention. Compared with edible oil such as rapeseed, soybean and the like, the preparation of the biodiesel by using the jatropha curcas seed oil not only reduces the preparation cost of the biodiesel, but also solves the contradiction between eating and production. Meanwhile, compared with non-edible oil plants such as pistacia chinensis bunge, cornus wilsoniana and the like, the jatropha curcas seeds have high oil content and strong adaptability to the growth environment, and can be planted in a large area in arid areas, so that the jatropha curcas seed oil becomes an ideal raw material for preparing biodiesel.
At present, alkaline or acid catalysts are mostly adopted to catalyze the transesterification reaction for preparing the biodiesel. However, the alkaline catalyst is not favorable for the production of biodiesel because it is likely to cause saponification reaction during the transesterification of the high acid value feedstock oil, and generates a large amount of by-products. The biodiesel prepared by using the acid catalyst has the characteristics of high raw material conversion rate and almost 100 percent of selectivity. Currently, acid catalysts are mainly classified as liquid acid catalysts (e.g., H)2SO4、HNO3Etc.) and solid acid catalysts (e.g., acidic zeolites, acidic resins, metal oxide-like SO4 2-/MxOyEtc.). The former can obtain high-yield biodiesel in the catalytic transesterification process, but has the problems of environmental pollution, serious equipment corrosion, difficult separation and utilization of the catalyst and the like. The solid acid catalyst can well solve the problems of liquid acid in the process of preparing the biodiesel, and is not influenced by the high acid value of the raw material oil, but the solid acid catalyst has poor catalytic performance, and the yield is not high when the biodiesel is prepared by catalytic transesterification.
Up to now, there has been no report on a high-efficiency solid catalyst for producing biodiesel through one-step catalytic transesterification of jatropha curcas seed oil under relatively mild conditions. Therefore, there is a need to develop a solid catalyst with high catalytic performance to increase the yield of biodiesel produced by transesterification of jatropha curcas seed oil.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides SO loaded with metal molybdenum4 2-/TiO2The invention relates to a solid catalyst and application thereof, which is prepared by adding solid super acid (SO)4 2-/TiO2) The method for loading metal molybdenum on the material obtains the solid catalyst with high-efficiency catalytic performance, and the solid catalyst is applied to catalyzing the barbadosnut seed oil transesterification reaction, so that the catalyst not only greatly improves the yield of the barbadosnut seed oil catalytic transesterification, but also solves the problem of catalyst inactivation of solid super acid in the catalysis of the barbadosnut seed oil catalytic transesterification reaction, and has industrial application value.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides SO loaded with metal molybdenum4 2-/TiO2A solid catalyst, the method of synthesis of the catalyst comprising the steps of:
S1、Ti(OH)4the synthesis of (2):
mixing TiCl4Slowly dropwise adding the precipitate into deionized water, adjusting the pH of the solution to 8-9 by using ammonia water, aging for 30min, and filtering and washing the obtained precipitate until no Cl exists in the precipitate-Drying and grinding the residue and the washed precipitate to obtain Ti (OH)4；
S2、SO4 2-/TiO2Synthesis of solid super acid:
taking appropriate amount of the above Ti (OH)4Adding 1-2.5 mol/L sulfuric acid solution into the mixture according to the material-liquid ratio (g/m L) of 1:10, carrying out magnetic stirring, then carrying out immersion acidification for 8-24 h, and then removing residual SO in the obtained solid by centrifugation4 2-Finally, drying the obtained solid, and roasting the dried solid to obtain SO4 2-/TiO2Solid super acid;
s3, SO of supported metal molybdenum4 2-/TiO2Synthesis of solid catalyst:
first to SO4 2-/TiO2Adding deionized water dropwise into solid superacid, calculating maximum water absorption amount, and adding molybdenum and SO4 2-/TiO2Preparing ammonium molybdate solution with the same amount as the maximum water absorption amount according to the weight ratio of the solid superacid, and adsorbing the ammonium molybdate solution to SO by adopting an isovolumetric immersion method4 2-/TiO2Naturally drying in solid superacid at room temperature for 24h, and finally drying and roasting to obtain SO loaded with metal molybdenum4 2-/TiO2A solid catalyst.
Preferably, the precipitate in S1 is AgNO with concentration of 1 mol/L3The solution was tested for the presence of Cl-And (4) remaining.
Preferably, the milling treatment described in S1 refers to milling the washed precipitate to a size of 200 mesh.
Preferably, the solid described in S2 is BaCl with a concentration of 1 mol/L2The solution is tested for the presence of SO4 2-And (4) remaining.
Preferably, the drying parameters of S1, S2 and S3 are all 120 ℃ and 24 h.
Preferably, the roasting parameters described in S2 and S3 are both 550 ℃ for 3 h.
Preferably, the metal molybdenum described in S3 is mixed with SO4 2-/TiO2The weight ratio of the solid superacid is 3-20%.
Preferably, the above-mentioned SO is provided as a molybdenum metal4 2-/TiO2The solid catalyst can be applied to the reaction for catalyzing the transesterification of the jatropha curcas seed oil to produce the biodiesel.
SO loaded with metallic molybdenum can be prepared by one skilled in the art by the following method4 2-/TiO2The solid catalyst is applied to the reaction for catalyzing the transesterification of the barbadosnut seed oil to synthesize the biodiesel:
respectively weighing barbadosnut seed oil, methanol and petroleum ether according to the weight ratio of 3:1:1, adding the barbadosnut seed oil, the methanol and the petroleum ether into a hydrothermal reaction kettle, heating to a certain temperature, and adding a proper amount of SO loaded with metal molybdenum4 2-/TiO2Sealing the solid super acidic catalyst, placing the sealed solid super acidic catalyst in a magnetic stirrer for reaction for 16h, taking out reaction liquid after the reaction is finished, placing the reaction liquid in a rotary evaporator for rotary evaporation for 15min under the conditions of 70 ℃ and 70rpm (rotating speed), then transferring the reaction liquid into a centrifugal machine for centrifugation for 8min at the rotating speed of 10000rpm, and obtaining supernatant which is the biodiesel.
Preferably, the metallic molybdenum-supporting SO4 2-/TiO2The dosage of the solid super acidic catalyst is 1.8 percent of the total weight of the barbadosnut seed oil, the methanol and the petroleum ether.
Compared with the prior art, the invention has the beneficial effects that:
the invention is in solid super acid (SO)4 2-/TiO2) The molybdenum is supported on solid super acid (SO) by an isovolumetric impregnation method4 2-/TiO2) So that the bifunctional catalyst with metal and acid catalysis is formed. First, new metal sites are introduced to make SO4 2-/TiO2The solid super acid is changed from simple acid catalysis transesterification into dual-function catalysis transesterification, is applied to catalysis of the barbadosnut seed oil transesterification, can obviously improve the yield of the biodiesel within the range of 5-20% of Mo load, and improves the yield of the biodiesel by 6.8-33.5% under the same condition; secondly, the presence of metallic molybdenum alters the simple SO4 2-/TiO2The catalytic site conception of the solid super acid improves the problem of catalyst deactivation of the solid super acid in the catalytic transesterification reaction of the jatropha curcas seed oil, so that the solid super acid can keep good stability in the transesterification process, the transesterification yield is only reduced by 14.1 percent after the reaction is repeated for five times, and the solid super acid has wider industrial application value.
Drawings
FIG. 1 is SO at 10% molybdenum loading4 2-/TiO2Of solid catalystsScanning an electron microscope image;
FIG. 2 is SO at 10% molybdenum loading4 2-/TiO2Transmission electron micrographs of the solid catalyst;
FIG. 3 is SO at 10% molybdenum loading4 2-/TiO2X-ray diffraction pattern of the solid catalyst (horizontal axis is scanning angle, vertical axis is intensity of diffraction peak);
FIG. 4 is SO at 10% molybdenum loading4 2-/TiO2The ammonia temperature programming of the solid catalyst is removed from the attached figure (the abscissa is desorption temperature, and the ordinate is TCD signal);
FIG. 5 is SO at 10% molybdenum loading4 2-/TiO2N of solid catalyst2The physical adsorption removal figure (the horizontal axis is relative pressure, and the vertical axis is adsorption capacity).
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1:
3% molybdenum loading (molybdenum metal and SO)4 2-/TiO23% by weight of solid superacid) of SO4 2-/TiO2Synthesizing a solid catalyst, wherein the synthesizing method of the catalyst comprises the following steps:
S1、Ti(OH)4the synthesis of (2):
taking a proper amount of deionized water, introducing the deionized water into a 500m L three-neck flask, and adding TiCl4Slowly dropwise adding the precipitate into deionized water, uniformly stirring, adjusting the pH of the solution to 8-9 by using ammonia water, aging for 30min, and filtering and washing the obtained precipitate until no Cl exists in the precipitate-Residual (with 1 mol/L AgNO)3Solution inspection), the washed precipitate is dried in an oven at 120 deg.C for 24h, and then ground to 200 mesh size to obtain Ti (OH)4(ii) a The chemical reaction equation for this step is as follows:
Figure BDA0002044917390000041
S2、SO4 2-/TiO2synthesis of solid super acid:
taking appropriate amount of the above Ti (OH)4Adding into a 100m L three-neck flask according to the material-liquid ratio (Ti (OH) of 1: 10)4G/m L) adding 1.5 mol/L sulfuric acid solution (the concentration of the sulfuric acid solution is 1-2.5 mol/L, the embodiment adopts 1.5 mol/L), magnetically stirring, soaking and acidifying for 12h (the soaking and acidifying time is 8-24 h, the embodiment adopts 12h), and then removing residual SO in the obtained solid by centrifugation4 2-(with 1 mol/L BaCl2Solution inspection), finally placing the obtained solid in a drying oven to be dried for 24 hours at 120 ℃, transferring the dried solid into a muffle furnace to be roasted for 3 hours at 550 ℃ to obtain SO4 2-/TiO2Solid super acid; the chemical reaction equation for this step is as follows:
Figure BDA0002044917390000042
s3, SO of supported metal molybdenum4 2-/TiO2Synthesis of solid catalyst:
first to SO4 2-/TiO2Adding deionized water dropwise into solid superacid, and reacting with SO4 2-/TiO2Calculating the maximum water absorption when the solid super acid reaches the maximum adsorption capacity, and then according to SO4 2-/TiO2Weight of solid super acid, and molybdenum and SO4 2-/TiO2The amount of molybdenum is calculated according to the proportion that the weight ratio of the solid superacid is 3 percent, and the molybdenum element is in ammonium molybdate [ (NH)4)Mo7O24·4H2O]The dosage of ammonium molybdate is calculated according to the molecular mass ratio in the process, and then the ammonium molybdate is prepared according to the maximum water absorption capacityEqual amount of ammonium molybdate solution is adopted to adsorb the ammonium molybdate solution to SO by an equal volume impregnation method4 2-/TiO2Naturally drying in solid super acid at room temperature for 24h, drying in a drying oven at 120 deg.C for 24h, transferring to a muffle furnace, and calcining at 550 deg.C for 3h to obtain SO with 3% molybdenum loading4 2-/TiO2A solid catalyst.
Example 2:
5% molybdenum loading (molybdenum metal and SO)4 2-/TiO23% by weight of solid superacid) of SO4 2-/TiO2Synthesizing a solid catalyst, wherein the synthesizing method of the catalyst comprises the following steps:
S1、Ti(OH)4the synthesis of (2):
taking a proper amount of deionized water, introducing the deionized water into a 500m L three-neck flask, and adding TiCl4Slowly dropwise adding the precipitate into deionized water, uniformly stirring, adjusting the pH of the solution to 8-9 by using ammonia water, aging for 30min, and filtering and washing the obtained precipitate until no Cl exists in the precipitate-Residual (with 1 mol/L AgNO)3Solution inspection), the washed precipitate is dried in an oven at 120 deg.C for 24h, and then ground to 200 mesh size to obtain Ti (OH)4(ii) a The chemical reaction equation for this step is as follows:
Figure BDA0002044917390000051
S2、SO4 2-/TiO2synthesis of solid super acid:
taking appropriate amount of the above Ti (OH)4Adding into a 100m L three-neck flask according to the material-liquid ratio (Ti (OH) of 1: 10)4G/m L) adding 1.5 mol/L sulfuric acid solution (the concentration of the sulfuric acid solution is 1-2.5 mol/L, the embodiment adopts 1.5 mol/L), stirring by magnetic force, dipping and acidifying for 12h, dipping and acidifying for 8-24 h, the embodiment adopts 12h), and removing the obtained solid by centrifugationResidual SO4 2-(with 1 mol/L BaCl2Solution inspection), finally placing the obtained solid in a drying oven to be dried for 24 hours at 120 ℃, transferring the dried solid into a muffle furnace to be roasted for 3 hours at 550 ℃ to obtain SO4 2-/TiO2Solid super acid; the chemical reaction equation for this step is as follows:
Figure BDA0002044917390000052
s3, SO of supported metal molybdenum4 2-/TiO2Synthesis of solid catalyst:
first to SO4 2-/TiO2Adding deionized water dropwise into solid superacid, and reacting with SO4 2-/TiO2Calculating the maximum water absorption when the solid super acid reaches the maximum adsorption capacity, and then according to SO4 2-/TiO2Weight of solid super acid, and molybdenum and SO4 2-/TiO2The amount of molybdenum is calculated according to the proportion that the weight ratio of the solid superacid is 5 percent, and the molybdenum element is in ammonium molybdate [ (NH)4)Mo7O24·4H2O]Calculating the use amount of ammonium molybdate according to the molecular mass ratio, preparing ammonium molybdate into ammonium molybdate solution with the same amount according to the maximum water absorption capacity, and adsorbing the ammonium molybdate solution to SO by adopting an isometric immersion method4 2-/TiO2Naturally drying in solid super acid at room temperature for 24h, drying in a drying oven at 120 deg.C for 24h, transferring to a muffle furnace, and calcining at 550 deg.C for 3h to obtain SO with 5% molybdenum load4 2-/TiO2A solid catalyst.
Example 3:
7% molybdenum loading (molybdenum metal and SO)4 2-/TiO23% by weight of solid superacid) of SO4 2-/TiO2Synthesizing a solid catalyst, wherein the synthesizing method of the catalyst comprises the following steps:
S1、Ti(OH)4the synthesis of (2):
taking a proper amount of deionized water, introducing the deionized water into a 500m L three-neck flask, and adding TiCl4Slowly dropwise adding the precipitate into deionized water, uniformly stirring, adjusting the pH of the solution to 8-9 by using ammonia water, aging for 30min, and filtering and washing the obtained precipitate until no Cl exists in the precipitate-Residual (with 1 mol/L AgNO)3Solution inspection), the washed precipitate is dried in an oven at 120 deg.C for 24h, and then ground to 200 mesh size to obtain Ti (OH)4(ii) a The chemical reaction equation for this step is as follows:
Figure BDA0002044917390000061
S2、SO4 2-/TiO2synthesis of solid super acid:
taking appropriate amount of the above Ti (OH)4Adding into a 100m L three-neck flask according to the material-liquid ratio (Ti (OH) of 1: 10)4G/m L) adding 1.5 mol/L of sulfuric acid solution (the concentration of the sulfuric acid solution is 1-2.5 mol/L, the embodiment adopts 1.5 mol/L), stirring by magnetic force, dipping and acidifying for 12 hours, dipping and acidifying for 8-24 hours, the embodiment adopts 12 hours), and then removing residual SO in the obtained solid by centrifugation4 2-(with 1 mol/L BaCl2Solution inspection), finally placing the obtained solid in a drying oven to be dried for 24 hours at 120 ℃, transferring the dried solid into a muffle furnace to be roasted for 3 hours at 550 ℃ to obtain SO4 2-/TiO2Solid super acid; the chemical reaction equation for this step is as follows:
Figure BDA0002044917390000062
s3, SO of supported metal molybdenum4 2-/TiO2Synthesis of solid catalyst:
first to SO4 2-/TiO2Adding deionized water dropwise into solid superacid, and reacting with SO4 2-/TiO2Calculating the maximum water absorption when the solid super acid reaches the maximum adsorption capacity, and then according to SO4 2-/TiO2Weight of solid super acid, and molybdenum and SO4 2-/TiO2The amount of molybdenum in the solid superacid is calculated according to the proportion of 7% by weight, and the molybdenum element is added in ammonium molybdate [ (NH)4)Mo7O24·4H2O]Calculating the use amount of ammonium molybdate according to the molecular mass ratio, preparing ammonium molybdate into ammonium molybdate solution with the same amount according to the maximum water absorption capacity, and adsorbing the ammonium molybdate solution to SO by adopting an isometric immersion method4 2-/TiO2Naturally drying in solid super acid at room temperature for 24h, drying in a drying oven at 120 deg.C for 24h, transferring to a muffle furnace, and calcining at 550 deg.C for 3h to obtain SO with 7% molybdenum load4 2-/TiO2A solid catalyst.
Example 4:
10% molybdenum loading (molybdenum metal and SO)4 2-/TiO23% by weight of solid superacid) of SO4 2-/TiO2Synthesizing a solid catalyst, wherein the synthesizing method of the catalyst comprises the following steps:
S1、Ti(OH)4the synthesis of (2):
taking a proper amount of deionized water, introducing the deionized water into a 500m L three-neck flask, and adding TiCl4Slowly dropwise adding the precipitate into deionized water, uniformly stirring, adjusting the pH of the solution to 8-9 by using ammonia water, aging for 30min, and filtering and washing the obtained precipitate until no Cl exists in the precipitate-Residual (with 1 mol/L AgNO)3Solution inspection), the washed precipitate is dried in an oven at 120 deg.C for 24h, and then ground to 200 mesh size to obtain Ti (OH)4(ii) a The chemical reaction equation for this step is as follows:
Figure BDA0002044917390000071
S2、SO4 2-/TiO2synthesis of solid super acid:
taking appropriate amount of the above Ti (OH)4Adding into a 100m L three-neck flask according to the material-liquid ratio (Ti (OH) of 1: 10)4G/m L) adding 1.5 mol/L of sulfuric acid solution (the concentration of the sulfuric acid solution is 1-2.5 mol/L, the embodiment adopts 1.5 mol/L), stirring by magnetic force, dipping and acidifying for 12 hours, dipping and acidifying for 8-24 hours, the embodiment adopts 12 hours), and then removing residual SO in the obtained solid by centrifugation4 2-(with 1 mol/L BaCl2Solution inspection), finally placing the obtained solid in a drying oven to be dried for 24 hours at 120 ℃, transferring the dried solid into a muffle furnace to be roasted for 3 hours at 550 ℃ to obtain SO4 2-/TiO2Solid super acid; the chemical reaction equation for this step is as follows:
Figure BDA0002044917390000072
s3, SO of supported metal molybdenum4 2-/TiO2Synthesis of solid catalyst:
first to SO4 2-/TiO2Adding deionized water dropwise into solid superacid, and reacting with SO4 2-/TiO2Calculating the maximum water absorption when the solid super acid reaches the maximum adsorption capacity, and then according to SO4 2-/TiO2Weight of solid super acid, and molybdenum and SO4 2-/TiO2The amount of molybdenum is calculated according to the proportion that the weight ratio of the solid superacid is 10 percent, and the molybdenum element is in ammonium molybdate [ (NH)4)Mo7O24·4H2O]Calculating the use amount of ammonium molybdate according to the molecular mass ratio, preparing ammonium molybdate into ammonium molybdate solution with the same amount according to the maximum water absorption capacity, and adsorbing the ammonium molybdate solution to SO by adopting an isometric immersion method4 2-/TiO2Naturally drying in solid super acid at room temperature for 24 hr, oven drying at 120 deg.C for 24 hr, and dryingTransferring the mixture to a muffle furnace to be roasted for 3 hours at the temperature of 550 ℃ to obtain SO with 10 percent of molybdenum load4 2-/TiO2A solid catalyst.
Example 5:
20% molybdenum loading (molybdenum metal and SO)4 2-/TiO23% by weight of solid superacid) of SO4 2-/TiO2Synthesizing a solid catalyst, wherein the synthesizing method of the catalyst comprises the following steps:
S1、Ti(OH)4the synthesis of (2):
taking a proper amount of deionized water, introducing the deionized water into a 500m L three-neck flask, and adding TiCl4Slowly dropwise adding the precipitate into deionized water, uniformly stirring, adjusting the pH of the solution to 8-9 by using ammonia water, aging for 30min, and filtering and washing the obtained precipitate until no Cl exists in the precipitate-Residual (with 1 mol/L AgNO)3Solution inspection), the washed precipitate is dried in an oven at 120 deg.C for 24h, and then ground to 200 mesh size to obtain Ti (OH)4(ii) a The chemical reaction equation for this step is as follows:
Figure BDA0002044917390000081
S2、SO4 2-/TiO2synthesis of solid super acid:
taking appropriate amount of the above Ti (OH)4Adding into a 100m L three-neck flask according to the material-liquid ratio (Ti (OH) of 1: 10)4G/m L) adding 1.5 mol/L of sulfuric acid solution (the concentration of the sulfuric acid solution is 1-2.5 mol/L, the embodiment adopts 1.5 mol/L), stirring by magnetic force, dipping and acidifying for 12 hours, dipping and acidifying for 8-24 hours, the embodiment adopts 12 hours), and then removing residual SO in the obtained solid by centrifugation4 2-(with 1 mol/L BaCl2Solution inspection), finally placing the obtained solid in a drying oven to be dried for 24 hours at 120 ℃, transferring the dried solid into a muffle furnace to be roasted for 3 hours at 550 ℃ to obtain SO4 2-/TiO2Solid state ultrasmallA strong acid; the chemical reaction equation for this step is as follows:
Figure BDA0002044917390000082
s3, SO of supported metal molybdenum4 2-/TiO2Synthesis of solid catalyst:
first to SO4 2-/TiO2Adding deionized water dropwise into solid superacid, and reacting with SO4 2-/TiO2Calculating the maximum water absorption when the solid super acid reaches the maximum adsorption capacity, and then according to SO4 2-/TiO2Weight of solid super acid, and molybdenum and SO4 2-/TiO2The amount of molybdenum is calculated according to the proportion that the weight ratio of the solid superacid is 20 percent, and the molybdenum element is in ammonium molybdate [ (NH)4)Mo7O24·4H2O]Calculating the use amount of ammonium molybdate according to the molecular mass ratio, preparing ammonium molybdate into ammonium molybdate solution with the same amount according to the maximum water absorption capacity, and adsorbing the ammonium molybdate solution to SO by adopting an isometric immersion method4 2-/TiO2Naturally drying in solid super acid at room temperature for 24h, drying in a drying oven at 120 deg.C for 24h, transferring to a muffle furnace, and calcining at 550 deg.C for 3h to obtain 20% molybdenum-loaded SO4 2-/TiO2A solid catalyst.
Comparative example:
comparative example is solid Superacid (SO)4 2-/TiO2) A method of synthesizing a catalyst, the method comprising the steps of:
S1、Ti(OH)4the synthesis of (2):
taking a proper amount of deionized water, introducing the deionized water into a 500m L three-neck flask, and adding TiCl4Slowly dropwise adding the precipitate into deionized water, uniformly stirring, adjusting the pH of the solution to 8-9 by using ammonia water, aging for 30min, and filtering and washing the obtained precipitate until no Cl exists in the precipitate-Residual (with 1 mol/L AgNO)3The solution is testedTest), the cleaned precipitate is firstly put into an oven to be dried for 24h at the temperature of 120 ℃, and then is ground to 200 meshes to obtain Ti (OH)4(ii) a The chemical reaction equation for this step is as follows:
Figure BDA0002044917390000091
S2、SO4 2-/TiO2synthesis of solid super acid:
taking appropriate amount of the above Ti (OH)4Adding into a 100m L three-neck flask according to the material-liquid ratio (Ti (OH) of 1: 10)4And sulfuric acid solution weight to volume ratio, g/m L) to which a 1.5 mol/L sulfuric acid solution was added, followed by magnetic stirring and immersion acidification for 12 hours, and then removal of residual SO in the resulting solid by centrifugation4 2-(with 1 mol/L BaCl2Solution inspection), finally placing the obtained solid in a drying oven to be dried for 24 hours at 120 ℃, transferring the dried solid into a muffle furnace to be roasted for 3 hours at 550 ℃ to obtain solid super acid (SO)4 2-/TiO2) A catalyst. The chemical reaction equation for this step is as follows:
Figure BDA0002044917390000092
SO loaded with molybdenum (Mo)4 2-/TiO2Characterization of solid catalyst
(1) SO at 10% Mo loading4 2-/TiO2The solid catalyst is a test sample, and is characterized and analyzed by a scanning electron microscope (SUPRA55, Care Caisis, Germany) under a high vacuum state and an accelerating voltage of 5kV, and a scanning electron microscope picture is shown in figure 1;
(2) SO at 10% Mo loading4 2-/TiO2The solid catalyst is a test sample, and is characterized and analyzed by a transmission electron microscope (JEM-2100 type, Japan Electron Co., Ltd.) under the conditions of 200kV accelerating voltage, 0.23nm point resolution and 0.14nm line resolution, and a transmission electron microscope picture is shown in FIG. 1;
as can be seen from FIG. 1, the SO supporting the metallic Mo4 2-/TiO2The solid catalyst is irregularly arranged in a granular form and is easily agglomerated, which is further illustrated by the transmission electron micrograph in FIG. 2, and the particle diameter is about 20nm, which is associated with solid Superacid (SO)4 2-/TiO2) The grain size of the catalysts is not very different (characterization of solid superacids references: ChenC, Cai L, Shangguan X, et al. heterogeneogous and efficient determination of Jatropha curcas L. seed oil to product biolobiodesel determined by nano-sized SO)4 2-/TiO2[J]Royal Society open science,2018,5(11):181331.) it can be seen that the introduction of metallic Mo does not destroy SO4 2-/TiO2Solid superacid grain size and morphology.
In addition, it is noted that SO was supported at 3% Mo4 2-/TiO2Solid catalyst, SO of 5% Mo loading4 2-/TiO2Solid catalyst, SO of 7% Mo loading4 2-/TiO2Solid catalyst, SO with 20% Mo loading4 2-/TiO2Solid catalyst and SO with 10% Mo loading4 2-/TiO2The characterization of the solid catalyst was substantially consistent.
Second, SO loaded with molybdenum (Mo)4 2-/TiO2Crystal structure of solid catalyst
SO at 10% Mo loading4 2-/TiO2The solid catalyst is used as a test sample and takes solid super acid (SO)4 2-/TiO2) The catalyst was used as a control, and the crystal structure of the Cu target was observed by an X-ray diffractometer (RIGAKU Ultima IV diffractometer, Japan scientific instruments Co., Ltd.) under a scanning range of 5 to 80 degrees, a scanning step number of 0.02 degrees, a working voltage of 40kV and a working current of 40mA, and the X-ray diffraction pattern is shown in FIG. 3.
As is apparent from the X-ray diffraction pattern of FIG. 3, SO supporting metallic Mo4 2-/TiO2The solid catalyst is at 25.38 deg. and 37.9 degThe diffraction peaks at 8 degrees, 48.08 degrees, 54.08 degrees, 55.18 degrees and 62.78 degrees are obvious and are in contact with solid super acid (SO)4 2-/TiO2) The diffraction peak structures of the catalysts were consistent, indicating that the introduction of metallic Mo did not destroy SO4 2-/TiO2The crystal structure of (1). In addition, in the X-ray diffraction pattern, the presence of Mo phase was not found, which indicates that metallic Mo was present in SO4 2-/TiO2The surface dispersion of (A) is very uniform, which indicates that SO with good metal dispersibility is prepared in the experiment4 2-/TiO2The Mo solid catalyst is loaded.
In addition, it is noted that SO was supported at 3% Mo4 2-/TiO2Solid catalyst, SO of 5% Mo loading4 2-/TiO2Solid catalyst, SO of 7% Mo loading4 2-/TiO2Solid catalyst, SO with 20% Mo loading4 2-/TiO2Solid catalyst and SO with 10% Mo loading4 2-/TiO2The crystal structure of the solid catalyst is basically consistent.
Thirdly, measuring SO of loaded metal molybdenum (Mo) by adopting ammonia temperature programmed desorption method4 2-/TiO2Acid strength of solid catalyst
SO at 10% Mo loading4 2-/TiO2The solid catalyst is used as a test sample and takes solid super acid (SO)4 2-/TiO2) The catalyst was placed in a Micromeritics ASAP 2920 apparatus (Michkok instruments, USA) and treated in helium at 450 deg.C for 1 hour, then reduced to 120 deg.C and adsorbed in a mixture of helium and ammonia (ammonia volume fraction of 10%) for 30 minutes, and finally flushed with pure helium for 1.5 hours, and the sample was raised from 120 deg.C to 600 deg.C at a temperature rise rate of 10 deg.C/min, and observed in NH by a Thermal Conductivity Detector (TCD)3The temperature-programmed desorption condition of ammonia is shown in figure 4.
In the ammonia temperature programmed desorption process, the higher the desorption temperature is, the stronger the acidity intensity is. Temperature programmed desorption of ammonia from FIG. 4As can be seen in the drawing, SO supporting metallic Mo4 2-/TiO2The solid catalyst has obvious desorption peaks in three temperature ranges of 117-177 deg.c, 257-317 deg.c and 447-517 deg.c, which correspond to weak acid site, medium acid site and strong acid site separately and are also mixed with solid super acid (SO)4 2-/TiO2) Compared with the catalyst, the SO with 10 percent of Mo loading is increased along with the increase of the Mo loading4 2-/TiO2The strong acid sites of the solid catalyst gradually decline, which shows that the introduction of the metal Mo can reduce SO4 2-/TiO2The acidity of the catalyst, but its catalytic activity was significantly increased (see SO supporting metallic molybdenum)4 2-/TiO2The solid catalyst catalyzes the transesterification of the jatropha curcas seed oil to synthesize the biodiesel part), which shows that the introduction of the metal Mo can promote the transesterification reaction.
In addition, it is noted that SO was supported at 3% Mo4 2-/TiO2Solid catalyst, SO of 5% Mo loading4 2-/TiO2Solid catalyst, SO of 7% Mo loading4 2-/TiO2Solid catalyst, SO with 20% Mo loading4 2-/TiO2Solid catalyst and SO with 10% Mo loading4 2-/TiO2The TCD signal intensity of the solid catalyst is different, and is represented by that the SO of the loaded metal Mo is increased along with the increase of the Mo loading amount within the range of 3-20 percent of the Mo loading amount4 2-/TiO2The lower the acid strength of the solid super acid, the lower the acid strength of the solid super acid is, but the acid strength is higher than that of the conventional solid super acid (SO)4 2-/TiO2) The temperature is small, and the change trends of the TCD signal intensity in three temperature ranges of 117-177 ℃, 257-317 ℃ and 447-517 ℃ are basically consistent.
IV, adopting N2Method for measuring SO of loaded metal molybdenum by physical adsorption method4 2-/TiO2Pore structure of solid catalyst
SO at 10% Mo loading4 2-/TiO2The solid catalyst is used as a test sample and takes solid super acid (SO)4 2-/TiO2) The catalyst was placed in a Micromeritics ASAP2020 adsorption apparatus (Mac instruments, USA) and degassed at 200 deg.C for 10 hr using-196 deg.C liquid nitrogen, and the measured sample was observed under N2In the case of physical adsorption and desorption, N2The physical adsorption desorption diagram is shown in figure 5.
From N of FIG. 52As can be seen in the figure for physical adsorption desorption, SO with 10% Mo loading4 2-/TiO2The presence of a pronounced hysteresis loop structure of type IV in the solid catalyst indicates that the SO supports the metal molybdenum4 2-/TiO2Solid catalyst and solid super acid (SO)4 2-/TiO2) The catalyst has the same mesoporous structure and is mainly formed by stacking catalyst grains.
In addition, it is noted that SO was supported at 3% Mo4 2-/TiO2Solid catalyst, SO of 5% Mo loading4 2-/TiO2Solid catalyst, SO of 7% Mo loading4 2-/TiO2Solid catalyst, SO with 20% Mo loading4 2-/TiO2Solid catalyst and SO with 10% Mo loading4 2-/TiO2The solid catalyst has similar mesoporous structure.
Fifthly, SO loaded with metal molybdenum (Mo)4 2-/TiO2The solid catalyst catalyzes the transesterification of the barbadosnut seed oil to synthesize the biodiesel:
(1) SO of 3% Mo load4 2-/TiO2The solid catalyst catalyzes the transesterification of the barbadosnut seed oil to synthesize the biodiesel:
respectively weighing 3g of barbadosnut seed oil, 1g of methanol and 1g of petroleum ether of the hemp according to the weight ratio of 3:1:1, adding the materials into a hydrothermal reaction kettle with the thickness of 25m L, heating to 100 ℃, and adding 0.09g of SO with 3% Mo loading4 2-/TiO2Sealing the solid catalyst, placing in a magnetic stirrer for reaction for 16h, taking out the reaction solution after the reaction is finished, placing in a rotary evaporator for rotary evaporation for 15min at 70 ℃ and 70rpm (rotating speed), and rotatingTransferring into a centrifuge, centrifuging at 10000rpm for 8min, and filtering the supernatant to obtain 7.11mg biodiesel with yield of 16.4% and selectivity of 99.8%.
The method for calculating the yield of the biodiesel comprises the following steps:
Figure BDA0002044917390000121
wherein,% FAMEs is the yield of fatty acid methyl esters (i.e., the major component of biodiesel), mMHRefers to the mass of the internal standard; a. theFRefers to the peak area of fatty acid methyl ester; f. ofMHRefers to a correction factor; a. theMHRefers to the peak area of the internal standard; m issRefers to the mass of the sample.
The catalyst selectivity was calculated as follows:
selectivity% (100-by-product ratio) × 100%
(2) SO of 5% Mo load4 2-/TiO2The solid catalyst catalyzes the transesterification of the barbadosnut seed oil to synthesize the biodiesel:
respectively weighing 3g of barbadosnut seed oil, 1g of methanol and 1g of petroleum ether according to the weight ratio of 3:1:1, adding the materials into a hydrothermal reaction kettle with the volume of 25m L, heating to 100 ℃, and adding 0.09g of SO with the loading of 5% Mo4 2-/TiO2Sealing the solid catalyst, placing the solid catalyst in a magnetic stirrer for reacting for 16h, taking out reaction liquid after the reaction is finished, placing the solid catalyst in a rotary evaporator for rotary evaporation for 15min under the conditions of 70 ℃ and 70rpm (rotating speed), then transferring the solid catalyst into a centrifugal machine for centrifuging for 8min at the rotating speed of 10000rpm, and filtering supernatant to obtain 15.88mg of biodiesel, wherein the yield is 36.7%, and the selectivity is 99.9%.
Wherein, the methods for calculating the yield of the biodiesel and the selectivity of the catalyst are the same as the above.
(3) SO of 7% Mo loading4 2-/TiO2The solid catalyst catalyzes the transesterification of the barbadosnut seed oil to synthesize the biodiesel:
respectively weighing 3g of barbadosnut seed oil, 1g of methanol and 1g of petroleum ether according to the weight ratio of 3:1:1, and adding water of 25m LIn a hot reaction kettle, heated to 100 ℃ and then charged with 0.09g of 7% Mo loaded SO4 2-/TiO2Sealing the solid catalyst, placing the solid catalyst in a magnetic stirrer for reacting for 16h, taking out reaction liquid after the reaction is finished, placing the solid catalyst in a rotary evaporator for rotary evaporation for 15min under the conditions of 70 ℃ and 70rpm (rotating speed), then transferring the solid catalyst into a centrifugal machine for centrifuging for 8min at the rotating speed of 10000rpm, and filtering supernatant to obtain 19.24mg of biodiesel, wherein the yield is 44.5%, and the selectivity is 99.9%.
Wherein, the methods for calculating the yield of the biodiesel and the selectivity of the catalyst are the same as the above.
(4) SO with 10% Mo loading4 2-/TiO2The solid catalyst catalyzes the transesterification of the barbadosnut seed oil to synthesize the biodiesel:
respectively weighing 3g of barbadosnut seed oil, 1g of methanol and 1g of petroleum ether according to the weight ratio of 3:1:1, adding the materials into a hydrothermal reaction kettle with the volume of 25m L, heating to 100 ℃, and adding 0.09g of SO with 10% Mo loading4 2-/TiO2Sealing the solid catalyst, placing the solid catalyst in a magnetic stirrer for reacting for 16h, taking out reaction liquid after the reaction is finished, placing the solid catalyst in a rotary evaporator for rotary evaporation for 15min under the conditions of 70 ℃ and 70rpm (rotating speed), then transferring the solid catalyst into a centrifugal machine for centrifuging for 8min at the rotating speed of 10000rpm, and filtering supernatant to obtain 26.95mg of biodiesel, wherein the yield is 62.3%, and the selectivity is 99.9%.
Wherein, the methods for calculating the yield of the biodiesel and the selectivity of the catalyst are the same as the above.
(5) SO with 20% Mo loading4 2-/TiO2The solid catalyst catalyzes the transesterification of the barbadosnut seed oil to synthesize the biodiesel:
respectively weighing 3g of barbadosnut seed oil, 1g of methanol and 1g of petroleum ether of the hemp according to the weight ratio of 3:1:1, adding the materials into a hydrothermal reaction kettle with the thickness of 25m L, heating to 100 ℃, and adding 0.09g of SO with 20% Mo loading4 2-/TiO2Sealing the solid catalyst, placing the solid catalyst in a magnetic stirrer for reaction for 16h, taking out reaction liquid after the reaction is finished, placing the solid catalyst in a rotary evaporator for rotary evaporation at 70 ℃ and 70rpm (rotating speed) for 15 hmin, then transferring the biodiesel to a centrifuge, centrifuging the biodiesel for 8min at 10000rpm, and filtering the supernatant to obtain 27.42mg of biodiesel with the yield of 63.4% and the selectivity of 99.9%.
Wherein, the methods for calculating the yield of the biodiesel and the selectivity of the catalyst are the same as the above.
(6) Solid Superacid (SO)4 2-/TiO2) The catalyst catalyzes the transesterification of the barbadosnut seed oil to synthesize the biodiesel:
respectively weighing 3g of barbadosnut seed oil, 1g of methanol and 1g of petroleum ether according to the weight ratio of 3:1:1, adding the materials into a hydrothermal reaction kettle with the volume of 25m L, heating to 100 ℃, and adding 0.09g of solid super acid (SO)4 2-/TiO2) The catalyst is sealed in a kettle and then placed in a magnetic stirrer to react for 16h, reaction liquid is taken out after the reaction is finished, the reaction liquid is placed in a rotary evaporator to be subjected to rotary evaporation for 15min under the conditions of 70 ℃ and 70rpm (rotating speed), then the reaction liquid is transferred to a centrifugal machine to be centrifuged for 8min at 10000rpm, and the supernatant is filtered to obtain 12.93mg of biodiesel, wherein the yield is 29.9%, and the selectivity is 99.9%.
Wherein, the methods for calculating the yield of the biodiesel and the selectivity of the catalyst are the same as the above.
SO passing through different Mo loadings in the above experiments (1) to (6)4 2-/TiO2Solid catalyst and solid super acid (SO)4 2-/TiO2) The yield of biodiesel synthesized by transesterification of barbadosnut seed oil catalyzed by the catalyst can be seen that in the range of 3-20% of Mo load, with the increase of Mo load, the SO loaded with metal Mo4 2-/TiO2The yield of the biodiesel synthesized by the solid catalyst through the transesterification of the barbadosnut seed oil is higher, but the rising speed of the yield of the biodiesel gradually tends to be gentle within the range of 10-20% of Mo load; in the range of 5 to 20 percent of Mo load, the SO of metal Mo is loaded4 2-/TiO2The solid catalyst catalyzes the transesterification of the barbadosnut seed oil to synthesize the biodiesel with higher yield than solid super acid (SO)4 2-/TiO2) The catalyst is high, the yield of the biodiesel is improved by 6.8 to 33.5 percent under the same condition, and obviously, the yield is improved by 5 to 20 percentSO of Mo load4 2-/TiO2The solid super acidic catalyst is applied to catalyzing the transesterification of the jatropha curcas seed oil, can obviously improve the yield of the biodiesel and has wider industrial application value; in addition, the experiment for synthesizing the biodiesel by catalyzing the transesterification of the jatropha curcas seed oil can also show that the SO is in the range of 3 to 5 percent of Mo load capacity4 2-/TiO2The catalytic activity of the solid superacid begins to change, and the transition from simple acid-catalyzed transesterification to bifunctional catalytic transesterification is started, so that the bifunctional catalyst with metal and acid catalysis is formed.
VI, SO loaded with metal molybdenum (Mo)4 2-/TiO2And (3) testing the stability of the solid catalyst in the reaction of catalyzing the transesterification of the jatropha curcas seed oil to synthesize the biodiesel:
SO at 10% Mo loading4 2-/TiO2The reaction of solid catalyst catalyzing the transesterification of Jatropha curcas seed oil to synthesize biodiesel is taken as an example, and SO loaded with metal molybdenum (Mo) is tested4 2-/TiO2The solid catalyst has the stability in the reaction of catalyzing the transesterification of the jatropha curcas seed oil to synthesize the biodiesel, and during the test, SO with 10 percent of Mo loading is added4 2-/TiO2The solid catalyst is repeatedly applied to the reaction for catalyzing the transesterification of the barbadosnut seed oil to synthesize the biodiesel five times, and the specific operation method of each reaction is as follows:
respectively weighing 3g of barbadosnut seed oil, 1g of methanol and 1g of petroleum ether according to the weight ratio of 3:1:1, adding the materials into a hydrothermal reaction kettle with the volume of 25m L, heating to 120 ℃, and adding 0.09g of SO with 10% Mo loading4 2-/TiO2The solid catalyst (the same catalyst is repeatedly utilized), the reaction solution is placed in a magnetic stirrer for reaction for 16h after the kettle is sealed, the reaction solution is taken out after the reaction is finished, the reaction solution is placed in a rotary evaporator for rotary evaporation for 15min under the conditions of 70 ℃ and 70rpm (rotating speed), then the reaction solution is transferred to a centrifugal machine for centrifugation for 8min at the rotating speed of 10000rpm, and the supernatant is filtered to obtain 26.95mg of biodiesel, wherein the yield is 62.3%, and the selectivity is 99.9%.
The test result shows that 38.64mg of biodiesel is obtained in the first reaction, the yield is 89.3%, and the selectivity is 99.7%; 36.36mg of biodiesel is obtained in the second reaction, the yield is 84.1 percent, and the selectivity is 99.5 percent; 35.21mg of biodiesel is obtained in the third reaction, the yield is 81.4 percent, and the selectivity is 99.4 percent; 33.50mg of biodiesel is obtained in the fourth reaction, the yield is 77.5 percent, and the selectivity is 99.5 percent; 32.52mg, 32.52mg biodiesel was obtained in the fifth reaction, with a yield of 75.2% and a selectivity of 99.9%.
From the above data, it can be seen that SO at 10% Mo loading4 2-/TiO2In the reaction of catalyzing the transesterification of the jatropha curcas seed oil to synthesize the biodiesel by the solid catalyst, the transesterification yield is only reduced by 14.1 percent after the reaction is repeated for five times; and solid super acid (SO)4 2-/TiO2) The catalyst has poor stability and low repeated utilization rate in the reaction of catalyzing the transesterification of the Jatropha curcas seed oil to synthesize the biodiesel (Chen C, Cai L, Shangguan X, et al4 2-/TiO2[J]Royal Society open science,2018,5(11): 181331.); it can be seen that the SO supporting the metal Mo4 2-/TiO2The solid catalyst can keep good stability in the reaction of catalyzing the transesterification of the jatropha curcas seed oil to synthesize the biodiesel, and has wider industrial application value.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.

Claims (8)

1. SO loaded with metal molybdenum4 2-/TiO2The application of the solid catalyst in the reaction of catalyzing the transesterification of the jatropha curcas seed oil to produce the biodiesel is characterized in that,
the synthesis method of the catalyst comprises the following steps:
S1、Ti(OH)4the synthesis of (2):
mixing TiCl4Slowly dropwise adding the precipitate into deionized water, adjusting the pH of the solution to 8-9 by using ammonia water, aging for 30min, and filtering and washing the obtained precipitate until no Cl exists in the precipitate-Drying and grinding the residue and the washed precipitate to obtain Ti (OH)4；
S2、SO4 2-/TiO2Synthesis of solid super acid:
taking appropriate amount of the above Ti (OH)4Adding 1-2.5 mol/L sulfuric acid solution according to the material-liquid ratio of 1:10, magnetically stirring, impregnating and acidifying for 8-24 h, and centrifuging to remove residual SO in the obtained solid4 2-Finally, drying the obtained solid, and roasting the dried solid to obtain SO4 2-/TiO2Solid super acid;
s3, SO of supported metal molybdenum4 2-/TiO2Synthesis of solid catalyst:
first to SO4 2-/TiO2Adding deionized water dropwise into solid superacid, calculating maximum water absorption amount, and adding molybdenum and SO4 2-/TiO2Preparing ammonium molybdate solution with the same amount as the maximum water absorption amount according to the weight ratio of the solid superacid, and adsorbing the ammonium molybdate solution to SO by adopting an isovolumetric immersion method4 2-/TiO2Naturally drying in solid superacid at room temperature for 24h, and finally drying and roasting to obtain SO loaded with metal molybdenum4 2-/TiO2A solid catalyst;
molybdenum and SO as described in S34 2-/TiO2The weight ratio of the solid superacid is 3-20%.
2. SO loaded with metallic molybdenum according to claim 14 2-/TiO2The application of the solid catalyst in the reaction of catalyzing the transesterification of the jatropha curcas seed oil to produce the biodiesel is characterized in that AgNO with the concentration of 1 mol/L is adopted as the precipitate in S13The solution is testedTest for Cl-And (4) remaining.
3. SO loaded with metallic molybdenum according to claim 14 2-/TiO2The application of the solid catalyst in the reaction of catalyzing the transesterification of the jatropha curcas seed oil to produce the biodiesel is characterized in that: the polishing treatment described in S1 is to polish the washed precipitate to a size of 200 mesh.
4. SO loaded with metallic molybdenum according to claim 14 2-/TiO2The application of the solid catalyst in the reaction of catalyzing the transesterification of the jatropha curcas seed oil to produce the biodiesel is characterized in that BaCl with the concentration of 1 mol/L is adopted as the solid in S22The solution is tested for the presence of SO4 2-And (4) remaining.
5. SO loaded with metallic molybdenum according to claim 14 2-/TiO2The application of the solid catalyst in the reaction of catalyzing the transesterification of the jatropha curcas seed oil to produce the biodiesel is characterized in that: the drying parameters of S1, S2 and S3 are all 120 ℃ and 24 h.
6. SO loaded with metallic molybdenum according to claim 14 2-/TiO2The application of the solid catalyst in the reaction of catalyzing the transesterification of the jatropha curcas seed oil to produce the biodiesel is characterized in that: the firing parameters described in S2 and S3 were 550 ℃ for 3 h.
7. SO loaded with metallic molybdenum according to claim 14 2-/TiO2The application of the solid catalyst in the reaction of catalyzing the transesterification of the jatropha curcas seed oil to produce the biodiesel is characterized in that: the application method comprises the following steps:
respectively weighing barbadosnut seed oil, methanol and petroleum ether according to the weight ratio of 3:1:1, adding the barbadosnut seed oil, the methanol and the petroleum ether into a hydrothermal reaction kettle, heating to a certain temperature, and adding a proper amount of SO loaded with metal molybdenum4 2-/TiO2Sealing the solid super acidic catalyst, placing the sealed solid super acidic catalyst in a magnetic stirrer for reaction for 16h, taking out reaction liquid after the reaction is finished, placing the reaction liquid in a rotary evaporator for rotary evaporation for 15min under the conditions of 70 ℃ and 70rpm, transferring the reaction liquid into a centrifugal machine for centrifugation for 8min at 10000rpm, and obtaining supernatant which is the biodiesel.
8. SO loaded with metallic molybdenum according to claim 74 2-/TiO2The application of the solid catalyst in the reaction of catalyzing the transesterification of the jatropha curcas seed oil to produce the biodiesel is characterized in that: SO of the supported metallic molybdenum4 2-/TiO2The dosage of the solid super acidic catalyst is 1.8 percent of the total weight of the barbadosnut seed oil, the methanol and the petroleum ether.
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