CN111729648B - Cu/mesoporous organic silicon oxide nanotube desulfurization adsorbent and preparation method thereof - Google Patents
Cu/mesoporous organic silicon oxide nanotube desulfurization adsorbent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a Cu/mesoporous organic silicon oxide nanotube desulfurization adsorbent and a preparation method thereof, belonging to the technical field of oil product refining and adsorption separation. According to the method, a bipyridyl group-containing organic silicon source is subjected to hydrolytic polycondensation under the guidance of P123, and metal copper is loaded on the surface and the inner wall of a nanotube in an in-situ coordination loading manner, so that the Cu/mesoporous organic silicon oxide nanotube desulfurization adsorbent is obtained. The adsorbent overcomes the technical defects of low mass transfer diffusion efficiency, poor metal dispersibility, easy shedding and high price of the traditional adsorbent, and has simple preparation process and low cost. When the adsorption desulfurization is carried out, the equilibrium adsorption capacity of the adsorbent of the invention to the thiophene sulfides is obviously higher than that of Cu-SBA-15 and is also higher than that of Cu-BTC by 24%, and the adsorbent has good application prospect in the field of deep adsorption desulfurization.
Description
Technical Field
The invention relates to a Cu/mesoporous organic silicon oxide nanotube desulfurization adsorbent and a preparation method thereof, belonging to the technical field of oil product refining and adsorption separation.
Background
The no-sulfuration of fuel oil such as gasoline, diesel oil and the like is the development trend in the world at present, and the removal of sulfur-containing compounds in the fuel oil is a big problem in the world at present. The traditional hydrodesulfurization can effectively remove most of simple organic sulfur-containing compounds such as ethanethiol, sulfide, disulfide and the like in fuel oil such as gasoline, diesel oil and the like; however, for some complex sulfur-containing compounds, such as thiophene, benzothiophene, dibenzothiophene and derivatives thereof, such as 4-methyl dibenzothiophene (4-MDBT) and 4, 6-dimethyl dibenzothiophene (4,6-DMDBT), it is difficult to remove them effectively without losing octane number, so that deep desulfurization cannot be achieved.
The adsorption desulfurization is a method for adsorbing sulfur-containing compounds to an adsorbent under mild conditions without hydrogen participation through the adsorption effect of the adsorbent and the sulfur-containing compounds, so that the aim of removing the sulfur-containing compounds from fuel oil is fulfilled. The adsorption desulfurization has better development prospect and advantages: for example, the octane number of fuel oil is hardly reduced, the operation cost is relatively low, the reaction conditions are mild, and the deep desulfurization can be achieved, and thus the method is favored by researchers. The adsorbent is the key to adsorption desulfurization.
In 2003, R T.Yang et al reported on Science that the adsorption desulfurization is carried out by utilizing molecular sieves such as CuY and AgY, and the results show that the adsorbent can have a good desulfurization effect on sulfur-containing compounds, particularly sulfur-containing compounds with low activity (benzothiophene, dibenzothiophene, derivatives thereof and the like) under mild experimental conditions, and a pi complexing mechanism is provided, so that great attention is paid to the desulfurization field, and the development of an adsorption desulfurization technology is powerfully promoted. Thereafter, around the pi-complexation mechanism, researchers have conducted a series of developments and studies on copper-based adsorbents, including Cu/AC, Cu/SiO2Cu-SBA-15, Cu-BTC, etc. The above adsorbents all have respective defects, such as Cu/AC, Cu/SiO2The removal rate of sulfur is not high, and the adsorption time is long; although the mesoporous channel of the Cu-SBA-15 is beneficial to liquid phase diffusion of thiophene sulfides, the active sites are not dispersed uniformly enough and are easy to run off; cu — BTC, a member of Metal Organic Framework (MOF) materials, has an extremely high specific surface area, but its organic framework is extremely unstable, easily collapses, and is relatively expensive. In order to solve the above problems, it is necessary to develop a deep desulfurization adsorbent having a stable structure, low cost, and high desulfurization efficiency.
Aiming at the technical problems, the invention develops the Cu/mesoporous organic silicon oxide nanotube desulfurization adsorbent for the first time, overcomes the technical defects of low mass transfer diffusion efficiency, poor dispersibility of metal active components, easy desorption and high price of the traditional desulfurization adsorbent, and has good application prospect.
Disclosure of Invention
The invention aims to provide a Cu/mesoporous organic silicon oxide nanotube desulfurization adsorbent, wherein a mesoporous organic silicon oxide nanotube is formed by condensation polymerization of a silicon source compound represented by a formula (I), and metal copper ions are loaded on the surface and the inner wall of the mesoporous organic silicon oxide nanotube in situ through coordination bonds; cu accounts for 1-8wt% of the mass of the adsorbent based on the weight of the metal
Furthermore, the tube inner diameter of the mesoporous organic silicon oxide nanotube in the Cu/mesoporous organic silicon oxide nanotube desulfurization adsorbent is 5-10nm, and the outer diameter is 18-25 nm.
The invention also aims to provide a preparation method of the Cu/mesoporous organic silicon oxide nanotube desulfurization adsorbent, which comprises the following steps:
dissolving the triblock copolymer P123 into HCl solution by taking the triblock copolymer P123 as a soft template agent, and stirring to fully dissolve the P123 to obtain solution (1); dissolving a silicon source shown in a formula (I) in ethanol, and fully stirring and dissolving to obtain a silicon source solution; dropwise adding the silicon source solution into the solution (1), adding a soluble copper salt solution to ensure that the molar ratio of the silicon source, the soft template agent and the metal copper in the solution system is 2-5:0.5-1:0.5-2, and continuously stirring for 5-24 hours; transferring the obtained mixed solution into a stainless steel reaction kettle with polytetrafluoroethylene, reacting for 20-48h at 80-120 ℃, naturally cooling to room temperature after the reaction is finished, filtering, and performing reflux extraction on the soft template agent in the filtered product by adopting ethanol to obtain the Cu/mesoporous organic silicon oxide nanotube desulfurization adsorbent.
Further, the concentration of the HCl solution is 0.5-2M.
Further, the concentration of the silicon source in the silicon source solution is 0.05-2M.
Further, the soluble copper salt is nitrate, sulfate or chloride of copper ions or cuprous ions.
Further, the concentration of the soluble copper salt solution is 0.02-0.1M.
Further, the reaction temperature in the stainless steel reaction kettle is preferably 100-110 ℃, and the reaction time is preferably 20-30 h.
Further, the temperature of the reflux extraction is 40-70 ℃, and the reflux time is 10-20 h.
According to the invention, a silicon source shown in formula (I) is subjected to hydrolytic polycondensation under the guiding action of a soft template agent P123. The triblock copolymer P123 can form micelles in an aqueous solution, and a silicon source is attached to the micelles and is subjected to hydrolytic polycondensation to form a nanotube structure. Meanwhile, PEO groups in the P123 also enter the condensed organic silicon oxide, and then the soft template agent is extracted and eluted by an organic solvent, so that the inner hole of the nanotube is exposed, and a mesopore is left in the wall of the silicon oxide. Meanwhile, metal copper ions are added into the raw materials, and the silicon source contains organic group bipyridyl which can form stable coordination bonds with metals, so that the copper ions can be stably complexed on the surface and the inner wall of the silicon oxide in an in-situ high-dispersion manner, and finally the Cu/mesoporous organic silicon oxide nanotube is obtained.
The Cu/mesoporous organic silicon oxide nanotube is used for adsorption desulfurization, and due to the existence of the mesopores and the nanotube structure, the active sites of the adsorbent are increased, and the mass transfer diffusion performance of macromolecules in fuel oil is greatly enhanced. And the metal copper with high dispersion and high stability can also effectively exert the pi complexation effect on the thiophene sulfides, so that the adsorbent can quickly adsorb and remove the thiophene sulfides.
The invention overcomes the technical defects of low mass transfer diffusion efficiency, poor metal active component dispersibility, easy shedding and high price of the traditional desulphurization adsorbent, and the used Cu/mesoporous organic silicon oxide nanotube has simple preparation process and low cost. When the Cu/mesoporous organic silicon oxide nanotube desulfurization adsorbent is used for adsorption desulfurization, the equilibrium adsorption quantity of thiophene sulfides by the Cu/mesoporous organic silicon oxide nanotube desulfurization adsorbent is obviously higher than that of Cu-SBA-15 and is also higher than that of Cu-BTC by 24%, and the Cu/mesoporous organic silicon oxide nanotube desulfurization adsorbent has a good application prospect.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Dissolving P123 in HCl solution with the concentration of 1M, and stirring to fully dissolve the P123 to obtain solution (1); dissolving a silicon source shown in a formula (I) in ethanol, and fully stirring and dissolving to obtain a silicon source solution with the concentration of 1M; dropwise adding the silicon source solution into the solution (1), adding a copper nitrate solution with the concentration of 0.05M to ensure that the molar ratio of the silicon source to the soft template agent to the metal copper in the solution system is 3:0.8:1, and continuously stirring for 8 hours; transferring the obtained mixed solution into a stainless steel reaction kettle with polytetrafluoroethylene, reacting at 100 ℃ for 24h, naturally cooling to room temperature after the reaction is finished, filtering, and performing reflux extraction on a soft template agent in a product obtained by filtering by using ethanol to obtain the Cu/mesoporous organic silicon oxide nanotube desulfurization adsorbent of the embodiment, wherein Cu accounts for 6.4 wt% of the mass of the adsorbent and is marked as the number S-1.
Example 2
Dissolving P123 in HCl solution with the concentration of 1.5M, and stirring to fully dissolve the P123 to obtain solution (1); dissolving a silicon source shown in a formula (I) in ethanol, and fully stirring and dissolving to obtain a silicon source solution with the concentration of 1.2M; dropwise adding the silicon source solution into the solution (1), adding a copper nitrate solution with the concentration of 0.05M to ensure that the molar ratio of the silicon source to the soft template agent to the metal copper in the solution system is 3:0.8:0.5, and continuously stirring for 8 hours; transferring the obtained mixed solution into a stainless steel reaction kettle with polytetrafluoroethylene, reacting at 110 ℃ for 20h, naturally cooling to room temperature after the reaction is finished, filtering, and performing reflux extraction on the soft template agent in the filtered product by using ethanol to obtain the Cu/mesoporous organic silicon oxide nanotube desulfurization adsorbent of the embodiment, wherein Cu accounts for 4.2 wt% of the mass of the adsorbent and is marked as the number S-2.
Example 3
Thiophene, benzothiophene, dibenzothiophene, 4-methyl-dibenzothiophene and n-hexane are adopted to prepare a simulated oil product, and the initial sulfur concentration is 300 mu g/g. And adding the prepared Cu/mesoporous organic silicon oxide nanotube desulfurization adsorbent into the prepared simulated oil product, adding 1g of adsorbent into each 100ml of the simulated oil product, and placing the simulated oil product in a shaking table for shaking adsorption for 5 hours at 40 ℃ to ensure that the adsorbent achieves adsorption balance. The sulfur concentration in the simulated oil product after adsorption equilibrium was determined using a microcoulomb sulfur meter, and the equilibrium adsorption sulfur capacity of the adsorbent was calculated and is listed in table 1. For comparison, Cu-SBA-15(Cu content 6 wt%) prepared by the immersion method and Cu-BTC prepared by the general hydrothermal method were also subjected to sulfur adsorption of the above-described mock oil, and the results are also shown in Table 1.
As can be seen from Table 1, the equilibrium adsorption capacity of the Cu/mesoporous organosilica nanotube desulfurization adsorbent of the invention on thiophene sulfides is obviously higher than that of Cu-SBA-15 and also higher than that of Cu-BTC by 24%, and the Cu/mesoporous organosilica nanotube desulfurization adsorbent has a potential application prospect.
TABLE 1 adsorption parameters of adsorbents for thiophenic sulfur in simulated oil
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (8)
1. Cu/mesoporous organic silicon oxide nanotube desulfurization absorberThe preparation method of the additive is characterized in that a triblock copolymer P123 is taken as a soft template agent, the P123 is dissolved in HCl solution, and the solution (1) is obtained by stirring the solution to be fully dissolved; dissolving a silicon source shown in a formula (I) in ethanol, and fully stirring and dissolving to obtain a silicon source solution; dropwise adding the silicon source solution into the solution (1), adding a soluble copper salt solution to ensure that the molar ratio of the silicon source, the soft template agent and the metal copper in the solution system is 2-5:0.5-1:0.5-2, and continuously stirring for 5-24 hours; transferring the obtained mixed solution into a stainless steel reaction kettle with polytetrafluoroethylene, reacting at 80-120 ℃ for 20-48h, naturally cooling to room temperature after the reaction is finished, filtering, and performing reflux extraction on a soft template agent in a product obtained by filtering by using ethanol to obtain a Cu/mesoporous organic silicon oxide nanotube desulfurization adsorbent;
（I）
the mesoporous organic silicon oxide nanotube is formed by condensation polymerization of a silicon source compound represented by a formula (I), and metal copper ions are loaded on the surface and the inner wall of the mesoporous organic silicon oxide nanotube in situ through coordination bonds; based on the weight of the metal, Cu accounts for 1-8wt% of the mass of the adsorbent.
2. The preparation method according to claim 1, wherein the tube inner diameter of the mesoporous organosilica nanotube in the Cu/mesoporous organosilica nanotube desulfurization adsorbent is 5-10nm, and the outer diameter is 18-25 nm.
3. The method of claim 1, wherein the HCl solution has a concentration of 0.5-2M.
4. The method according to claim 1, wherein the concentration of the silicon source in the silicon source solution is 0.05 to 2M.
5. The method of claim 1, wherein the soluble copper salt is a nitrate, sulfate or chloride of copper ion or cuprous ion.
6. The method according to claim 1, wherein the concentration of the soluble copper salt solution is 0.02-0.1M.
7. The preparation method as claimed in claim 1, wherein the reaction temperature in the stainless steel reaction kettle is 100 ℃ and 110 ℃, and the reaction time is 20-30 h.
8. The preparation method according to claim 1, wherein the temperature of the reflux extraction is 40-70 ℃ and the reflux time is 10-20 h.
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| CN101822971A (en) * | 2010-05-27 | 2010-09-08 | 南京工业大学 | Mesoporous molecular sieve adsorbent, preparation method and application thereof in gasoline desulphurization |
| CN105126747A (en) * | 2015-09-23 | 2015-12-09 | 扬州石化有限责任公司 | Preparation method of copper-containing mesoporous adsorbent for gasoline desulfurization |
| CN105833662A (en) * | 2016-05-17 | 2016-08-10 | 浙江大学 | Method for adsorbing and separating sulfur-containing acid gas |
| CN107175133A (en) * | 2017-05-10 | 2017-09-19 | 中国科学院福建物质结构研究所 | A kind of silicon dioxide carried copper dipyridyl catalyst and preparation method thereof |
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| CN101822971A (en) * | 2010-05-27 | 2010-09-08 | 南京工业大学 | Mesoporous molecular sieve adsorbent, preparation method and application thereof in gasoline desulphurization |
| CN105126747A (en) * | 2015-09-23 | 2015-12-09 | 扬州石化有限责任公司 | Preparation method of copper-containing mesoporous adsorbent for gasoline desulfurization |
| CN105833662A (en) * | 2016-05-17 | 2016-08-10 | 浙江大学 | Method for adsorbing and separating sulfur-containing acid gas |
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