CN110723741B - Green preparation method of AgY molecular sieve for adsorption desulfurization - Google Patents
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- C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
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Abstract
The invention relates to a green preparation method and application of an AgY molecular sieve for adsorption desulfurization, belonging to the fields of comprehensive utilization of wastes and oil product refining. The AgY molecular sieve is prepared by taking solid waste lithium slag as a basic raw material, adding a silicon source and silver nitrate into the raw material, and regulating the silicon-aluminum ratio of the raw material through in-situ one-step hydrothermal synthesis. Compared with the conventional ion exchange method, the AgY molecular sieve prepared by the method has the advantages of strong metal binding force, high dispersibility and difficult shedding, omits the subsequent ion exchange step in the traditional preparation method, simplifies the preparation process and reduces the energy consumption. The method has the advantages of easily obtained raw materials and low cost, can effectively solve the problems of lithium slag accumulation and environmental pollution, and has wide application prospect because the obtained product is applied to deep adsorption desulfurization of oil products and has higher adsorption and removal capacity on thiophenic sulfur and derivatives thereof.
Description
Technical Field
The invention relates to a green preparation method of an AgY molecular sieve for adsorption desulfurization, belonging to the fields of comprehensive utilization of wastes and oil product refining.
Background
Thiophene sulfides are the sulfides with the highest content (accounting for about 70 percent of the total sulfur mass percent) in FCC gasoline, and the sulfides are difficult to effectively remove by the traditional hydrodesulfurization mode. Therefore, the development of a new technology for realizing the efficient removal of the thiophene sulfides in the fuel oil becomes a research hotspot of researchers. Among the desulfurization technologies, the selective adsorption desulfurization technology is the first choice of the new generation desulfurization technology due to the advantages of mild conditions, good quality of oil products and low cost. The key point of the selective desulfurization technology lies in the development of a high-efficiency desulfurization adsorbent, wherein the Y-type molecular sieve has definite pore cavity distribution, specific pore size, extremely large specific surface area and better heat resistance and is widely used for adsorption desulfurization. Meanwhile, students load other active metal components on the surface of the Y-type molecular sieve to further improve the desulfurization performance of the Y-type molecular sieve, such as Ni, Zn, Cu, Ag and the like, and find that the Y-type molecular sieve after metal exchange can effectively remove thiophene sulfides, and the adsorption performance of the Y-type molecular sieve on the thiophene sulfides is still better when aromatic hydrocarbon, olefin or a mixture thereof exists.
In the process of producing lithium carbonate by using spodumene (ore) as a raw material and using a sulfuric acid method, a large amount of waste slag (lithium slag) is generated, and nearly 10 tons of lithium slag (lithium slag) are generated for producing 1 ton of lithium carbonate product. At present, only a very small amount of lithium slag is used as a raw material of building materials such as cement, concrete and the like, and a large amount of lithium slag is buried or piled in the open airThe method not only occupies the field, but also runs off with wind and rain and pollutes the environment. The main component of the lithium slag is SiO2And Al2O3The sum of the two is up to more than 96 percent, the content of other metal oxides is lower, and the composition is similar to the synthesis raw material of the molecular sieve, so that a scholars successfully synthesizes the NaA molecular sieve (CN109485062A) and the NaX molecular sieve (the NaX molecular sieve synthesized from the lithium slag is characterized in structure and the adsorption characteristic is researched, HuXin and the like, the university journal of chemical engineering, 2017, 4 (27): 708-.
In view of the prior art, the inventor of the invention has conducted a great deal of research for a long time, and has used lithium slag as a basic raw material, supplemented with a silicon source and silver nitrate, and hydrothermally synthesized the AgY molecular sieve in situ in one step by adjusting the silicon-aluminum ratio of the raw material. Silver nitrate in the molecular sieve is added into a hydrothermal precursor, and silver ions can participate in the recombination of a silicon source and an aluminum source and are doped into aluminosilicate in the hydrothermal reaction process. Compared with the conventional ion exchange method, the AgY molecular sieve prepared by the method has the advantages of strong metal binding force, high dispersibility and difficult shedding, can save the subsequent ion exchange step, simplifies the preparation process and saves the energy consumption. The method adopts solid waste lithium slag as a raw material, has low cost, can effectively solve the problems of accumulation of the lithium slag and environmental pollution, is applied to deep adsorption desulfurization, has higher adsorption and removal capacity on thiophenic sulfur and derivatives thereof, and has wide application prospect.
Disclosure of Invention
The invention aims to provide a preparation method of an AgY molecular sieve for adsorption desulfurization, which takes lithium slag as a basic raw material, supplements silicon source and silver nitrate in the raw material, and synthesizes the AgY molecular sieve by in-situ hydrothermal synthesis by adjusting the silicon-aluminum ratio of the raw material. Silver nitrate in the molecular sieve is added into a hydrothermal precursor, and silver ions can participate in the recombination of a silicon source and an aluminum source and are doped into aluminosilicate in the hydrothermal reaction process. The sulfur-containing composite material is applied to deep adsorption desulfurization, and has higher adsorption and removal capacity on thiophenic sulfur and derivatives thereof.
Specifically, the preparation method of the AgY molecular sieve for adsorption desulfurization comprises the following steps:
(1) grinding and crushing raw material lithium slag, washing with water to remove impurities, and sieving with a 60-200-mesh sieve to remove large particles;
(2) uniformly mixing the lithium slag obtained in the step (1) with an alkali fusing agent according to the mass ratio of 0.2-5, placing the mixture in a muffle furnace, and roasting the mixture for 2-15h at the temperature of 500-;
(3) dissolving the alkali-fused lithium slag obtained in the step (2) in deionized water in a solid-to-liquid ratio of 1:3-10(g/ml) to form sol, and supplementing silica sol into the sol to adjust the molar ratio of silica to aluminum in the raw material solution (SiO is used as the SiO2/Al2O3Metering) is 4-7, and stirring is continuously carried out uniformly; dissolving silver nitrate in deionized water to form 0.5-1mol/L silver nitrate solution, dropwise adding ammonia water into the silver nitrate solution to form a precipitate, and continuously dropwise adding ammonia water to dissolve the precipitate to obtain a silver-ammonium complex; adding the silver ammonium complex into the raw material liquid in an amount which enables the molar ratio of silver to silicon in the solution to be 0.5-0.8, continuously stirring, and aging at room temperature for 2-24 h;
(4) and (4) transferring the precursor solution obtained in the step (3) into a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal crystallization at the temperature of 100 ℃ and 250 ℃ for 5-24h, naturally cooling to room temperature, filtering, washing, drying and roasting to obtain the AgY molecular sieve.
Wherein, the inert quartz in the lithium slag is activated by alkali fusion in the step (2) to be converted into active sodium metasilicate for synthesizing the molecular sieve; the alkali flux is sodium hydroxide, sodium carbonate or sodium bicarbonate, and sodium hydroxide is preferred.
The alkali-fused lithium slag contains a certain amount of alkali, and the alkali can react with nitrate after being dissolved in water to generate insoluble silver compound precipitate, so that the assembly of the subsequent hydrothermal crystallization process is influenced; the silver nitrate solution and ammonia water react to generate a silver-ammonium complex which can stably exist in an alkaline solution, and the existence of the silver-ammonium complex can further improve the dispersibility of the solution, so that the raw materials can be more uniformly assembled on a molecular layer, and the obtained molecular sieve has the advantages of regular appearance and uniform and controllable particle size.
The process of room temperature aging can promote the nucleation of the raw materials, avoid the generation of mixed crystals in the subsequent hydrothermal crystallization process, and the aging time is preferably 3-12 h.
The hydrothermal crystallization is preferably carried out at 120-200 ℃, and the crystallization time is preferably 6-10 h.
After hydrothermal crystallization reaction, washing the product with deionized water to remove alkali remained on the molecular sieve, heating to 60-150 ℃ and drying for 2-10 hours; roasting in air atmosphere at the roasting temperature of 300-800 ℃.
The invention also aims to provide an application method of the AgY molecular sieve in deep adsorption desulfurization, which specifically comprises the steps of adding the prepared AgY molecular sieve into an oil product containing thiophene and derivatives thereof, wherein the initial sulfur concentration of the oil product is 100-1000 mu g/g, the liquid-solid ratio is 50-200(ml/g), oscillating and adsorbing at 20-60 ℃ for 2-10h to achieve adsorption balance, and measuring the sulfur concentration of the oil product after adsorption balance, so as to calculate the static sulfur capacity of the AgY molecular sieve.
Under the adsorption condition, the static adsorption sulfur capacity of the AgY molecular sieve obtained by the invention can reach 20mg/g at most, and the AgY molecular sieve is superior to the AgY molecular sieve prepared by the existing ion exchange method.
According to the invention, a large amount of waste residues generated in the process of producing lithium carbonate by a spodumene sulfuric acid method are used as raw materials, and the AgY molecular sieve is synthesized by alkali fusion, silicon supplement and in-situ one-step hydrothermal synthesis and is used for deep adsorption desulfurization. Compared with the prior art, the invention has the beneficial effects that:
(1) compared with the conventional ion exchange method, the AgY molecular sieve prepared by the invention has the advantages of strong metal binding force, high dispersibility and difficult shedding;
(2) the method adopts in-situ one-step hydrothermal synthesis, saves the subsequent ion exchange step compared with the conventional ion exchange method, simplifies the preparation process and saves the energy consumption;
(3) the invention adopts solid waste lithium slag as raw material, has low cost, can effectively solve the problems of accumulation of lithium slag and environmental pollution, changes waste into valuable and has extremely high environmental and economic values;
(4) the AgY molecular sieve prepared by the invention is applied to deep adsorption desulfurization of oil products, has better adsorption and removal capacity on thiophenic sulfur and derivatives thereof compared with common molecular sieve adsorbents, and has wide application prospect.
Drawings
FIG. 1 is an XRD pattern of an AgY molecular sieve prepared by the invention.
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
(1) Grinding and crushing raw material lithium slag, washing with water to remove impurities, and sieving with a 60-mesh sieve to remove large particles;
(2) uniformly mixing the lithium slag obtained in the step (1) with an alkali flux in a mass ratio of 1.5:1, placing the mixture in a muffle furnace, and roasting the mixture for 6 hours at 600 ℃ to obtain alkali-fused lithium slag;
(3) dissolving the alkali-fused lithium slag obtained in the step (2) in deionized water according to the solid-to-liquid ratio of 1:6g/ml to form sol, supplementing silica sol into the sol to adjust the molar ratio of silica to aluminum in the raw material liquid to be 5, and continuously and uniformly stirring; dissolving silver nitrate in deionized water to form a 0.8mol/L silver nitrate solution, dropwise adding ammonia water into the silver nitrate solution to enable the silver nitrate solution to form a precipitate, and continuously dropwise adding ammonia water to enable the precipitate to be dissolved to obtain a silver-ammonium complex; adding the silver ammonium complex into the raw material liquid in an amount which enables the molar ratio of silver to silicon in the solution to be 0.7, continuously stirring, and aging at room temperature for 4 hours;
(4) and (4) transferring the precursor solution obtained in the step (3) into a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal crystallization at 180 ℃ for 8 hours, naturally cooling to room temperature, filtering, washing, drying and roasting to obtain the AgY molecular sieve. Is marked as AgY-1.
Example 2
(1) Grinding and crushing raw material lithium slag, washing with water to remove impurities, and sieving with a 60-mesh sieve to remove large particles;
(2) uniformly mixing the lithium slag obtained in the step (1) with an alkali fusing agent in a mass ratio of 1:1, placing the mixture in a muffle furnace, and roasting the mixture for 6 hours at 600 ℃ to obtain alkali fused lithium slag;
(3) dissolving the alkali-fused lithium slag obtained in the step (2) in deionized water according to a solid-to-liquid ratio of 1:7(g/ml) to form sol, supplementing silica sol into the sol to adjust the molar ratio of silica to alumina in the raw material liquid to 7, and continuously and uniformly stirring; dissolving silver nitrate in deionized water to form a 0.8mol/L silver nitrate solution, dropwise adding ammonia water into the silver nitrate solution to enable the silver nitrate solution to form a precipitate, and continuously dropwise adding ammonia water to enable the precipitate to be dissolved to obtain a silver-ammonium complex; adding the silver ammonium complex into the raw material liquid in an amount which enables the molar ratio of silver to silicon in the solution to be 0.8, continuously stirring, and aging at room temperature for 4 hours;
(4) and (4) transferring the precursor solution obtained in the step (3) into a stainless steel reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal crystallization at 210 ℃ for 10 hours, naturally cooling to room temperature, filtering, washing, drying and roasting to obtain the AgY molecular sieve. Is marked as AgY-2.
Fig. 1 is an XRD pattern of AgY molecular sieve obtained by the present invention. As can be seen from FIG. 1, the AgY molecular sieve prepared by the invention has similar characteristic diffraction peaks and no impurity peaks compared with commercial NaY molecular sieve standard samples, which indicates that the AgY molecular sieve prepared by the invention is a pure-phase molecular sieve and no impurity crystals appear, and also indicates that Ag enters the molecular sieve in a doped form.
The elemental composition of the AgY molecular sieve prepared by the invention is analyzed by X-ray fluorescence spectroscopy, as shown in Table 1.
TABLE 1 elemental composition of AgY molecular sieves
Example 3
Thiophene, benzothiophene, dibenzothiophene and n-hexane are adopted to prepare a simulated oil product, and the initial sulfur concentration is 500 mug/g. And adding the AgY molecular sieve obtained by the preparation into the simulated oil product, adding the AgY molecular sieve into the simulated oil product, wherein the liquid-solid ratio is 100ml/g, oscillating and adsorbing the AgY molecular sieve for 4 hours at 50 ℃ to achieve adsorption balance, and measuring the sulfur concentration of the oil product after adsorption balance so as to calculate the static sulfur capacity of the AgY molecular sieve. Table 2 shows the equilibrium sulfur capacity of the AgY molecular sieve prepared by the invention under the adsorption condition. For comparison, the AgY molecular sieve (noted AgY-3) prepared by the conventional ion exchange method is used for adsorption desulfurization under the same conditions, and the results are shown in Table 2. As can be seen from Table 2, the static equilibrium adsorption sulfur capacity of the AgY molecular sieve prepared by the method can reach 20.07mg/g, is improved by about 19% compared with the AgY molecular sieve prepared by the conventional ion exchange method, and has higher application value.
TABLE 2 static adsorption sulfur capacity of AgY molecular sieves
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. The green preparation method of the AgY molecular sieve for adsorption desulfurization is characterized by comprising the following preparation steps:
(1) grinding and crushing raw material lithium slag, washing with water to remove impurities, and sieving with a 60-200-mesh sieve to remove large particles;
(2) uniformly mixing the lithium slag obtained in the step (1) with an alkali fusing agent according to the mass ratio of 0.2-5, placing the mixture in a muffle furnace, and roasting the mixture for 2-15h at the temperature of 500-;
(3) dissolving the alkali-fused lithium slag obtained in the step (2) in deionized water according to the solid-to-liquid ratio of 1:3-10g/ml to form sol, and supplementing silica sol into the sol to adjust the molar ratio of silica to alumina in the raw material liquid to form SiO2/Al2O3Counting as 4-7, and continuously stirring uniformly; dissolving silver nitrate in deionized water to form 0.5-1mol/L silver nitrate solution, dropwise adding ammonia water into the silver nitrate solution to form a precipitate, and continuously dropwise adding ammonia water to dissolve the precipitate to obtain a silver-ammonium complex; adding the silver ammonium complex into the raw material liquid in an amount which enables the molar ratio of silver to silicon in the solution to be 0.5-0.8, continuously stirring, and aging at room temperature for 2-24 h;
(4) and (4) transferring the precursor solution obtained in the step (3) into a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal crystallization at the temperature of 100 ℃ and 250 ℃ for 5-24h, naturally cooling to room temperature, filtering, washing, drying and roasting to obtain the AgY molecular sieve.
2. The process according to claim 1, wherein the alkali flux is sodium hydroxide, sodium carbonate or sodium bicarbonate.
3. The process according to claim 1, wherein the aging time is preferably 3 to 12 hours.
4. The preparation method as claimed in claim 1, wherein the hydrothermal crystallization is preferably carried out at 120-200 ℃ and the crystallization time is preferably 6-10 h.
5. The method of claim 1, wherein after the hydrothermal crystallization reaction, the product is washed with deionized water.
6. The method according to claim 1, wherein the drying temperature is 60 to 150 ℃ and the drying time is 2 to 10 hours.
7. The method as claimed in claim 1, wherein the firing is performed in an air atmosphere at a firing temperature of 300-800 ℃.
8. The application of the AgY molecular sieve prepared by the method as claimed in claim 1 in deep adsorption desulfurization, which is characterized in that the AgY molecular sieve is added into an oil product containing thiophene and derivatives thereof, the initial sulfur concentration of the oil product is 100-1000 μ g/g, the liquid-solid ratio is 50-200 ml/g, the oil product is subjected to oscillation adsorption at 20-60 ℃ for 2-10h to achieve adsorption balance, and the sulfur concentration of the oil product after the adsorption balance is measured, so that the static sulfur capacity of the AgY molecular sieve is calculated.
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| CN101624191A (en) * | 2009-08-03 | 2010-01-13 | 南京工业大学 | Method for preparing 13 X molecular sieve by using lithium slag as raw materials |
| WO2013001296A2 (en) * | 2011-06-27 | 2013-01-03 | Susan Jones | Zeolites and composites incorporating zeolites |
| CN103191697A (en) * | 2013-03-18 | 2013-07-10 | 北京化工大学 | Desulfurizing adsorbent Ag2O/NaY based on molecular screen and preparation method thereof |
| CN108079941A (en) * | 2016-11-23 | 2018-05-29 | 韩会义 | A kind of AgCeY adsorbent of molecular sieve |
| CN109485062A (en) * | 2018-12-27 | 2019-03-19 | 中国矿业大学(北京) | A kind of low temperature preparation method of lithium slag base NaA molecular sieve |
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| CN101624191A (en) * | 2009-08-03 | 2010-01-13 | 南京工业大学 | Method for preparing 13 X molecular sieve by using lithium slag as raw materials |
| WO2013001296A2 (en) * | 2011-06-27 | 2013-01-03 | Susan Jones | Zeolites and composites incorporating zeolites |
| CN103191697A (en) * | 2013-03-18 | 2013-07-10 | 北京化工大学 | Desulfurizing adsorbent Ag2O/NaY based on molecular screen and preparation method thereof |
| CN108079941A (en) * | 2016-11-23 | 2018-05-29 | 韩会义 | A kind of AgCeY adsorbent of molecular sieve |
| CN109485062A (en) * | 2018-12-27 | 2019-03-19 | 中国矿业大学(北京) | A kind of low temperature preparation method of lithium slag base NaA molecular sieve |
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