CN114014331A - Method for preparing SAPO-34 molecular sieve by using yeast DNA as template, molecular sieve and application thereof - Google Patents
Method for preparing SAPO-34 molecular sieve by using yeast DNA as template, molecular sieve and application thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 62
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 240000004808 Saccharomyces cerevisiae Species 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 8
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 40
- 235000014680 Saccharomyces cerevisiae Nutrition 0.000 claims description 35
- 239000013078 crystal Substances 0.000 claims description 13
- 239000003345 natural gas Substances 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 108060004795 Methyltransferase Proteins 0.000 claims description 5
- 241000235342 Saccharomycetes Species 0.000 claims description 5
- 239000007984 Tris EDTA buffer Substances 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 230000003321 amplification Effects 0.000 claims description 5
- 239000001963 growth medium Substances 0.000 claims description 5
- 238000009630 liquid culture Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000003199 nucleic acid amplification method Methods 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 241000235347 Schizosaccharomyces pombe Species 0.000 claims description 2
- 210000002421 cell wall Anatomy 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 2
- 241000582914 Saccharomyces uvarum Species 0.000 claims 1
- 239000002028 Biomass Substances 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- ZYWFEOZQIUMEGL-UHFFFAOYSA-N chloroform;3-methylbutan-1-ol;phenol Chemical compound ClC(Cl)Cl.CC(C)CCO.OC1=CC=CC=C1 ZYWFEOZQIUMEGL-UHFFFAOYSA-N 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 244000061456 Solanum tuberosum Species 0.000 description 3
- 235000002595 Solanum tuberosum Nutrition 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000012154 double-distilled water Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000006166 lysate Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 235000019674 grape juice Nutrition 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/104—Carbon dioxide
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
- C10L2290/542—Adsorption of impurities during preparation or upgrading of a fuel
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Abstract
The invention provides a method for preparing an SAPO-34 molecular sieve by using yeast DNA as a template, the molecular sieve and application thereof. The preparation method of the SAPO-34 molecular sieve comprises the following steps of: mixing Al2O3Is added to H3PO4Stirring the solution vigorously; mixing SiO2Uniformly adding the mixture into a stirred TEA solution, adding deionized water containing yeast DNA, and violently stirring; and uniformly mixing the two stirred raw material liquids to obtain an original gel, and adding the original gel into a reaction kettle to perform hydrothermal crystallization reaction. Then vacuum filtering and dryingDrying and calcining to remove the template agent, and preparing the SAPO-34 molecular sieve. The invention adopts cheap and environment-friendly biomass to replace organic template agent which is used in large quantity 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 a multi-stage pore canal through a microstructure of biomass, so that the gas selectivity and the adsorption capacity are increased.
Description
Technical Field
The invention relates to a molecular sieve technology, in particular to a method for preparing an SAPO-34 molecular sieve by using yeast DNA as a template, the molecular sieve and application thereof.
Background
The main component of natural gas is CH4And CO in underground-mined acid-rich natural gas and artificial fermentation natural gas2The content is higher, which not only reduces the heat value of the natural gas but also influences the transportation of the natural gas. Especially CO2As a greenhouse gas, excessive emissions thereof cause climate warming and have become an environmental problem of concern worldwide. Scholars at home and abroad aiming at CO in natural gas2Many studies of separation methods have been conducted. The traditional natural gas purification technology, such as an alcohol ammonia method, a low temperature/fractionation method and the like, has 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 much attention due to its low energy consumption and low cost, especially in the separation of methane and carbon dioxide.
The SAPO-34 molecular sieve is a silicoaluminophosphate molecular sieve with a typical topological structure, the pore diameter of the molecular sieve is 0.38nm, and the pore volume of the molecular sieve is 0.42cm3The/g, space symmetry group is R3m, is a trigonal system, has good thermal stability and chemical stability as an adsorbent, and has relatively high selectivity. In recent years, the synthesis of nano SAPO-34 molecular sieve particles draws special attention of researchers, and due to the large specific surface area and the special pore channel structure, the nano SAPO-34 molecular sieve particles are widely applied to gas separation and methanol-to-olefin reaction, and particularly the application effect in the aspect of gas and liquid separation is obviously improved.
The development of the traditional adsorbent can involve the use of organic solvents, and environmental pollution can be generated in the preparation process. And multilayer, multidimensional and multi-scale natural hard template structures evolved in the natural environment for a long time and some natural 'soft' biomolecules with multilayer and multidimensional structures can provide a new idea for the design and preparation of the multilevel-structure nano material. The method for preparing the metal oxide by directly using the chemical reagent as the template is usually contrary to the environmental protection and economic concepts, and the preparation of the metal oxide with the complex porous structure by using the green and environment-friendly biomass and the derivative thereof as the template through simple preparation conditions is more consistent with the sustainable development requirement. In addition, biomass in nature can synthesize materials with various special spatial structures, and the structural complexity of the biomass exceeds the degree which can be achieved by physical or chemical methods at present.
Disclosure of Invention
The invention aims to provide a method for preparing an SAPO-34 molecular sieve by using yeast DNA as a template, aiming at the problems of high cost and environmental pollution caused by using a large amount of organic amine template in the traditional process, wherein cheap and environment-friendly biomass, namely the yeast DNA, is adopted for substitution, so that the use of the organic template is reduced; and a microstructure of biomass is adopted to provide a multistage pore passage for the molecular sieve, so that the gas selectivity and the adsorption capacity are increased.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for preparing SAPO-34 molecular sieve by using yeast DNA as a template comprises the following steps:
step 1: quickly weighing a proper amount of Al2O3Gradually adding into H diluted by deionized water3PO4The mass ratio of the two solutions is 1: 2-1: 3;
step 2: quickly weighing proper amount of SiO2Gradually adding the mixture into a stirred TEA solution, wherein the mass ratio of the TEA solution to the TEA solution is 1: 5-1: 6; then, violently stirring for 12-16 h;
and step 3: quickly weighing a proper amount of commercial SAPO-34 molecular sieve crystal seeds, and gradually adding SiO2In the mixed solution of the seed crystal and the TEA, the adding proportion of the seed crystal is 0.0035-0.0039: 1(/ MS)iO2) And uniformly stirring;
step (ii) of4: mixing the mixed solution (containing SiO) obtained in the step 32TEA and seed crystal) was added dropwise to the mixture of step 1 (containing Al)2O3And H3PO4) Fully stirring for several hours;
and 5: activating pure yeast strain at normal temperature, and inoculating to liquid culture medium (beer yeast, grape juice yeast or fission yeast) for amplification culture;
step 6: and (3) crushing the cell walls of the saccharomycetes in the step (5) by using a helicase solution, wherein the concentration of the helicase solution is 20-30 mg/mL-1The adding ratio is 0.1-0.15: 1 (mass ratio); collecting the extracted DNA, placing the DNA in a TE buffer solution, and storing the DNA in a refrigerator at 4 ℃ for later use;
and 7: diluting the standby DNA into the rest deionized water, adding the diluted DNA into the mixed solution in the step (4), and stirring at a constant speed for 24-48 h; the adding proportion of the DNA is 0.0025-0.005: 1 (mass ratio) of the molecular sieve raw material liquid;
and 8: controlling the pH value of the original sol to be 8-10 by adopting ammonia water;
and step 9: adding the stirred gel into a hydrothermal reaction kettle, and synthesizing by adopting a two-step method, wherein the hydrothermal crystallization is carried out for 4-8 h at 110 ℃, and then the hydrothermal crystallization is carried out for 20-24 h at 180-200 ℃;
step 10: carrying out vacuum filtration on the crystallization liquid taken out of the reaction kettle, and continuously adding deionized water for washing until the solution is neutral; taking out the crystal, and drying the crystal in an oven at 0-100 ℃ for 10-12 h;
step 11: the sample was subjected to the following calcination procedure: heating the sample from 30 ℃ for 120min to 120-150 ℃, keeping the temperature for 200-240 min, heating to 550-600 ℃, keeping the temperature for 360-400 min, and finally cooling to 30 ℃ for 30 min.
The invention also discloses an SAPO-34 molecular sieve prepared by the method.
Furthermore, the particle size of the SAPO-34 molecular sieve is 1-3 μm, the microstructure of the biomass provides a multi-stage pore channel for the molecular sieve, the SAPO-34 molecular sieve has good gas selectivity and adsorption capacity, and the problems of high cost, environmental pollution and the like caused by the large use of organic template in the traditional process are solved.
Another purpose of the invention is to disclose the SAPO-34 molecular sieve which is prepared by using CH in natural gas4/CO2Use in the field of separations.
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 using the yeast 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, the use of organic amine is reduced by doping biomass, so that the preparation cost of the SAPO-34 molecular sieve is greatly reduced.
2) According to the invention, the SAPO-34 molecular sieve is in a multi-stage layered structure by adding the yeast 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 carried out from the environmental protection perspective, and the long-term environmental economic benefit can be generated by reducing the use of a large amount of organic solvents in the traditional preparation method.
Drawings
FIG. 1 is an XRD spectrum of SAPO-34 molecular sieve doped with DNA multi-stage structure and containing 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 spectrums of samples synthesized by yeast DNA suspension liquid with different contents.
Detailed Description
The invention is further illustrated by the following examples:
example 1
The embodiment discloses a method for preparing SAPO-34 molecular sieve by using yeast DNA as a template, which specifically comprises the following steps:
activating pure saccharomycete strain at normal temperature, inoculating to potato glucose liquid culture medium for amplification culture, and extracting DNA from the collected bacterial thallus. First, 3mL of yeast was cultured at 12000 r.min-1Centrifuging for 5min, adding 300 mu L PBS buffer solution into the precipitate (thallus) to resuspend the thallus, and repeating the centrifuging and resuspending processes for 1-2 times. Is connected withThen 20 mg/mL of the precipitate was added-1The helicase solution is 100 μ L, the lysate is 350 μ L, and the reaction is carried out at 45 ℃ for 4 h. Adding equal volume of phenol-chloroform-isoamyl alcohol into the suspension, slightly reversing and mixing evenly, and 12000 r.min-1Centrifuging for 5min, collecting supernatant, adding equal volume of phenol-chloroform-isoamyl alcohol, and extracting once again. Adding 2-3 times of anhydrous ethanol into the supernatant, gently mixing, standing at room temperature for 30min, and 12000 r.min-1Centrifuging for 10min, collecting precipitate (DNA), washing with 75% ethanol for 2 times, naturally drying, dissolving in 50 μ L sterile double distilled water, adding 3 μ L10 mg/mL-1The RNaseA is subjected to warm bath at 37 ℃ for 30min, is naturally cooled and then stored, and is added with TE buffer solution after extraction is finished and is stored in a refrigerator at 4 ℃ for later use.
3ml of H with 5ml of deionized water3PO4(85%) diluted and 2.4g of Al2O3Slowly adding diluted H3PO4And (4) stirring the solution vigorously for 4-6 hours. Thereafter 4g of TEA and 0.8g of SiO were weighed2And mixing SiO2And uniformly adding the mixture into the stirred TEA solution, then adding the rest deionized water (14.85ml) containing 30mg of yeast DNA, vigorously stirring for 4-6 h, uniformly mixing the two stirred raw material solutions, and controlling the pH value of the synthesized sample gel to be 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 filtration on the crystallization liquid taken out of the reaction kettle, and continuously adding deionized water for washing until the solution is neutral. The crystal is taken out and placed in an oven at 80 ℃ for drying for 10 h. And finally, calcining the sample after the crystallization is finished according to the following steps: the temperature of the sample is raised to 120 ℃ from 30 ℃ for 120min and kept for 200min, and then the temperature is raised to 550 ℃ and kept for 360 min. Finally, the temperature is reduced to 30 ℃ after 30 min. And calcining to prepare the multistage SAPO-34 molecular sieve.
In FIG. 1, S1 is the XRD pattern of SAPO-34 molecular sieve prepared by the method with 30mg yeast DNA as the template. As shown, the high peak intensity and no baseline shift indicate that all samples are highly crystalline and free of impurities, the corresponding characteristic peaks at 2 θ ═ 9.5 °, 13 °, 16.1 °, 17.8 ° and 20.7 °, and the diffraction doublets at 26 ° and 31 ° are the peaks characteristic of SAPO-34, indicating that the synthesized samples are all SAPO-34 molecular sieves, indicating that the samples still maintain the intact CHA structure of the SAPO-34 molecular sieves, while the samples are highly crystalline.
Example 2
The embodiment discloses a method for preparing SAPO-34 molecular sieve by using yeast DNA as a template, which specifically comprises the following steps:
activating pure saccharomycete strain at normal temperature, inoculating to potato glucose liquid culture medium for amplification culture, collecting bacterial thallus and extracting DNA. First, 4mL of yeast was cultured at 12000 r.min-1Centrifuging for 8min, adding 400 mu L PBS buffer solution into the precipitate (thallus) to resuspend the thallus, and repeating the centrifuging and resuspending processes for 1-2 times. Then, 25 mg/mL of the precipitate was added-1Snail enzyme solution, 400 μ L lysate, and 5 hr at 48 deg.C. Adding equal volume of phenol-chloroform-isoamyl alcohol into the suspension, slightly reversing and mixing evenly, and 12000 r.min-1Centrifuging for 8min, collecting supernatant, adding equal volume of phenol-chloroform-isoamyl alcohol, and extracting once again. Adding 2-3 times of anhydrous ethanol into the supernatant, gently mixing, standing at room temperature for 30min, and 12000 r.min-1Centrifuging for 5min, collecting precipitate (DNA), washing with 75% ethanol for 2 times, naturally drying, dissolving in 50 μ L sterile double distilled water, adding 4 μ L10 mg/mL-1The RNaseA is subjected to warm bath at 37 ℃ for 30min, is naturally cooled and then stored, and is added with TE buffer solution after extraction is finished and is stored in a refrigerator at 4 ℃ for later use.
3ml of H with 5ml of deionized water3PO4(85%) diluted and 2.2g of Al2O3Slowly adding diluted H3PO4And (3) solution. And stirring vigorously for 4-6 h. Thereafter 5g of TEA and 1.0g of SiO were weighed2And mixing SiO2And uniformly adding the mixture into the stirred TEA solution, then adding the rest deionized water (14.85ml) containing 40mg of yeast DNA, vigorously stirring for 4-6 h, uniformly mixing the two stirred raw material solutions, and controlling the pH value of the synthesized sample gel to be 9 by adopting ammonia water.
And adding the gel obtained after stirring into a hydrothermal reaction kettle, adding the gel obtained after stirring into the hydrothermal reaction kettle, performing hydrothermal crystallization for 5 hours at the temperature of 110 ℃, and performing hydrothermal crystallization for 22 hours at the temperature of 190 ℃. And then carrying out vacuum filtration on the crystallization liquid taken out of the reaction kettle, and continuously adding deionized water for washing until the solution is neutral. The crystal is taken out and placed in an oven at 90 ℃ for drying for 11 h. And finally, calcining the sample after the crystallization is finished according to the following steps: the temperature of the sample is raised to 135 ℃ from 30 ℃ for 120min and kept for 220min, and then raised to 575 ℃ and kept for 380 min. Finally, the temperature is reduced to 30 ℃ after 30 min. And calcining to prepare the multistage SAPO-34 molecular sieve.
In FIG. 1, S2 is the XRD pattern of SAPO-34 molecular sieve prepared by the method with 40mg yeast DNA as the template. As shown, the high peak intensity and no baseline shift indicate that all samples are high in crystallinity and free of impurities, the corresponding characteristic peaks are found at 2 θ ═ 9.5 °, 13 °, 16.1 °, 17.8 ° and 20.7 °, and the diffraction doublets at 26 ° and 31 ° are the peaks specific to the SAPO-34 molecular sieve, indicating that the synthesized samples are all SAPO-34, indicating that the samples still maintain the intact CHA structure of the SAPO-34 molecular sieve, while the crystallinity of the samples is high.
Example 3
The embodiment discloses a method for preparing SAPO-34 molecular sieve by using yeast DNA as a template, which specifically comprises the following steps:
activating pure saccharomycete strain at normal temperature, inoculating to potato glucose liquid culture medium for amplification culture, collecting bacterial thallus and extracting DNA. First, 5mL of yeast was cultured at 12000 r.min-1Centrifuging for 10min, adding 500 mu L PBS buffer solution into the precipitate (thallus) to resuspend the thallus, and repeating the centrifuging and resuspending processes for 1-2 times. Then, 30 mg/mL of the precipitate was added-1Snail enzyme solution, 500 μ L lysate, and 50 deg.C for 6 hr. Adding equal volume of phenol-chloroform-isoamyl alcohol into the suspension, slightly reversing and mixing evenly, and 12000 r.min-1Centrifuging for 10min, collecting supernatant, adding equal volume of phenol-chloroform-isoamyl alcohol, and extracting once again. Adding 2-3 times of anhydrous ethanol into the supernatant, gently mixing, standing at room temperature for 30min, and 12000 r.min-1Centrifuging for 5min, collecting precipitate (DNA), washing with 75% ethanol for 2 times, naturally drying, dissolving in 50 μ L sterile double distilled water, adding 5 μ L10 mg/mL-1Of (2) anseA, bathing at 37 deg.C for 30min, naturally cooling, storing, extracting, adding TE buffer solution, and storing in refrigerator at 4 deg.C.
3ml of H with 5ml of deionized water3PO4(85%) diluted and 2.3g of Al2O3Slowly adding diluted H3PO4And (3) solution. And stirring vigorously for 4-6 h. 6g of TEA and 1.2g of SiO were then weighed2And mixing SiO2And uniformly adding the mixture into the stirred TEA solution, then adding the rest deionized water (14.85ml) containing 50mg of yeast DNA, vigorously stirring for 4-6 h, uniformly mixing the two stirred raw material solutions, and controlling the pH value of the synthesized sample gel to be 8.5 by adopting ammonia water.
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 filtration on the crystallization liquid taken out of the reaction kettle, and continuously adding deionized water for washing until the solution is neutral. The crystal is taken out and placed in an oven at 100 ℃ for drying for 12 h. And finally, calcining the sample after the crystallization is finished according to the following steps: the temperature of the sample is raised to 150 ℃ from 30 ℃ for 120min and kept for 240min, and then raised to 600 ℃ and kept for 400 min. Finally, the temperature is reduced to 30 ℃ after 30 min. And calcining to prepare the multistage SAPO-34 molecular sieve.
In FIG. 1, S3 is the XRD pattern of SAPO-34 molecular sieve prepared by using 50mg yeast DNA as template in the present example. As shown, the high peak intensity and no baseline shift indicate that all samples are high in crystallinity and free of impurities, the corresponding characteristic peaks are found at 2 θ ═ 9.5 °, 13 °, 16.1 °, 17.8 ° and 20.7 °, and the diffraction doublets at 26 ° and 31 ° are peaks characteristic of SAPO-34, indicating that the synthesized samples are all SAPO-34, indicating that the samples still maintain the intact CHA structure of the SAPO-34 molecular sieve, while the crystallinity of the samples is high. Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for preparing SAPO-34 molecular sieve by using yeast DNA as a template is characterized by comprising the following steps:
step 1: rapidly weighing Al2O3Gradually adding into H diluted by deionized water3PO4The solution is prepared by mixing a solvent and a solvent,
step 2: rapidly weighing SiO2Gradually adding into the stirred TEA solution;
and step 3: quickly weighing SAPO-34 molecular sieve crystal seeds and gradually adding SiO2And TEA, and uniformly stirring;
and 4, step 4: dropwise adding the mixed solution obtained in the step (3) into the mixed solution obtained in the step (2), and fully stirring;
and 5: activating pure yeast strains at normal temperature, and inoculating the pure yeast strains into a liquid culture medium for amplification culture;
step 6: crushing the cell wall of the saccharomycete in the step 5 by using a helicase solution, collecting the extracted DNA, and putting the DNA into a TE buffer solution to be stored in a refrigerator at 4 ℃ for later use;
and 7: diluting the standby DNA into the rest deionized water, adding the diluted DNA into the mixed solution in the step (4), and stirring at a constant speed;
and 8: controlling the pH value of the original gel to be 8-10 by adopting ammonia water;
and step 9: adding the gel obtained after stirring into a hydrothermal reaction kettle, and synthesizing by adopting a two-step method, wherein the hydrothermal crystallization is carried out for 4-8 h at the temperature of 110 ℃, and then the hydrothermal crystallization is carried out for 20-24 h at the temperature of 180-200 ℃;
step 10, carrying out vacuum filtration on the crystallization liquid taken out of the reaction kettle, and continuously adding deionized water for washing until the solution is neutral; taking out the crystal and drying;
step 11, the sample was subjected to the following calcination procedure: heating the sample from 30 ℃ for 120min to 120-150 ℃, keeping the temperature for 200-240 min, heating to 550-600 ℃, keeping the temperature for 360-400 min, and finally cooling to 30 ℃ for 30 min.
2. The method for preparing SAPO-34 molecular sieve based on yeast DNA as template according to claim 1, wherein Al in step 12O3And H3PO4The mass ratio of the water solution to the water solution is 1: 2-1: 3.
3. The method for preparing SAPO-34 molecular sieve based on yeast DNA as template according to claim 1, wherein SiO in step 22The mass ratio of the TEA solution to the TEA solution is 1: 5-1: 6; and stirring vigorously for 12-16 h.
4. The method for preparing SAPO-34 molecular sieve by using yeast DNA as a template according to claim 1, wherein the seed crystal adding proportion in the step 3 is 0.0035-0.0039: 1(/ MS)iO2)。
5. The method for preparing SAPO-34 molecular sieve using yeast DNA as template according to claim 1, wherein the yeast in step 5 is one of Saccharomyces cerevisiae, Saccharomyces uvarum, or Schizosaccharomyces pombe.
6. The method for preparing SAPO-34 molecular sieve by using yeast DNA as a template according to claim 1, wherein the concentration of the helicase solution in the step 6 is 20-30 mg-mL-1The addition ratio is 0.1-0.15: 1.
7. The method for preparing the SAPO-34 molecular sieve by using the yeast DNA as the template according to claim 1, wherein the step 7 is carried out at a constant stirring speed for 24-48 h; the adding proportion of the DNA is 0.0025-0.005: 1 of the molecular sieve raw material liquid.
8. The method for preparing the SAPO-34 molecular sieve by using the yeast DNA as the template according to claim 1, wherein the crystals taken out in the step 10 are dried in an oven at 0-100 ℃ for 10-12 h.
9. A SAPO-34 molecular sieve, characterized in that it has been prepared by the process according to any one of claims 1 to 8.
10. The SAPO-34 molecular sieve of claim 9, wherein the CH is in natural gas4/CO2Use in the field of separations.
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| CN114849643A (en) * | 2022-04-27 | 2022-08-05 | 西安建筑科技大学 | Coal gangue-based porous material taking actinomycetes as template and preparation method thereof |
| CN115709084A (en) * | 2022-10-24 | 2023-02-24 | 河南师范大学 | Preparation method of Fe-Mo heterojunction multi-core micro-nano material based on sexual propagation yeast regulation |
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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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| CN115709084A (en) * | 2022-10-24 | 2023-02-24 | 河南师范大学 | Preparation method of Fe-Mo heterojunction multi-core micro-nano material based on sexual propagation yeast regulation |
| CN115709084B (en) * | 2022-10-24 | 2024-02-06 | 河南师范大学 | Preparation method of Fe-Mo heterojunction polynuclear micro-nano material based on sexual propagation yeast regulation and control |
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