CN115445639A - Solid super acidic catalyst, preparation method and application thereof - Google Patents
Solid super acidic catalyst, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a solid super acidic catalyst, a preparation method and application thereof, belonging to the field of catalysis. The preparation method of the solid super acidic catalyst is to recover TiO from the waste SCR catalyst by using an alkaline leaching method 2 Recovering the obtained TiO 2 Stirring and mixing with sulfuric acid, filtering, washing, drying and high-temperature calcining to obtain the catalyst. The preparation method is simple to operate, mild in condition and beneficial to large-scale production and application. And by recovering TiO 2 The method promotes the recycling of titanium resources, reduces the pollution of the waste SCR catalyst to the environment, and is beneficial to environmental protection. The prepared solid super acidic catalyst has high surface area and macroporosity, higher total acid strength, better modification effect, higher catalytic activity and more stable performance, and is particularly suitable for serving as a catalyst for ester exchange reaction, for exampleAs a catalyst for the ester exchange reaction of ethyl acetate and n-butanol, the conversion rate of the reaction raw material n-butanol reaches 92%.
Description
Technical Field
The invention belongs to the field of catalysis, and particularly relates to a solid super acidic catalyst, and a preparation method and application thereof.
Background
In recent years, solid super acidic catalysts have been receiving much attention due to their high catalytic activity, excellent thermal stability, strong acidity, reusability and non-polluting properties, and they have been used as catalysts for various organic reactions such as isomerization, alkylation, catalytic reforming of alkanes, cracking, esterification and transesterification reactions, and especially their use for heterogeneous catalytic transesterification reactions has become a hot point of research, and as heterogeneous catalysts, they have advantages of high activity and selectivity to target products, easy separation from the reaction medium, low corrosivity and good recyclability.
The current research on solid super acidic catalysts focuses on TiO which has been shown to have better performance than other metal oxides 2 /SO 4 2- Solid super acidic catalyst. Especially for pure TiO used for transesterification 2 Many studies have been made on modified solid superacid catalysts, these being pure TiO 2 The modified super acidic catalyst has shown excellent catalytic activity. Literature (heterogenous and effective transformation of Jatropha curcas L. Seed oil to product biolesel analyzed by nano-sized SO) 4 2- /TiO 2 Royal Society Open Science,2018,5 (11), 181331; biodiesel production by the transestification of conjugated oil by solid acid catalysts, front. Chem. Eng. China,2007,1 (1), 11-15) discloses the use of pure TiO by 2 Prepared TiO 2 /SO 4 2- Cottonseed catalyzed by solid super acidic catalystThe yield of the biodiesel oil reaches 85.3 percent and 90 percent respectively through the ester exchange reaction of the oil and the jatropha curcas oil. Though by pure TiO 2 Prepared TiO 2 /SO 4 2- Solid superacid catalysts have numerous advantages, but produce TiO 2 /SO 4 2- Pure TiO of solid super acidic catalyst 2 Mainly by using expensive chemical agents such as titanium tetrachloride, tetrabutyl titanate and titanium isopropoxide, and thus its price is expensive, resulting in TiO 2 /SO 4 2- The production cost of the solid superacid catalyst is high, and TiO is 2 /SO 4 2- The activity of the solid super acidic catalyst for catalyzing the ester exchange reaction needs to be further improved.
Disclosure of Invention
The invention aims at the problems in the prior art, and provides a method for utilizing TiO recovered from waste SCR in a first aspect 2 Synthesis of TiO 2 /SO 4 2- Method for solid super acidic catalyst, said method reducing TiO 2 /SO 4 2- The cost of production of the solid super acidic catalyst. In a second aspect, there is provided a TiO prepared by the above method having high surface area and macroporosity 2 /SO 4 2- A solid super acidic catalyst. In a third aspect, there is provided TiO prepared by the above method 2 /SO 4 2- Use of solid super acidic catalyst in ester exchange reaction, said TiO 2 /SO 4 2- The solid super acidic catalyst has the advantages of better catalytic activity, more stable performance and the like.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
firstly, a preparation method of the solid super acidic catalyst is provided, which comprises the following steps:
(1) Dissolving the waste SCR catalyst in an alkali solution, and adding Na into the solution 3 PO 4 ·12H 2 O, leaching, filtering and washing to obtain filter residue, soaking the filter residue in sulfuric acid, washing and drying the soaked filter residue to obtain TiO 2 (ii) a The waste SCR catalyst is specifically subjected to physical cleaning, crushing and calciningThe spent SCR catalyst of (a);
(2) TiO obtained in the step (1) 2 Soaking in sulfuric acid, stirring, filtering to obtain suspension, washing the suspension with deionized water, drying and calcining to obtain the solid super acidic catalyst.
Further, the waste SCR catalyst, the alkali solution and Na in the step (1) 3 PO 4 ·12H 2 The dosage ratio of O is 2-4g:20-40mL:0.4-0.5g.
Further, the TiO in the step (2) 2 The dosage ratio of the sulfuric acid is 0.5-1.5g:10-20mL.
Further, the concentration of the sulfuric acid in the step (2) is 0.4-0.7M.
Further, the alkali solution in the step (1) is a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 3-7M.
Further, the leaching temperature in the step (1) is 90-110 ℃, preferably 100 ℃, the leaching time is 2.5-3.5h, preferably 3h, and the drying temperature is room temperature.
Further, the stirring time in the step (2) is 3.5-4.5h, preferably 4h, the drying temperature is 90-110 ℃, preferably 100 ℃, and the drying time is 7.5-8.5h, preferably 8h.
Further, the calcining temperature in the step (2) is 450-550 ℃, preferably 500 ℃, and the calcining time is 2.5-3.5h, preferably 3h.
Secondly, the solid super acidic catalyst obtained by the preparation method is provided.
Finally, the solid super acidic catalyst obtained by the preparation method or the application of the solid super acidic catalyst in catalyzing ester exchange reaction is provided.
In some embodiments, the transesterification reaction is a reaction of ethyl acetate and n-butanol catalyzed by a solid super acidic catalyst.
The transesterification reaction of ethyl acetate and n-butanol comprises the following steps: in a reactor, ethyl acetate, n-butanol and the TiO prepared above are added 2 /SO 4 2- Solid super acidic catalyst, heating under stirring for reaction, and centrifugal separation.
Further, the dosage ratio of the ethyl acetate, the n-butanol and the solid super acidic catalyst is 0.9-1.1mol:1.0-1.2mol:1-4g, the reaction temperature is 15-120 ℃, and the reaction time is 15-180min.
Preferably, the using ratio of the ethyl acetate to the n-butanol to the solid super acidic catalyst is 1mol:1mol:2-4g, the reaction temperature is 90-120 ℃, preferably 100 ℃, and the reaction time is 120-180min, preferably 180min.
In some embodiments, the method for preparing the solid super acidic catalyst comprises the following steps:
(1) Dissolving the waste SCR catalyst after physical cleaning, crushing and calcining in alkali solution, and then adding Na into the solution 3 PO 4 ·12H 2 O, filtering, washing the obtained filter residue, soaking the washed filter residue in sulfuric acid, continuously stirring for a certain time, washing the obtained filter residue, and drying to obtain the recovered TiO 2 ；
(2) Recovering TiO from the step (1) 2 Soaking in sulfuric acid, stirring for a certain time, filtering the obtained suspension, washing with deionized water, and removing TiO 2 Drying the mixture with sulfuric acid at a certain temperature, and drying the dried TiO 2 Calcining the mixture of the sulfuric acid and the mixture at high temperature to obtain TiO 2 /SO 4 2- A solid super acidic catalyst.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method has the advantages of low raw material cost, simple preparation process and mild conditions, and is favorable for large-scale production and application; by recovering TiO 2 The recycling of titanium resources is promoted, the pollution of the waste SCR catalyst to the environment is reduced, and the method is beneficial to environmental protection;
(2) The solid super acidic catalyst prepared by the invention has high surface area and macroporosity, effectively increases the total acid strength, has better modification effect, higher catalytic activity and more stable performance, is particularly suitable for serving as a catalyst of ester exchange reaction, for example, serving as a catalyst of ester exchange reaction of ethyl acetate and n-butyl alcohol, and can reach the conversion rate of the n-butyl alcohol serving as a reaction raw material up to 92 percent.
Drawings
FIG. 1 is (R) -recovered TiO 2 And TiO 2 2 /SO 4 2- X-ray diffraction pattern of the sample.
FIG. 2 is a schematic diagram: (a) N is a radical of hydrogen 2 Adsorption-desorption isotherms, (b) recovered TiO 2 And TiO 2 /SO 4 2- Pore size distribution curve of the catalyst.
FIG. 3 shows the recovered TiO 2 And TiO 2 /SO 4 2- FTIR spectrum of the sample.
FIG. 4 shows the recovered TiO 2 And TiO 2 2 /SO 4 2- NH of solid superacid sample 3 -TPD spectra.
Detailed Description
It should be noted that the raw materials used in the present invention are all common commercial products, and the sources thereof are not particularly limited.
Example 1
TiO 2 /SO 4 2- Preparation of solid super acidic catalyst
3g of the physically washed, pulverized and calcined spent SCR catalyst was dissolved in 30ml of a 5M NaOH solution under continuous stirring, and 0.465g of Na was added to the above solution 3 PO 4 ·12H 2 And O. After leaching at 100 ℃ for 3 hours, the mixture is filtered, the filter residue is then washed thoroughly and the washed filter residue is soaked in 30ml of a 5.5% strength by mass sulphuric acid solution for 2 hours with continuous stirring. Washing the filter residue obtained after sulfuric acid soaking with deionized water, and recovering TiO obtained after washing 2 Drying at room temperature.
1g of the above-recovered TiO 2 The resulting solution was immersed in 15ml of 0.5M sulfuric acid and stirred for 4 hours. The resulting suspension was filtered and then washed with deionized water. Then adding TiO 2 And sulfuric acid at 100 ℃ for 8 hours, and then at 500 ℃ calcinationFor 3 hours to obtain TiO 2 /SO 4 2- Solid super acidic catalyst.
For the above prepared TiO 2 /SO 4 2- The structure of the solid super acidic catalyst is characterized:
(1) X-ray diffraction: the crystallinity of the sample was measured with an X-ray diffractometer (XRD) (D/MAX-RB, rigaku, japan diffractometer) and the scanning rate of Cu-Ka rays (. Lamda. =0.15406 nm) was 0.2 °/min in the 2 θ range of 5 ° to 80 °. The crystal size is calculated from the full width at half maximum of anatase (101) based on the Debye-Scherrer equation
Where K is the particle shape factor, λ is the wavelength of the CuK α radiation, β is the physical broadening of the (101) diffraction peak, and θ is the angle of incidence of the X-rays.
(2) Surface area measurement: nitrogen physical adsorption (N-adsorption) measurements specific surface areas, pore size distributions and pore volumes of samples were calculated by an automated surface area and porosity measurement system (ASAP 2460, micro-meters, USA) at a liquid nitrogen temperature of-196 ℃ using Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halenda (BJH) methods.
(3) FT-IR absorption: FT-IR (Fourier transform Infrared) absorption spectra were obtained using a Shimadzu IR Affinity-1 spectrometer (Japan) at 400-4000cm -1 Using KBr powder at 2cm -1 Resolution of 32 scans.
(4) Measurement of surface acidity: temperature programmed desorption (NH) of ammonia 3 TPD) was performed by AutoChem1 II 2920 with a thermal conductivity detector for continuous monitoring of desorbed ammonia. A sample of solid acid catalyst (0.100 g) was pretreated in a stream of ultrapure He (50 ml/min) at 550 ℃ for 1 hour and saturated with ammonia gas at 50 ℃ for 30 minutes. After purging with He gas (50 ml/ml) at 50 ℃ for 1 hour to remove physically absorbed ammonia, the sample was heated from 50 ℃ to 550 ℃ at a heating rate of 10 ℃/min.
FIGS. 1, 2 (a), 2 (b), 3 and 4 show the recovered TiO, respectively 2 And TiO 2 /SO 4 2- X-ray diffraction pattern, N, of a sample 2 Adsorption-desorption isothermsLine, pore size distribution, FTIR spectrum, NH 3 -TPD spectra. Wherein XRD results (calculation of average particle size of crystal plane (101) perpendicular to anatase phase of tetragonal titanium dioxide from XRD pattern using Debye-Scherrer method, results are 10.26nm and 10.30nm, respectively) showed that TiO 2 The crystal structure is not damaged after the recovery process and the sulfuric acid treatment; recycled TiO 2 Has a large surface area (79.23 m) 2 /g)，TiO 2 /SO 4 2- The BET and BJH results of the solid super acidic catalyst respectively show that the solid super acidic catalyst has higher surface area (41.83 m) 2 G) and greater porosity (0.301 cm) 3 Per gram), high specific surface area and large porosity are key factors for improving catalytic activity; 1148.56 and 1045.96cm -1 FT-IR results of band absorption indicate SO 4 2- Radical with TiO 2 The coordination is bidentate and has the following structure:
NH 3 the temperature of desorption was 400-500 ℃, confirming the formation of superacid sites. The structural characteristics of the catalyst promote the improvement of the catalytic activity of the catalyst.
Example 2
TiO 2 /SO 4 2- Preparation of solid super acidic catalyst
2g of the physically washed, pulverized and calcined used SCR catalyst was dissolved in 20ml of 7MNaOH solution with continuous stirring, and 0.400g of Na was added to the solution 3 PO 4 ·12H 2 And O. After leaching at 90 ℃ for 3.5 hours, the mixture is filtered, the filter residue is then washed thoroughly and the washed filter residue is soaked for 2 hours in 30ml of a 5.5% strength by mass sulphuric acid solution with continuous stirring. Washing the filter residue obtained after sulfuric acid soaking with deionized water, and recovering TiO obtained after washing 2 Drying at room temperature.
0.5g of the above-recovered TiO was added 2 The resulting solution was immersed in 1 ml of 0.7M sulfuric acid and stirred for 3.5 hours. The resulting suspension was filtered and,and then washed with deionized water. Then adding TiO 2 And sulfuric acid at 100 ℃ for 8 hours, and then at 500 ℃ for 3 hours to obtain TiO 2 /SO 4 2- Solid super acidic catalyst.
Example 3
TiO 2 /SO 4 2- Preparation of solid super acidic catalyst
4g of the physically washed and pulverized calcined waste SCR catalyst was dissolved in 40ml of a 3M NaOH solution under continuous stirring, and 0.500g of Na was added to the solution 3 PO 4 ·12H 2 And O. After leaching at 110 ℃ for 2.5 hours, the mixture is filtered, the filter residue is then washed thoroughly and the washed filter residue is soaked for 2 hours in 30ml of a 5.5% strength by mass sulphuric acid solution with continuous stirring. Washing filter residue obtained after being soaked in sulfuric acid with deionized water, and recovering TiO obtained after washing 2 Drying at room temperature.
1.5g of the above-recovered TiO was added 2 The resulting mixture was immersed in 20ml of 0.4M sulfuric acid and stirred for 4.5 hours. The resulting suspension was filtered and then washed with deionized water. Then adding TiO 2 And sulfuric acid at 100 ℃ for 8 hours, and then at 500 ℃ for 3 hours to obtain TiO 2 /SO 4 2- A solid super acidic catalyst.
Example 4
TiO 2 /SO 4 2- Preparation of solid super acidic catalyst
1.6g of the physically cleaned and crushed calcined spent SCR catalyst was dissolved in 45ml of a 5M NaOH solution with continuous stirring, and 0.550g of Na was added to the solution 3 PO 4 ·12H 2 And O. After leaching at 100 ℃ for 3 hours, the mixture is filtered, the filter residue is then washed thoroughly and the washed filter residue is soaked in 30ml of a 5.5% strength by mass sulphuric acid solution for 2 hours with continuous stirring. Washing filter residue obtained after being soaked in sulfuric acid with deionized water, and recovering TiO obtained after washing 2 Drying at room temperature.
1g of the above-recovered TiO 2 The resulting solution was immersed in 15ml of 0.5M sulfuric acid and stirred for 4 hours. The resulting suspension was filtered and then washed with deionized water. Then adding TiO 2 And sulfuric acid at 100 ℃ for 8 hours, and then at 500 ℃ for 3 hours to obtain TiO 2 /SO 4 2- Solid super acidic catalyst.
Example 5
TiO 2 /SO 4 2- Preparation of solid super acidic catalyst
3g of the physically washed, pulverized and calcined spent SCR catalyst was dissolved in 30ml of a 5M NaOH solution under continuous stirring, and 0.465g of Na was added to the above solution 3 PO 4 ·12H 2 And O. After leaching at 100 ℃ for 3 hours, the mixture is filtered, the filter residue is then washed thoroughly and the washed filter residue is soaked in 30ml of a 5.5% strength by mass sulphuric acid solution for 2 hours with continuous stirring. Washing the filter residue obtained after sulfuric acid soaking with deionized water, and recovering TiO obtained after washing 2 Drying at room temperature.
0.4g of the above-recovered TiO was added 2 The mixture was immersed in 22ml of 0.5M sulfuric acid and stirred for 4 hours. The resulting suspension was filtered and then washed with deionized water. Then adding TiO 2 And sulfuric acid at 100 ℃ for 8 hours, and then at 500 ℃ for 3 hours to obtain TiO 2 /SO 4 2- Solid super acidic catalyst.
Examples of the experiments
TiO obtained in examples 1 to 5 2 /SO 4 2- The solid super acidic catalyst is used for catalyzing the ester exchange reaction of ethyl acetate and n-butyl alcohol.
In a 100ml round bottom flask equipped with a reflux condenser were added 10ml of ethyl acetate, 9.3ml of n-butanol (molar ratio 1 2 /SO 4 2- Solid superacid catalyst, the reaction mixture is reacted for 3 hours at 100 ℃ with stirring (400 rpm). The sample was separated from the reaction mixture using a centrifuge, and the conversion of n-butanol is shown in table 1.
TABLE 1
| Catalyst and process for producing the same | Conversion rate/% |
| Example 1 | 92 |
| Example 2 | 91 |
| Example 3 | 91.5 |
| Example 4 | 85 |
| Example 5 | 86 |
The conversion of n-butanol was calculated based on GC analysis using the following equation:
(references: interpretation of organic acids over zeolites H β, HY and HZSM5, S.R.Kirumakki et al/Applied Catalysis A: general,2006 (299): 185-192).
The product analysis method comprises the following steps: the samples were analyzed by gas chromatography (GC-2014-SHIMADZU) equipped with a Flame Ionization Detector (FID) and a capillary column RTX-5 (length 30.0m, inner diameter 0.25mm, film thickness 0.25 mm). The temperature of the detector was 240 ℃ and the temperature of the injector was 2 ℃00 ℃, the programmed heating rate of the oven is 10 ℃/min, and the temperature range is 40-200 ℃. N is a radical of 2 The gas flow rate of (2) was 17.5ml/min, and the sample amount was 0.2. Mu.L.
Finally, it should be noted that the above-mentioned contents are only used for illustrating the technical solutions of the present invention, and do not limit the protection scope of the present invention, and those skilled in the art can make simple modifications or equivalent substitutions on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The preparation method of the solid super acidic catalyst is characterized by comprising the following steps:
(1) Dissolving the waste SCR catalyst in an alkali solution, and adding Na into the solution 3 PO 4 ·12H 2 O, leaching, filtering and washing to obtain filter residue, soaking the filter residue in sulfuric acid, washing and drying the soaked filter residue to obtain TiO 2 ；
(2) TiO obtained in the step (1) 2 Soaking in sulfuric acid, stirring, filtering to obtain suspension, washing the suspension with deionized water, drying and calcining to obtain the solid super acidic catalyst.
2. The method according to claim 1, wherein the spent SCR catalyst, the alkali solution, na in step (1) 3 PO 4 ·12H 2 The dosage ratio of O is 2-4g:20-40mL:0.4-0.5g.
3. The method according to claim 1, wherein the TiO in the step (2) 2 The dosage ratio of the sulfuric acid is 0.5-1.5g:10-20mL.
4. The method according to claim 1, wherein the concentration of the sulfuric acid in the step (2) is 0.4 to 0.7M.
5. The method according to claim 1, wherein the alkali solution in the step (1) is a sodium hydroxide solution having a concentration of 3 to 7M.
6. The method according to claim 1, wherein the leaching temperature in step (1) is 90-110 ℃ and the leaching time is 2.5-3.5h.
7. The method of claim 1, wherein the stirring time in the step (2) is 3.5 to 4.5 hours, the drying temperature is 90 to 110 ℃, and the drying time is 7.5 to 8.5 hours.
8. The preparation method of claim 1, wherein the calcination in step (2) is carried out at a temperature of 450-550 ℃ for a time of 2.5-3.5 hours.
9. A solid super acidic catalyst obtained by the process of any one of claims 1 to 8.
10. Use of the solid super acidic catalyst obtained by the process of any one of claims 1 to 8 or the solid super acidic catalyst of claim 9 for the catalysis of transesterification.
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| 刘康强;旷成秀;张新华;: "固体超强酸S_2O_8~(2-)/TiO_2的溶胶-凝胶法制备与表征", 工业催化, no. 06 * |
| 崔爱莉;欧伦宇;王烨;谢天择;殷方锐;虢中浩;杨波;谈可意;: "废弃V-W/Ti脱硝催化剂碱体系络合除As工艺方法", 中国科技论文, no. 06 * |
| 戚春萍等: ""燃煤电厂废旧SCR脱硝催化剂中TiO2载体的回收与再利用"", 《化工学报》, vol. 68, no. 11, pages 1 * |
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