CN115445639B - Solid super acidic catalyst and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a solid super acid catalyst, a preparation method and application thereof, and belongs 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 Mixing with sulfuric acid under stirring, filtering, washing, drying, and calcining at high temperature. The preparation method is simple to operate, mild in condition and beneficial to large-scale production and application. And 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 environment is protected. The prepared solid super acidic catalyst has high surface area and large porosity, higher total acid strength, better modification effect, higher catalytic activity and more stable performance, is particularly suitable for being used as a catalyst for transesterification, for example, as a catalyst for transesterification of ethyl acetate and n-butanol, and has the conversion rate of the n-butanol as a reaction raw material as high as 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 superacid catalysts have been receiving more attention because of 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, and in particular, their use for heterogeneous catalytic transesterification has become a hot spot of research, and they have advantages of high activity and selectivity for target products, easy separation from reaction media, low corrosiveness, and good reusability as heterogeneous catalysts.
Current research on solid superacid catalysts focuses on TiO that has been shown to have better performance than other metal oxides 2 /SO 4 2- Solid superacid catalyst. In particular for pure TiO for transesterification reactions 2 Many studies have been made on modified solid superacid catalysts, these pure TiO 2 Modified superacid catalysts have shown excellent catalytic activity. Literature (Heterogeneous and efficient transesterification of Jatropha curcas L.seed oil to produce biodiesel catalysed by nano-sized SO 4 2- /TiO 2 Royal Society Open Science,2018,5 (11), 181331; biodiesel production by the transesterification of cottonseed oil by solid acid catalysts, front. Chem. Eng. China,2007,1 (1), 11-15) discloses the use of pure TiO 2 Prepared TiO 2 /SO 4 2- The solid superacid catalyst catalyzes the transesterification reaction of the cotton seed oil and the jatropha oil, and the biodiesel yield reaches 85.3% and 90% respectively. Although by pure TiO 2 Prepared TiO 2 /SO 4 2- Solid superacid catalysts have many advantages, but produce TiO 2 /SO 4 2- Pure TiO of solid super acid catalyst 2 Is mainly prepared by using expensive chemical reagents such as titanium tetrachloride, tetrabutyl titanate and titanium isopropoxide, and the like, so the cost is relatively high to lead to TiO 2 /SO 4 2- The solid super acid catalyst has high production cost and TiO 2 /SO 4 2- The activity of the solid superacid catalyst for catalyzing the transesterification reaction needs to be further improved.
Disclosure of Invention
The present invention addresses the problems of the prior art by providing, in a first aspect, a method for utilizing TiO recovered from spent SCR 2 Synthesis of TiO 2 /SO 4 2- Method for preparing solid superacid catalyst, said method reducing TiO 2 /SO 4 2- Cost of production of solid superacid catalyst. In a second aspect, there is provided TiO having a high surface area and a large porosity prepared by the method described above 2 /SO 4 2- Solid superacid catalysts. In a third aspect, there is provided TiO as prepared by the method 2 /SO 4 2- Use of solid superacid catalysts in transesterification reactions, the TiO 2 /SO 4 2- The solid super acid catalyst has the advantages of better catalytic activity, more stable performance and the like.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
firstly, a preparation method of a solid super acid catalyst is provided, which comprises the following steps:
(1) Dissolving waste SCR catalyst in alkali solution, 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 The method comprises the steps of carrying out a first treatment on the surface of the The waste SCR catalyst is specifically a waste SCR catalyst subjected to physical cleaning, crushing and calcining;
(2) The TiO obtained in the step (1) is treated 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, 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.
Further, the TiO in step (2) 2 The dosage ratio of sulfuric acid is 0.5-1.5g:10-20mL.
Further, the concentration of sulfuric acid in the step (2) is 0.4-0.7M.
Further, the alkali solution in the step (1) is sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 3-7M.
Further, the leaching in step (1) is carried out at a temperature of 90-110 ℃, preferably 100 ℃, for a time of 2.5-3.5 hours, preferably 3 hours, and the drying is carried out at room temperature.
Further, the stirring time in the step (2) is 3.5-4.5 hours, preferably 4 hours, the drying temperature is 90-110 ℃, preferably 100 ℃, and the drying time is 7.5-8.5 hours, preferably 8 hours.
Further, the calcination temperature in step (2) is 450-550 ℃, preferably 500 ℃, and the calcination time is 2.5-3.5h, preferably 3h.
Secondly, a solid super acidic catalyst obtained by the preparation method is provided.
Finally, a solid super acid catalyst obtained by the preparation method or application of the solid super acid catalyst in catalyzing transesterification is provided.
In some embodiments, the transesterification reaction is a reaction of ethyl acetate and n-butanol under the catalysis of a solid super acid catalyst.
The transesterification reaction of ethyl acetate and n-butanol comprises the following steps: adding ethyl acetate, n-butanol and the TiO prepared by the method into a reactor 2 /SO 4 2- The solid super acidic catalyst is heated under stirring to fully react, and the product is centrifugally separated.
Further, the dosage ratio of the ethyl acetate to the n-butanol to the solid super acid catalyst is 0.9-1.1mol:1.0 to 1.2mol:1-4g, wherein the reaction temperature is 15-120 ℃, and the reaction time is 15-180min.
Preferably, the dosage ratio of the ethyl acetate to the n-butanol to the solid super acid catalyst is 1mol:1mol:2-4g, wherein 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 superacid catalyst comprises the steps of:
(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, leaching, filtering, washing to obtain 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 recovered TiO 2 ；
(2) Recovering the TiO obtained in the step (1) 2 Immersing in sulfuric acid, stirring for a certain time, filtering to obtain suspension, washing with deionized water, and adding TiO 2 Drying the mixture with sulfuric acid at a certain temperature, and drying the dried TiO 2 Calcining the mixture with sulfuric acid at high temperature to obtain TiO 2 /SO 4 2- Solid superacid catalysts.
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 beneficial to large-scale production and application; by recovering TiO 2 The recycling of titanium resources is promoted, the pollution of waste SCR catalysts to the environment is reduced, and the environment is protected;
(2) The solid super acidic catalyst prepared by the method has high surface area and large porosity, simultaneously effectively increases the total acid strength, has better modification effect, higher catalytic activity and more stable performance, is particularly suitable for being used as a catalyst for transesterification, for example, as a catalyst for transesterification of ethyl acetate and n-butanol, and can reach a conversion rate of the n-butanol serving as a reaction raw material of 92 percent.
Drawings
FIG. 1 (R) -recovered TiO 2 And TiO 2 /SO 4 2- X-ray diffraction pattern of the sample.
Fig. 2: (a) N (N) 2 Adsorption-desorption isotherms, (b) recovered TiO 2 And TiO 2 /SO 4 2- Catalyst poresA radius distribution curve.
FIG. 3 is a diagram of recovered TiO 2 And TiO 2 /SO 4 2- FTIR spectra of the samples.
FIG. 4 is a diagram of recovered TiO 2 And TiO 2 /SO 4 2- NH of solid super acid sample 3 -TPD spectrum.
Detailed Description
It is to 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 superacid catalyst
3g of the waste SCR catalyst after physical washing and pulverizing calcination was dissolved in 30ml of 5M NaOH solution under continuous stirring, and 0.465g of Na was added to the above solution 3 PO 4 ·12H 2 O. After leaching at 100 ℃ for 3 hours, the mixture was filtered, and the filter residue was then washed thoroughly, and the washed filter residue was immersed in 30ml of a sulfuric acid solution with a mass percentage concentration of 5.5% for 2 hours under continuous stirring. Washing the filter residue obtained after being soaked in sulfuric acid with deionized water, and recovering TiO (titanium dioxide) obtained after washing 2 Drying at room temperature.
1g of the recovered TiO was treated with 2 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 TiO is added 2 The mixture with sulfuric acid was dried at 100℃for 8 hours and then calcined at 500℃for 3 hours to obtain TiO 2 /SO 4 2- Solid superacid catalysts.
For the TiO prepared above 2 /SO 4 2- The structure of the solid super acid catalyst is characterized:
(1) X-ray diffraction: the crystallinity of the sample was measured by X-ray diffraction (XRD) (D/MAX-RB, rigaku, japan diffractometer), and the scanning rate of Cu-K.alpha.rays (lambda= 0.15406 nm) was 0.2 DEG/min in the 2. Theta. Range of 5 DEG to 80 deg. The crystal size is calculated from the full width at half maximum of anatase (101) based on the Debye-Scherrer equation, which is given byWhere K is the particle form factor, λ is the wavelength of the CuK alpha 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 physisorption (N-adsorption) measurements were performed by an automated surface area and porosity measurement system (ASAP 2460, micro-Metrics, USA) at liquid nitrogen temperatures of-196℃and specific surface area, pore size distribution and pore volume of the samples were calculated using Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halenda (BJH) methods.
(3) FT-IR absorption: FT-IR (Fourier transform infrared) absorption spectrum was measured at 400-4000cm by Shimadzu IR Affinity-1 spectrometer (Japan) -1 Using KBr powder at 2cm -1 Obtained from 32 scans of resolution.
(4) Measurement of surface acidity: programmed temperature desorption (NH) 3 TPD) is carried out by an AutoChem1 II 2920 with a thermal conductivity detector for continuous monitoring of the desorbed ammonia. A sample of the solid acid catalyst (0.100 g) was pretreated in a stream of ultra-pure 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℃per minute.
FIGS. 1, 2 (a), 2 (b), 3, 4 are respectively recovered TiO 2 And TiO 2 /SO 4 2- X-ray diffraction pattern, N, of a sample 2 Adsorption-desorption isotherms, pore size distribution curves, FTIR spectra, NH 3 -TPD spectrum. Wherein XRD results (average particle size of crystal face (101) of each sample perpendicular to tetragonal titania anatase phase was calculated from XRD pattern using Debye-Scherrer method, results of 10.26nm and 10.30nm, respectively) showed TiO 2 After the recovery process and sulfuric acid treatment, the crystal structure is not destroyed; recovered TiO 2 Has a large surface area (79.23 m 2 /g)，TiO 2 /SO 4 2- BET and BJH results of the solid super acid catalyst showed that it had a higher surface area (41.83 m 2 /g) and greater porosity(0.301cm 3 High specific surface area and large porosity are key factors for improving catalytic activity; 1148.56 and 1045.96cm -1 FT-IR results at band absorption indicate SO 4 2- Radicals and TiO 2 The coordination is bidentate and has the following structure:
NH 3 the desorption temperature was 400-500 ℃, confirming the formation of superacid sites. The structural characteristics of the catalyst promote the improvement of the catalytic activity.
Example 2
TiO 2 /SO 4 2- Preparation of solid superacid catalyst
2g of the waste SCR catalyst after physical washing and pulverizing calcination was dissolved in 20ml of 7M NaOH solution under continuous stirring, and 0.400g of Na was added to the above solution 3 PO 4 ·12H 2 O. After leaching for 3.5 hours at 90 ℃, the mixture was filtered, and the filter residue was then washed thoroughly, and the washed filter residue was immersed in 30ml of a sulfuric acid solution having a mass percentage concentration of 5.5% for 2 hours under continuous stirring. Washing the filter residue obtained after being soaked in sulfuric acid with deionized water, and recovering TiO (titanium dioxide) obtained after washing 2 Drying at room temperature.
0.5g of the recovered TiO was reacted with 2 Immersed in 10ml of 0.7M sulfuric acid and stirred for 3.5 hours. The resulting suspension was filtered and then washed with deionized water. Then TiO is added 2 The mixture with sulfuric acid was dried at 100℃for 8 hours and then calcined at 500℃for 3 hours to obtain TiO 2 /SO 4 2- Solid superacid catalysts.
Example 3
TiO 2 /SO 4 2- Preparation of solid superacid catalyst
4g of the waste SCR catalyst after physical washing and pulverizing calcination was dissolved in 40ml of 3M NaOH solution under continuous stirring, and 0.500g of Na was added to the above solution 3 PO 4 ·12H 2 O. After leaching for 2.5 hours at 110 ℃, the mixture was filtered, and the filter residue was then washed thoroughly, and the washed filter residue was immersed in 30ml of a sulfuric acid solution having a mass percentage concentration of 5.5% for 2 hours under continuous stirring. Washing the filter residue obtained after being soaked in sulfuric acid with deionized water, and recovering TiO (titanium dioxide) obtained after washing 2 Drying at room temperature.
1.5g of the recovered TiO was reacted with 2 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 TiO is added 2 The mixture with sulfuric acid was dried at 100℃for 8 hours and then calcined at 500℃for 3 hours to obtain TiO 2 /SO 4 2- Solid superacid catalysts.
Example 4
TiO 2 /SO 4 2- Preparation of solid superacid catalyst
1.6g of the waste SCR catalyst after physical washing and pulverizing calcination was dissolved in 45ml of 5M NaOH solution under continuous stirring, and 0.550g of Na was added to the above solution 3 PO 4 ·12H 2 O. After leaching at 100 ℃ for 3 hours, the mixture was filtered, and the filter residue was then washed thoroughly, and the washed filter residue was immersed in 30ml of a sulfuric acid solution with a mass percentage concentration of 5.5% for 2 hours under continuous stirring. Washing the filter residue obtained after being soaked in sulfuric acid with deionized water, and recovering TiO (titanium dioxide) obtained after washing 2 Drying at room temperature.
1g of the recovered TiO was treated with 2 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 TiO is added 2 The mixture with sulfuric acid was dried at 100℃for 8 hours and then calcined at 500℃for 3 hours to obtain TiO 2 /SO 4 2- Solid superacid catalysts.
Example 5
TiO 2 /SO 4 2- Preparation of solid superacid catalyst
3g of the waste SCR catalyst after physical washing and crushing calcination was dissolved in 30ml of 5M NaOH under continuous stirringTo the solution, 0.465g Na was added 3 PO 4 ·12H 2 O. After leaching at 100 ℃ for 3 hours, the mixture was filtered, and the filter residue was then washed thoroughly, and the washed filter residue was immersed in 30ml of a sulfuric acid solution with a mass percentage concentration of 5.5% for 2 hours under continuous stirring. Washing the filter residue obtained after being soaked in sulfuric acid with deionized water, and recovering TiO (titanium dioxide) obtained after washing 2 Drying at room temperature.
0.4g of the recovered TiO was reacted with 2 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 TiO is added 2 The mixture with sulfuric acid was dried at 100℃for 8 hours and then calcined at 500℃for 3 hours to obtain TiO 2 /SO 4 2- Solid superacid catalysts.
Experimental example
TiO obtained in examples 1 to 5 2 /SO 4 2- The solid superacid catalyst is used for catalyzing transesterification of ethyl acetate and n-butanol.
Into a 100ml round-bottomed flask equipped with a reflux condenser were charged 10ml of ethyl acetate, 9.3ml of n-butanol (molar ratio 1:1) and 0.4g of TiO prepared in example 1 above 2 /SO 4 2- The reaction mixture was reacted at 100℃for 3 hours with stirring (400 rpm) using a solid superacid catalyst. The samples were separated from the reaction mixture using a centrifuge and the conversion of n-butanol is shown in table 1.
TABLE 1
| Catalyst | Conversion/% |
| 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: (ref. AEsterification of alcohols withacetic acid over zeolites H. Beta., HY and HZSM5, S.R. Kirumakki et al./Applied Catalysis A: general,2006 (299): 185-192).
The product analysis method comprises the following steps: samples were analyzed by gas chromatography (GC-2014-SHIMADZU) equipped with a Flame Ionization Detector (FID) and a capillary column RTX-5 (30.0 m long, 0.25mm inner diameter, 0.25mm film thickness). The temperature of the detector is 240 ℃, the temperature of the injector is 200 ℃, the temperature programming rate of the oven is 10 ℃/min, and the temperature range is 40-200 ℃. N (N) 2 The gas flow rate of (C) was 17.5ml/min, and the sample amount was 0.2. Mu.L.
Finally, it should be noted that the above description is only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and that the simple modification and equivalent substitution of the technical solution of the present invention can be made by those skilled in the art without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. The preparation method of the solid super acidic catalyst is characterized by comprising the following steps:
(1) Dissolving waste SCR catalyst in alkali solution, 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) The TiO obtained in the step (1) is treated 2 Soaking in sulfuric acid, stirring, filtering to obtain suspension, washing the suspension with deionized water, drying, and calcining to obtain solid super acidic catalyst;
the waste SCR catalyst, alkali solution and Na in the step (1) 3 PO 4 ·12H 2 The dosage ratio of O is 3g:30mL:0.465g; the alkali solution is sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 3-7M.
2. The method according to claim 1, wherein the TiO in step (2) 2 The dosage ratio of sulfuric acid is 0.5-1.5g:10-20mL.
3. The process according to claim 1, wherein the concentration of sulfuric acid in step (2) is 0.4 to 0.7M.
4. The process according to claim 1, wherein the temperature of the leaching in step (1) is 90-110 ℃ and the time of leaching is 2.5-3.5h.
5. The method according to 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.
6. The method according to claim 1, wherein the calcination temperature in step (2) is 450 to 550 ℃ and the calcination time is 2.5 to 3.5 hours.
7. A solid superacid catalyst obtainable by the process of any one of claims 1 to 6.
8. Use of the solid super acid catalyst obtained by the preparation method according to any one of claims 1 to 6 or the solid super acid catalyst according to claim 7 for catalyzing transesterification.
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