Method for preparing TS-1 zeolite molecular sieve from fly ash

Abstract

The invention discloses a novel method for preparing a TS-1 zeolite molecular sieve from fly ash, which comprises the following steps: mixing and grinding fly ash and anhydrous sodium carbonate (Na2CO3) according to a certain proportion, and roasting for a certain time to obtain nepheline (NaAlSiO4); the preparation method comprises the following steps: mixing nepheline with hydrochloric acid (HCl) with a certain concentration according to a certain solid-to-liquid ratio, stirring for a certain time, and then filtering, washing, drying and grinding to obtain SiO2 powder; the method comprises the following steps: weighing a certain mass of SiO2, tetrapropylammonium hydroxide (TPAOH) and deionized water according to a molar ratio of SiO2: TPAOH: H2O of 1: 0.4: 50 at normal temperature, mixing and stirring to obtain a solution A, slowly melting a certain mass of tetrabutyl titanate into isopropanol to obtain a solution B, adding the solution B into the solution A to obtain a solution C, heating and stirring the solution C at 80-90 DEG C for 1 hour, putting the solution C into a crystallization reaction kettle, and carrying out crystallization for 2-3 hours at the temperature of 80-90 DEG C; crystallizing for a period of time at a certain temperature; after the crystallization is completed, filtering, washing and drying to obtain the TS-1 molecular sieve. The novel method for preparing the TS-1 zeolite molecular sieve from the fly ash is simple and safe to operate and relatively low in cost, and has the characteristics of small crystal grains and multiple mesopores. Meanwhile, industrial solid waste can be utilized, the production cost is reduced, a new method is provided for comprehensive utilization of the fly ash, the additional value of the fly ash is improved, and the method has very important practical significance on actual industrial production.

Description

Technical Field

[0001] The present invention belongs to the technical field of inorganic non-metals, and particularly relates to a new method for preparing TS-1 zeolite molecular sieve from fly ash. Background Art

[0002] At present, carbon-based energy is still the main part of the energy structure, and the released carbon dioxide (CO 2 2) is one of the main gases causing the atmospheric greenhouse effect. Among the current global greenhouse gas (GHG) emissions, CO 2 contributes the most to the greenhouse effect, and the concentration of CO 2 in the atmosphere is increasing year by year. At the current emission rate, it is expected to increase to 560 ppm in 2100. Carbon dioxide capture and storage (CCS) technology is an effective means to control carbon emissions and is also considered one of the most important technologies to address global climate change in the short term. Adsorbents are key components in CO 2 capture technology. Molecular sieves are often used in the adsorption field because of their rich pore structures and ability to selectively separate different gases. TS-1 zeolite molecular sieve has been widely used in catalysis, adsorption, separation, and membrane materials due to its developed pore system, excellent hydrophobicity, and adsorption and diffusion properties. At the same time, the synthesis conditions of TS-1 are simple and it has good hydrothermal stability. Therefore, TS-1 zeolite molecular sieve is an important component in gas adsorption catalysts.

[0003] The main oxide components of fly ash are silicon dioxide (SiO 2 2) and aluminum oxide (Al 2 2 3 O 2 3), among which the SiO 2 content accounts for about 33.9% - 59.7%. The chemical compositions of fly ash in different regions are also different. Fly ash is a typical industrial solid waste with rich production and low price, and is an ideal silicon source for synthesizing molecular sieves. Using fly ash as a raw material to extract SiO 2 2 to synthesize zeolite molecular sieve can not only turn fly ash into a valuable resource, but also reduce production costs. Moreover, the synthesized molecular sieve has the characteristics of small crystal grains and many mesopores. Summary of the Invention

[0004] The present invention aims to provide a new method for preparing TS-1 zeolite molecular sieve from fly ash.

[0005] The specific steps for preparing TS-1 zeolite molecular sieve from fly ash in the present invention are as follows: Mix fly ash with anhydrous sodium carbonate (Na 2 2 3 CO 4 3) in a certain proportion, grind them, and calcine for a certain time to obtain nepheline (NaAlSiO4 ).

[0006] Mix nepheline with hydrochloric acid (HCl) at a certain concentration according to a certain solid-liquid ratio, stir for a certain time, then filter, wash, dry, and grind to obtain SiO 2 powder.

[0007] At room temperature, weigh a certain mass of SiO 2 : TPAOH: H 2 O = 1:0.4:50 in molar ratio, mix and stir, denoted as solution A. Slowly dissolve a certain mass of tetrabutyl titanate in isopropanol, denoted as solution B. Then add solution B to solution A to obtain solution C. Heat and stir solution C at 80 - 90 °C for 1 h, then put it into a crystallization reactor and crystallize at a certain temperature for a certain period of time. After crystallization, filter, wash, and dry to obtain TS-1 zeolite molecular sieve. 2

[0008] The mass ratio of fly ash to Na 2 CO 3 is 1:0.6 - 1:2.

[0009] The roasting temperature is 750 - 850 °C, and the roasting time is 75 - 150 min.

[0010] The concentration of HCl is 2 - 5 moles.

[0011] The ratio of NaAlSiO 4 to HCl is 1:10 (g / mL), and the stirring time is 1 - 4 h.

[0012] The crystallization time is 6 - 60 h.

[0013] The crystallization temperature is 130 - 170 °C.

[0014] The molar ratio of SiO 2 to TiO 2 is 30 - 70.

[0015] The new method for preparing TS-1 zeolite molecular sieve from fly ash of the present invention is simple, safe to operate, and has a low cost. The TS-1 zeolite molecular sieve prepared by the present invention using fly ash has the characteristics of small crystal grains and many mesopores.

[0016] The present invention prepares TS-1 type zeolite molecular sieve from fly ash, which can effectively utilize solid waste, provides a new method for comprehensive utilization of fly ash, improves the added value of fly ash, and at the same time reduces the cost of TS-1 zeolite molecular sieve. It has very important practical significance for actual industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is the XRF data of silicon dioxide extracted from fly ash. The data shows that silicon dioxide was successfully extracted from fly ash as raw material. Figure 2 This is the XRD diagram of TS-1 zeolite molecular sieve prepared from fly ash, in which obvious characteristic peaks of TS-1 zeolite molecular sieve appear. Figure 3 This is the SEM image of TS-1 zeolite molecular sieve prepared from fly ash. The sample in the image shows regular long block crystals. Figure 4 This is the UV-Vis graph of TS-1 zeolite molecular sieve prepared from fly ash. The presence of characteristic peaks in the graph indicates that the synthesized TS-1 zeolite molecular sieve has a high framework titanium structure. From the analysis of the graph, it can be seen that TS-1 zeolite molecular sieve was successfully prepared from fly ash soil. DETAILED DESCRIPTION

[0018] The present invention is further described in detail below with reference to the embodiments, but is not limited thereto. Example

[0019] Fly ash and anhydrous sodium carbonate (Na 2 CO 3 ) are mixed and ground in a certain proportion and roasted for a certain period of time to obtain nepheline (NaAlSiO 4 ).

[0020] Mix nepheline with a certain concentration of hydrochloric acid (HCl) according to a certain solid-liquid ratio, stir for a certain period of time, and then filter, wash, dry and grind to obtain SiO 2 powder.

[0021] At room temperature, SiO 2 :TPAOH:H 2 O=1:0.4:50 molar ratio Weigh a certain mass of SiO 2 , tetrapropylammonium hydroxide (TPAOH) and deionized water are mixed and stirred, which is recorded as solution A. A certain mass of tetrabutyl titanate is slowly dissolved in isopropanol, which is recorded as solution B. Then, solution B is added to solution A to obtain solution C. Solution C is heated and stirred at 80-90°C for 1 hour and then placed in a crystallization reactor to crystallize at a certain temperature for a period of time. After the crystallization is completed, it is filtered, washed and dried to obtain TS-1 molecular sieve.

[0022] Fly ash and Na 2 CO 3 The mass ratio is 1:0.6-1:2.

[0023] The calcination temperature is 850°C and the calcination time is 100 min.

[0024] The concentration of HCl is 5 mol.

[0025] NaAlSiO 4 The ratio with HCl was 1:10 (g / mL), and the stirring time was 4 h.

[0026] The crystallization time is 48h.

[0027] The crystallization temperature is 170°C.

[0028] SiO 2 With TiO 2 The molar ratio is 40. Example

[0029] Fly ash and anhydrous sodium carbonate (Na 2 CO 3 ) are mixed and ground in a certain proportion and roasted for a certain period of time to obtain nepheline (NaAlSiO 4 ).

[0030] Mix nepheline with a certain concentration of hydrochloric acid (HCl) according to a certain solid-liquid ratio, stir for a certain period of time, and then filter, wash, dry and grind to obtain SiO 2 powder.

[0031] At room temperature, SiO 2 :TPAOH:H 2 O=1:0.4:50 molar ratio Weigh a certain mass of SiO 2 , tetrapropylammonium hydroxide (TPAOH) and deionized water are mixed and stirred, which is recorded as solution A. A certain amount of tetrabutyl titanate is slowly dissolved in isopropanol, which is recorded as solution B. Then, solution B is added to solution A to obtain solution C. Solution C is heated and stirred at 80-90°C for 1 hour and then placed in a crystallization reactor to crystallize at a certain temperature for a period of time. After the crystallization is completed, it is filtered, washed and dried to obtain TS-1 molecular sieve.

[0032] Fly ash and Na 2 CO 3 The mass ratio is 1:1.

[0033] The calcination temperature is 750-850°C and the calcination time is 100 minutes.

[0034] The concentration of HCl is 5 mol.

[0035] NaAlSiO 4 The ratio with HCl was 1:10 (g / mL), and the stirring time was 4 h.

[0036] The crystallization time is 48h.

[0037] The crystallization temperature is 170°C.

[0038] SiO 2 With TiO 2 The molar ratio is 40. Example

[0039] Fly ash and anhydrous sodium carbonate (Na 2 CO 3 ) are mixed and ground in a certain proportion and roasted for a certain period of time to obtain nepheline (NaAlSiO 4 ).

[0040] Mix nepheline with a certain concentration of hydrochloric acid (HCl) according to a certain solid-liquid ratio, stir for a certain period of time, and then filter, wash, dry and grind to obtain SiO 2 powder.

[0041] At room temperature, SiO 2 :TPAOH:H 2 O=1:0.4:50 molar ratio Weigh a certain mass of SiO 2 , tetrapropylammonium hydroxide (TPAOH) and deionized water are mixed and stirred, which is recorded as solution A. A certain amount of tetrabutyl titanate is slowly dissolved in isopropanol, which is recorded as solution B. Then, solution B is added to solution A to obtain solution C. Solution C is heated and stirred at 80-90°C for 1 hour and then placed in a crystallization reactor to crystallize at a certain temperature for a period of time. After the crystallization is completed, it is filtered, washed and dried to obtain TS-1 molecular sieve.

[0042] Fly ash and Na 2 CO 3 The mass ratio is 1:1.

[0043] The calcination temperature is 850°C and the calcination time is 75-150min.

[0044] The concentration of HCl is 5 mol.

[0045] NaAlSiO 4 The ratio with HCl was 1:10 (g / mL), and the stirring time was 4 h.

[0046] The crystallization time is 48h.

[0047] The crystallization temperature is 170°C.

[0048] SiO 2 With TiO 2 The molar ratio is 40. Example

[0049] Fly ash and anhydrous sodium carbonate (Na 2 CO 3(0) Mix and grind in a certain proportion and calcine for a certain time to obtain nepheline (NaAlSiO 4 ).

[0050] Mix nepheline with hydrochloric acid (HCl) at a certain concentration according to a certain solid-liquid ratio, stir for a certain time, then filter, wash, dry, and grind to obtain SiO 2 powder.

[0051] At room temperature, weigh a certain mass of SiO 2 : TPAOH: H 2 2O in a molar ratio of 1:0.4:50, mix and stir, denoted as solution A. Slowly dissolve a certain mass of tetrabutyl titanate in isopropanol, denoted as solution B. Then add solution B to solution A to obtain solution C. Heat and stir solution C at 80 - 90 °C for 1 h and then put it into a crystallization reactor and crystallize at a certain temperature for a certain period of time. After crystallization is completed, filter, wash, and dry to obtain TS-1 molecular sieve. 2

[0052] The mass ratio of fly ash to Na 2 2CO 3 3 is 1:1.

[0053] The calcination temperature is 850 °C and the calcination time is 100 min.

[0054] The concentration of HCl is 2 - 5 mol.

[0055] The ratio of NaAlSiO 4 to HCl is 1:10 (g / mL), and the stirring time is 4 h.

[0056] The crystallization time is 48 h.

[0057] The crystallization temperature is 170 °C.

[0058] The molar ratio of SiO 2 to TiO 2 2 is 40. Example

[0059] Mix fly ash with anhydrous sodium carbonate (Na 2 2CO 3 3) in a certain proportion, mix and grind, and calcine for a certain time to obtain nepheline (NaAlSiO 4 ).

[0060] Mix nepheline with hydrochloric acid (HCl) at a certain concentration according to a certain solid-liquid ratio, stir for a certain time, then filter, wash, dry, and grind to obtain SiO 2 powder.​

[0061] At room temperature, SiO 2 :TPAOH:H 2 O=1:0.4:50 molar ratio Weigh a certain mass of SiO 2 , tetrapropylammonium hydroxide (TPAOH) and deionized water are mixed and stirred, which is recorded as solution A. A certain amount of tetrabutyl titanate is slowly dissolved in isopropanol, which is recorded as solution B. Then, solution B is added to solution A to obtain solution C. Solution C is heated and stirred at 80-90°C for 1 hour and then placed in a crystallization reactor to crystallize at a certain temperature for a period of time. After the crystallization is completed, it is filtered, washed and dried to obtain TS-1 molecular sieve.

[0062] Fly ash and Na 2 CO 3 The mass ratio is 1:1.

[0063] The calcination temperature is 850°C and the calcination time is 100 min.

[0064] The concentration of HCl is 5 mol.

[0065] NaAlSiO 4 The ratio with HCl was 1:10 (g / mL), and the stirring time was 4 h.

[0066] The crystallization time is 6-60h.

[0067] The crystallization temperature is 170°C.

[0068] SiO 2 With TiO 2 The molar ratio is 40. Example

[0069] Fly ash and anhydrous sodium carbonate (Na 2 CO 3 ) are mixed and ground in a certain proportion and roasted for a certain period of time to obtain nepheline (NaAlSiO 4 ).

[0070] Mix nepheline with a certain concentration of hydrochloric acid (HCl) according to a certain solid-liquid ratio, stir for a certain period of time, and then filter, wash, dry and grind to obtain SiO 2 powder.

[0071] Weigh a certain amount of deionized water, SiO 2 The mixture is mixed with tetrapropylammonium hydroxide (TPAOH), stirred, and then transferred to a crystallization reactor to crystallize at a certain temperature for a period of time. After the crystallization is completed, it is filtered, washed, and dried to obtain Silicalite-1 molecular sieve.

[0072] Fly ash and Na 2 CO 3 The mass ratio is 1:1.

[0073] The calcination temperature is 850°C and the calcination time is 100 min.

[0074] The concentration of HCl is 5 mol.

[0075] NaAlSiO 4 The ratio with HCl was 1:10 (g / mL), and the stirring time was 4 h.

[0076] The crystallization time is 48h.

[0077] The crystallization temperature is 130-170°C.

[0078] SiO 2 With TiO 2 The molar ratio is 40. Example

[0079] Fly ash and anhydrous sodium carbonate (Na 2 CO 3 ) are mixed and ground in a certain proportion and roasted for a certain period of time to obtain nepheline (NaAlSiO 4 ).

[0080] Mix nepheline with a certain concentration of hydrochloric acid (HCl) according to a certain solid-liquid ratio, stir for a certain period of time, and then filter, wash, dry and grind to obtain SiO 2 powder.

[0081] At room temperature, SiO 2 :TPAOH:H 2 O=1:0.4:50 molar ratio Weigh a certain mass of SiO 2 , tetrapropylammonium hydroxide (TPAOH) and deionized water are mixed and stirred, which is recorded as solution A. A certain amount of tetrabutyl titanate is slowly dissolved in isopropanol, which is recorded as solution B. Then, solution B is added to solution A to obtain solution C. Solution C is heated and stirred at 80-90°C for 1 hour and then placed in a crystallization reactor to crystallize at a certain temperature for a period of time. After the crystallization is completed, it is filtered, washed and dried to obtain TS-1 molecular sieve.

[0082] Fly ash and Na 2 CO 3 The mass ratio is 1:1.

[0083] The calcination temperature is 850°C and the calcination time is 100 min.

[0084] The concentration of HCl is 5 mol.

[0085] NaAlSiO 4 The ratio with HCl is 1:10 (g / mL), and the stirring time is 4 h.

[0086] The crystallization time is 48 h.

[0087] The crystallization temperature is 170 °C.

[0088] SiO 2 and TiO 2 The molar ratio is 30 - 70.

[0089] The experimental data of Examples 1 - 7 of the present invention show that the mass ratio of fly ash to Na 2 CO 3 is 1:1. The roasting temperature is 850 °C, and the roasting time is 100 min. The concentration of HCl is 5 mol. The ratio of NaAlSiO 4 to HCl is 1:10 (g / mL), and the stirring time is 4 h. The crystallization time is 48 h, the crystallization temperature is 170 °C, and when the molar ratio of SiO 2 to TiO 2 is 40, the effect of preparing TS-1 type molecular sieve from fly ash is better.

[0090] The above are only preferred embodiments of the present invention. It is easy for those skilled in the art to understand that the embodiments are not used to limit the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A new method for preparing TS-1 zeolite molecular sieve from fly ash, comprising the following steps: Nepheline (NaAlSiO4) is obtained by mixing fly ash and anhydrous sodium carbonate (Na2CO3) in a certain proportion, grinding them, and roasting them for a certain period of time.

2. Mix nepheline with a certain concentration of hydrochloric acid (HCl) in a certain solid-liquid ratio, stir for a certain period of time, and then filter, wash, dry and grind to obtain SiO2 powder.

3. At room temperature, a certain mass of SiO2, tetrapropylammonium hydroxide (TPAOH) and deionized water were weighed and mixed in a molar ratio of SiO2:TPAOH:H2O=1:0.4:50, which was recorded as solution A. A certain mass of tetrabutyl titanate was slowly dissolved in isopropanol, which was recorded as solution B. Then, solution B was added to solution A to obtain solution C. Solution C was heated and stirred at 80-90°C for 1h, then placed in a crystallization reactor, and crystallized at a certain temperature for a period of time. After crystallization, it was filtered, washed and dried to obtain TS-1 molecular sieve.

4. The novel method for preparing TS-1 zeolite molecular sieve from fly ash as claimed in claim 1, characterized in that: The mass ratio of fly ash to Na2CO3 is 1:0.6-1:

2.

5. The novel method for preparing TS-1 zeolite molecular sieve from fly ash as claimed in claim 1, characterized in that: The calcination temperature is 750-850°C, and the calcination time is 75-150min.

6. The novel method for preparing TS-1 zeolite molecular sieve from fly ash as claimed in claim 1, characterized in that: The concentration of HCl is 2-5 molar and the stirring time is 1-4h.

7. The novel method for preparing TS-1 zeolite molecular sieve from fly ash as claimed in claim 1, characterized in that: The crystallization time is 6-60h.

8. The novel method for preparing TS-1 zeolite molecular sieve from fly ash as claimed in claim 1, characterized in that: The crystallization temperature is 130-170°C.

9. The novel method for preparing TS-1 zeolite molecular sieve from fly ash as claimed in claim 1, characterized in that: The molar ratio of SiO2 to TiO2 is 30-70.

Images