CN114014331B - Method for preparing SAPO-34 molecular sieve by taking saccharomycete DNA as template, molecular sieve and application thereof - Google Patents
Method for preparing SAPO-34 molecular sieve by taking saccharomycete DNA as template, molecular sieve and application thereof Download PDFInfo
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Abstract
The invention provides a method for preparing a SAPO-34 molecular sieve by taking saccharomycete DNA as a template, the molecular sieve and application thereof. The preparation method of the SAPO-34 molecular sieve comprises the following steps: al is added with 2 O 3 Added to H 3 PO 4 Stirring the solution vigorously; siO is made of 2 Uniformly adding the mixture into the stirred TEA solution, adding deionized water containing saccharomycete DNA, and stirring vigorously; and adding the original gel obtained by uniformly mixing the two stirred raw material liquids into a reaction kettle for hydrothermal crystallization reaction. And then vacuum filtering, drying and calcining are carried out to remove the template agent, thus obtaining the SAPO-34 molecular sieve. The invention adopts cheap and environment-friendly biomass to replace a large amount of organic template used in the traditional process, thereby solving the problems of high cost and environmental pollution of the traditional process; the SAPO-34 molecular sieve prepared by the invention provides multistage pore channels through the microstructure of biomass, and increases the gas selectivity and adsorption capacity.
Description
Technical Field
The invention relates to a molecular sieve technology, in particular to a method for preparing an SAPO-34 molecular sieve by taking saccharomycete DNA as a template, the molecular sieve and application thereof.
Background
The main component of natural gas is CH 4 While CO in underground mined acid-rich natural gas and artificially fermented natural gas 2 The content is higher, so that the heat value of the natural gas is reduced and the transportation of the natural gas is influenced. In particular CO 2 As a greenhouse gas, excessive emissions cause climate warming and have become a concern for the global environment. Domestic and foreign scholars aim at CO in natural gas 2 Removal many studies of the separation method have been conducted. Conventional natural gas purification techniques, e.g. ammonia-alcohol processes and cryogenic/minThe distillation method and the like have the problems of high cost and serious secondary pollution. The molecular sieve is used as an adsorbent, can selectively adsorb gas and can be quickly desorbed in a short time. The separation and purification of gas mixtures by adsorption has become an important unit operation in the chemical and chemical industries. Molecular sieve adsorption technology has received great attention, especially in the separation of methane and carbon dioxide, due to its low energy consumption and low cost.
The SAPO-34 molecular sieve is a silicon aluminum phosphate molecular sieve with a typical topological structure, the pore diameter is 0.38nm, and the pore volume is 0.42cm 3 And/g, the space symmetry group is R3m, and the adsorbent is in a trigonal system, has good thermal stability and chemical stability, and has relatively high selectivity. In recent years, the synthesis of nano SAPO-34 molecular sieve particles has attracted particular attention from researchers, and has been widely applied to gas separation and methanol-to-olefin reaction due to the large specific surface area and special pore structure, and particularly has obviously improved application effect in gas and liquid separation.
The development of traditional adsorbents involves the use of organic solvents and environmental pollution can occur during the preparation process. The multi-layer, multi-dimensional and multi-scale natural hard template structure formed by long-term evolution in natural environment and some natural soft biomolecules with multi-layer and multi-dimensional structures can provide new ideas for the design and preparation of multi-level structure nanometer materials. The preparation of metal oxide by directly using chemical reagent as template often goes against the environmental protection and economy concepts, and the preparation of metal oxide with complex porous structure by using green and environment-friendly biomass and its derivative as template through simple preparation conditions meets the requirement of sustainable development. In addition, biomass in nature can synthesize various materials with special spatial structures, and the structural complexity is even more than the current physical or chemical method can achieve.
Disclosure of Invention
Aiming at the problems of high cost and environmental pollution caused by using a large amount of organic amine template agent in the traditional process, the invention provides a method for preparing the SAPO-34 molecular sieve by taking saccharomycete DNA as a template, wherein the method adopts cheap and environment-friendly biomass, namely saccharomycete DNA, to replace, thereby reducing the use of the organic template agent; and the microstructure of biomass is adopted to provide multistage pore channels for the molecular sieve, so that the gas selectivity and the adsorption capacity are increased.
In order to achieve the above purpose, the invention adopts the following technical scheme: a method for preparing a SAPO-34 molecular sieve by taking saccharomycete DNA as a template comprises the following steps:
step 1: rapidly weigh proper amount of Al 2 O 3 Gradually adding H diluted by deionized water 3 PO 4 The mass ratio of the solution to the solution is 1:2-1:3;
step 2: rapidly weigh an appropriate amount of SiO 2 Gradually adding the mixture into the stirred TEA solution, wherein the mass ratio of the TEA solution to the stirred TEA solution is 1:5-1:6; then vigorously stirring for 12-16 h;
step 3: rapidly weighing a proper amount of commercial SAPO-34 molecular sieve seed crystal and gradually adding SiO 2 In the mixed solution of TEA and the seed crystal, the seed crystal adding proportion is 0.0035-0.0039:1 (/ MS) i O 2 ) Uniformly stirring;
step 4: mixing the mixture obtained in step 3 (containing SiO) 2 TEA and seed crystal were added dropwise to the mixture of step 1 (containing Al) 2 O 3 And H 3 PO 4 ) Fully stirring for a plurality of hours;
step 5: activating pure strain of yeast at normal temperature, and inoculating into liquid culture medium (one of Saccharomyces cerevisiae, grape juice yeast or Schizosaccharomyces cerevisiae) for expansion culture;
step 6: crushing the yeast cell wall in the step 5 by using a snailase solution, wherein the concentration of the snailase solution is 20-30 mg.mL -1 The adding proportion is 0.1-0.15:1 (mass ratio); collecting the extracted DNA, placing into TE buffer solution, and storing in refrigerator at 4deg.C for use;
step 7: diluting the standby DNA into the residual deionized water, adding the residual DNA into the mixed solution in the step 4, and uniformly stirring for 24-48 h; the DNA adding proportion is 0.0025-0.005:1 (mass ratio) of the molecular sieve raw material liquid;
step 8: ammonia water is adopted to control the pH value of the original sol to be 8-10;
step 9: the gel obtained after stirring is added into a hydrothermal reaction kettle to be synthesized by adopting a two-step method, and is subjected to hydrothermal crystallization for 4-8 hours at 110 ℃ and then subjected to hydrothermal crystallization for 20-24 hours at 180-200 ℃;
step 10: the crystallization liquid taken out of the reaction kettle is subjected to vacuum suction filtration, and deionized water is continuously added for washing until the solution is neutral; taking out the crystal, and placing the crystal in a baking oven at 0-100 ℃ for drying for 10-12 h;
step 11: the sample was subjected to the following calcination procedure: the temperature of the sample is raised to 120-150 ℃ from 30 ℃ for 120min, kept for 200-240 min, then raised to 550-600 ℃ and kept for 360-400 min, and finally cooled to 30 ℃ for 30 min.
The invention also discloses a SAPO-34 molecular sieve prepared by the method.
Further, the particle size of the SAPO-34 molecular sieve is 1-3 mu m, the microstructure of the biomass provides multistage pore channels for the molecular sieve, the molecular sieve has good gas selectivity and adsorption capacity, and the problems of high cost, environmental pollution and the like caused by using a large amount of organic template agent in the traditional process are solved.
Another object of the present invention is also to disclose a SAPO-34 molecular sieve for CH in natural gas 4 /CO 2 Use in the separation field.
Aiming at the problems of higher cost and environmental pollution of the traditional organic amine template agent, the method for preparing the SAPO-34 molecular sieve by taking the saccharomycete DNA as the template reduces the use of the traditional organic template by doping biomass, and has the following advantages compared with the prior art:
1) According to the invention, through doping of biomass, the use of organic amine is reduced, so that the preparation cost of the SAPO-34 molecular sieve is greatly reduced.
2) According to the invention, the SAPO-34 molecular sieve has a multi-stage layered structure by adding the saccharomycete DNA, so that the adsorption capacity and selective separation performance of the SAPO-34 molecular sieve on gas are effectively improved.
3) According to the invention, through doping of biomass, long-term analysis is performed from the environmental protection perspective, so that the large-scale use of organic solvents in the traditional preparation method is reduced, and longer-term environmental economic benefits can be generated.
Drawings
FIG. 1 is an XRD spectrum of a SAPO-34 molecular sieve doped with a DNA multilevel structure and containing a SAPO-34 molecular sieve standard card, S is an XRD spectrum of a sample synthesized by deionized water, and S1, S2 and S3 are XRD spectra of samples synthesized by saccharomycete DNA suspensions with different contents.
Detailed Description
The invention is further illustrated by the following examples:
example 1
The embodiment discloses a method for preparing a SAPO-34 molecular sieve by taking saccharomycete DNA as a template, which specifically comprises the following steps:
activating pure strain of saccharomycete at normal temperature, inoculating the pure strain into potato glucose liquid culture medium for expanding culture, and extracting DNA from the collected bacterial thallus. First, 3mL of yeast is cultured and the temperature is 12000 r.min -1 Centrifuging for 5min, then taking precipitate (thallus), adding 300 mu L PBS buffer solution to resuspend the thallus, and repeating the centrifugation and resuspension processes for 1-2 times. Next, 20 mg/mL of the solution was added to the precipitate -1 Snailase solution 100. Mu.L, 350. Mu.L lysate, and 45℃for 4h. Adding equal volume of phenol-chloroform-isoamyl alcohol into the suspension, gently reversing and mixing uniformly, 12000 r.min -1 Centrifuging for 5min, collecting supernatant, adding equal volume of phenol-chloroform-isoamyl alcohol, and extracting again. Adding 2-3 times of absolute ethyl alcohol into the supernatant, gently mixing, standing at room temperature for 30min,12000 r.min -1 Centrifuging for 10min, washing precipitate (DNA) with 75% ethanol for 2 times, naturally drying, dissolving in 50 μl of sterile double distilled water, adding 3 μl of 10mg.mL -1 Is subjected to warm bath at 37 ℃ for 30min, is naturally cooled and is preserved, TE buffer is added after extraction is finished, and the obtained product is preserved in a refrigerator at 4 ℃ for standby.
3ml of H was treated with 5ml of deionized water 3 PO 4 (85%) diluted, 2.4g Al was added 2 O 3 Slowly add diluted H 3 PO 4 The solution is vigorously stirred for 4-6 hours. Thereafter, 4g of TEA and 0.8g of SiO were weighed 2 And SiO is combined with 2 Uniformly adding to the stirred TEA solution, and adding 30mg of fermentThe remaining deionized water (14.85 ml) of the parent bacteria DNA is vigorously stirred for 4-6 hours, then the two stirred raw material liquids are uniformly mixed, and the pH of the sample synthesis gel is controlled at 8 by adopting ammonia water.
And adding the gel obtained after stirring into a hydrothermal reaction kettle, performing hydrothermal crystallization for 4 hours at 110 ℃, and performing hydrothermal crystallization for 20 hours at 180 ℃. And then carrying out vacuum suction filtration on the crystallization liquid taken out of the reaction kettle, and continuously adding deionized water for washing until the solution is neutral. The crystals were taken out and dried in an oven at 80℃for 10h. Finally, the sample after crystallization is subjected to the following calcination procedure: the sample is heated from 30 ℃ to 120 ℃ for 120min, kept for 200min, and then heated to 550 ℃ and kept for 360min. Finally, the temperature is reduced to 30 ℃ after 30 min. The multi-stage SAPO-34 molecular sieve is prepared after calcination.
In FIG. 1, S1 is the XRD pattern of the present example for the preparation of a SAPO-34 molecular sieve containing 30mg of yeast DNA as a template. As shown, the high peak intensity and no baseline drift indicates that all samples were high in crystallinity and free of impurities, with corresponding characteristic peaks at 2θ=9.5 °, 13 °, 16.1 °, 17.8 ° and 20.7 °, and diffraction double peaks at 26 ° and 31 ° were peaks specific to SAPO-34, indicating that the synthesized samples were all SAPO-34 molecular sieves, indicating that the samples still maintained the complete CHA structure of the SAPO-34 molecular sieves, while the crystallinity of the samples was higher.
Example 2
The embodiment discloses a method for preparing a SAPO-34 molecular sieve by taking saccharomycete DNA as a template, which specifically comprises the following steps:
activating pure strain of saccharomycete at normal temperature, inoculating the pure strain into potato glucose liquid culture medium for expanding culture, and collecting bacterial thallus for DNA extraction. First, 4mL of yeast is cultured and the temperature is 12000 r.min -1 Centrifuging for 8min, then taking precipitate (thallus), adding 400 mu L PBS buffer solution to resuspend thallus, and repeating the centrifugation and resuspension processes for 1-2 times. Next, 25 mg/mL of the precipitate was added -1 Snailase solution, 400. Mu.L lysate, at 48℃for 5h. Adding equal volume of phenol-chloroform-isoamyl alcohol into the suspension, gently reversing and mixing uniformly, 12000 r.min -1 Centrifuging for 8min, collecting supernatant, adding equal volume of phenol-chloroform-isopentaneThe alcohol is extracted once more. Adding 2-3 times of absolute ethyl alcohol into the supernatant, gently mixing, standing at room temperature for 30min,12000 r.min -1 Centrifuging for 5min, washing precipitate (DNA) with 75% ethanol for 2 times, naturally drying, dissolving in 50 μl of sterile double distilled water, adding 4 μl of 10mg.mL -1 Is subjected to warm bath at 37 ℃ for 30min, is naturally cooled and is preserved, TE buffer is added after extraction is finished, and the obtained product is preserved in a refrigerator at 4 ℃ for standby.
3ml of H was treated with 5ml of deionized water 3 PO 4 (85%) diluted, 2.2g Al was added 2 O 3 Slowly add diluted H 3 PO 4 A solution. And (5) stirring vigorously for 4-6 h. Thereafter, 5g of TEA and 1.0g of SiO were weighed 2 And SiO is combined with 2 After adding uniformly to the TEA solution under stirring, the remaining deionized water (14.85 ml) containing 40mg of yeast DNA was added, and the mixture was vigorously stirred for 4 to 6 hours, and then the two stirred stock solutions were mixed uniformly, and the pH of the sample synthesis gel was controlled at 9 using ammonia.
And adding the gel obtained after stirring into a hydrothermal reaction kettle, and adding the gel obtained after stirring into the hydrothermal reaction kettle, performing hydrothermal crystallization for 5 hours at 110 ℃ and then performing hydrothermal crystallization for 22 hours at 190 ℃. And then carrying out vacuum suction filtration on the crystallization liquid taken out of the reaction kettle, and continuously adding deionized water for washing until the solution is neutral. The crystals were taken out and dried in an oven at 90℃for 11h. Finally, the sample after crystallization is subjected to the following calcination procedure: the sample is heated to 135 ℃ from 30 ℃ for 120min, kept for 220min, and then heated to 575 ℃ and kept for 380min. Finally, the temperature is reduced to 30 ℃ after 30 min. The multi-stage SAPO-34 molecular sieve is prepared after calcination.
In FIG. 1, S2 is the XRD pattern of the present example for the preparation of SAPO-34 molecular sieves containing 40mg of yeast DNA as template. As shown, the high peak intensity and no baseline drift indicates that all samples were high in crystallinity and free of impurities, with corresponding characteristic peaks at 2θ=9.5 °, 13 °, 16.1 °, 17.8 ° and 20.7 °, and diffraction double peaks at 26 ° and 31 ° were peaks specific to SAPO-34 molecular sieves, indicating that the synthesized samples were all SAPO-34, indicating that the samples still maintained the complete CHA structure of the SAPO-34 molecular sieves, while the crystallinity of the samples was higher.
Example 3
The embodiment discloses a method for preparing a SAPO-34 molecular sieve by taking saccharomycete DNA as a template, which specifically comprises the following steps:
activating pure strain of saccharomycete at normal temperature, inoculating the pure strain into potato glucose liquid culture medium for expanding culture, and collecting bacterial thallus for DNA extraction. Firstly, culturing 5mL of saccharomycetes at 12000 r.min -1 Centrifuging for 10min, then taking precipitate (thallus), adding 500 mu L PBS buffer solution to resuspend thallus, and repeating the centrifugation and resuspension processes for 1-2 times. Then 30 mg/mL was added to the precipitate -1 Snailase solution, 500. Mu.L lysate, at 50℃for 6h. Adding equal volume of phenol-chloroform-isoamyl alcohol into the suspension, gently reversing and mixing uniformly, 12000 r.min -1 Centrifuging for 10min, collecting supernatant, adding equal volume of phenol-chloroform-isoamyl alcohol, and extracting again. Adding 2-3 times of absolute ethyl alcohol into the supernatant, gently mixing, standing at room temperature for 30min,12000 r.min -1 Centrifuging for 5min, washing precipitate (DNA) with 75% ethanol for 2 times, naturally drying, dissolving in 50 μl of sterile double distilled water, adding 5 μl of 10mg.mL -1 Is subjected to warm bath at 37 ℃ for 30min, is naturally cooled and is preserved, TE buffer is added after extraction is finished, and the obtained product is preserved in a refrigerator at 4 ℃ for standby.
3ml of H was treated with 5ml of deionized water 3 PO 4 (85%) diluted, 2.3g Al was added 2 O 3 Slowly add diluted H 3 PO 4 A solution. And (5) stirring vigorously for 4-6 h. Thereafter 6g of TEA and 1.2g of SiO were weighed out 2 And SiO is combined with 2 After adding uniformly to the TEA solution under stirring, the remaining deionized water (14.85 ml) containing 50mg of yeast DNA was added, and the mixture was vigorously stirred for 4 to 6 hours, and then the two stirred stock solutions were mixed uniformly, and the pH of the sample synthesis gel was controlled at 8.5 using ammonia.
And adding the gel obtained after stirring into a hydrothermal reaction kettle, performing hydrothermal crystallization for 6 hours at 110 ℃, and performing hydrothermal crystallization for 24 hours at 180 ℃. And then carrying out vacuum suction filtration on the crystallization liquid taken out of the reaction kettle, and continuously adding deionized water for washing until the solution is neutral. The crystals were taken out and dried in an oven at 100℃for 12h. Finally, the sample after crystallization is subjected to the following calcination procedure: the sample is heated to 150 ℃ from 30 ℃ for 120min, kept for 240min, and then heated to 600 ℃ and kept for 400min. Finally, the temperature is reduced to 30 ℃ after 30 min. The multi-stage SAPO-34 molecular sieve is prepared after calcination.
S3 in FIG. 1 is the XRD pattern of the SAPO-34 molecular sieve prepared by using 50mg of yeast DNA as a template in the present example. As shown in the figure, the peak intensity is high and no baseline drift shows that all samples have high crystallinity and no impurities, corresponding characteristic peaks are arranged at 2 theta = 9.5 °, 13 °, 16.1 °, 17.8 ° and 20.7 °, and diffraction double peaks of 26 ° and 31 ° are peaks specific to SAPO-34, so that the synthesized samples are all SAPO-34, and the samples still maintain the complete CHA structure of the SAPO-34 molecular sieve, and meanwhile, the crystallinity of the samples is higher. Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The method for preparing the SAPO-34 molecular sieve by taking saccharomycete DNA as a template is characterized by comprising the following steps of:
step 1: rapidly weigh Al 2 O 3 Gradually adding H diluted by deionized water 3 PO 4 The solution is prepared into a liquid preparation,
step 2: rapidly weigh SiO 2 Gradually adding into the stirred TEA solution;
step 3: rapidly weighing seed crystal of SAPO-34 molecular sieve and gradually adding SiO 2 Mixing with TEA, and stirring uniformly;
step 4: dropwise adding the mixed solution obtained in the step (3) into the mixed solution obtained in the step (2), and fully stirring;
step 5: activating pure strain of saccharomycete at normal temperature, and inoculating the pure strain of saccharomycete into a liquid culture medium for expansion culture;
step 6: crushing the cell walls of the saccharomycetes in the step 5 by using a snailase solution, collecting the extracted DNA, and putting the extracted DNA into a TE buffer solution for storage at a refrigerator of 4 ℃ for later use;
step 7: diluting the standby DNA into the residual deionized water, adding the residual deionized water into the mixed solution in the step 4, and stirring at a constant speed;
step 8: ammonia water is adopted to control the pH value of the original gel to be 8-10;
step 9: adding the gel obtained after stirring into a hydrothermal reaction kettle, synthesizing by adopting a two-step method, performing hydrothermal crystallization for 4-8 hours at 110 ℃, and performing hydrothermal crystallization for 20-24 hours at 180-200 ℃;
step 10, vacuum suction filtering is carried out on the crystallization liquid taken out from the reaction kettle, and deionized water is continuously added for washing until the solution is neutral; taking out the crystal and drying;
step 11, the sample is subjected to the following calcination procedure: the temperature of the sample is raised to 120-150 ℃ from 30 ℃ for 120min, kept for 200-240 min, then raised to 550-600 ℃ and kept for 360-400 min, and finally cooled to 30 ℃ for 30 min.
2. The method for preparing SAPO-34 molecular sieve with yeast DNA as template according to claim 1, wherein in step 1, al 2 O 3 And H is 3 PO 4 The mass ratio of the aqueous solution to the water solution is 1:2-1:3.
3. The method for preparing SAPO-34 molecular sieve with yeast DNA as template according to claim 1, wherein in step 2, siO 2 The mass ratio of the aqueous solution to the TEA solution is 1:5-1:6; and (5) stirring vigorously for 12-16 h.
4. The method for preparing SAPO-34 molecular sieve with saccharomycete DNA as template according to claim 1, wherein the adding ratio of seed crystal to silicon dioxide in the step 3 is 0.0035-0.0039:1.
5. The method for preparing the SAPO-34 molecular sieve with yeast DNA as a template according to claim 1, wherein the yeast in the step 5 is one of lager brewing yeast, grape juice yeast and schizosaccharomyces.
6. The method for preparing SAPO-34 molecular sieve with saccharomycete DNA as template according to claim 1, wherein the concentration of the helicase solution in the step 6 is 20-30 mg.mL -1 The addition ratio is 0.1-0.15:1.
7. The method for preparing the SAPO-34 molecular sieve with saccharomycete DNA as a template according to claim 1, wherein the step 7 is stirred at a constant speed for 24-48 h; the DNA adding proportion is 0.0025-0.005:1 of the molecular sieve raw material liquid.
8. The method for preparing the SAPO-34 molecular sieve with the saccharomycete DNA as a template according to claim 1, wherein the step 10 is to take out crystals and dry the crystals in an oven at 0-100 ℃ for 10-12 hours.
9. A SAPO-34 molecular sieve, characterized in that it is prepared by the method of any one of claims 1 to 8.
10. A CH of a SAPO-34 molecular sieve of claim 9 in natural gas 4 /CO 2 Use in the separation field.
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| WO2015063800A2 (en) * | 2013-11-01 | 2015-05-07 | Council Of Scientific & Industrial Research | Chiral siliceous composition useful as chiral heterogeneous catalyst and a process for the preparation thereof |
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| CN103055823A (en) * | 2012-12-14 | 2013-04-24 | 江苏大学 | Preparation method of surface print adsorbent of yeast template hollow silica-based material for adsorbing and separating strontium ions and application thereof |
| WO2015063800A2 (en) * | 2013-11-01 | 2015-05-07 | Council Of Scientific & Industrial Research | Chiral siliceous composition useful as chiral heterogeneous catalyst and a process for the preparation thereof |
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