CN110339811B - Microbial-based carbon molecular sieve and preparation method and application thereof - Google Patents
Microbial-based carbon molecular sieve and preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
- B01D2257/7025—Methane
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
A microbial-based carbon molecular sieve is prepared by the following steps: centrifuging a culture solution of microorganisms, washing with water to obtain a microorganism precipitate, mixing the microorganism precipitate with an alcohol-water mixed solution, stirring, centrifuging, washing and drying to obtain a biomass material, calcining the biomass material at 400-550 ℃ under an inert atmosphere for 0.5-2 h, cooling, grinding to obtain a primary carbonized material, adding a binder and water, kneading uniformly, pressing to form a molding material, placing the molding material in a tubular furnace, introducing an inert gas for secondary carbonization, keeping the final carbonization temperature at 650-1000 ℃ for 30-180 min, adjusting the temperature to 600-850 ℃, and adding N to the temperature of 600-850 DEG C2The carbon molecular sieve is used for carrying gas, meanwhile, water vapor is introduced for activation, the activation time is 1-4 hours, and then the carbon molecular sieve is cooled to room temperature under the inert atmosphere to obtain a finished product.
Description
(I) technical field
The invention relates to a microbial-based carbon molecular sieve, a preparation method thereof and application thereof in gas separation.
(II) background of the invention
Carbon Molecular Sieves (CMS) are a carbonaceous adsorbent material with a relatively uniform microporous structure developed at the end of the 20 th century. Because of the special pore structure, CMS has the characteristic of selective adsorption of gases of different molecular sizes, and is widely used in PSA gas separation and purification, catalyst support, and other fields. Most of carbon molecular sieves in the market at present use coal, fruit shells and fruit pits as carbon sources, the product aperture is mainly suitable for preparing nitrogen or oxygen by air separation, and the product has the defects of poor strength, poor reproducibility, easy fluctuation of service performance limited by conditions, serious reduction of screening performance along with the increase of service time and the like.
The invention adopts common microorganisms in nature such as chlorella, blue algae, photosynthetic bacteria and the like as main carbon sources, and expands the raw material sources of the carbon molecular sieve. Meanwhile, the original microstructure of the microorganism is beneficial to obtaining the carbon molecular sieve with a specific microporous structure, and the traditional application field is favorably expanded. The mechanical strength and the adsorption capacity of the material can be obviously improved by adding the binder and activating water vapor. The microbial-based carbon molecular sieve can bring hopes for the construction of a carbon molecular sieve material with a better structure and better performance.
Disclosure of the invention
The invention aims to provide a carbon molecular sieve prepared by using microorganisms common in the nature as a main carbon source, and the raw materials of the carbon molecular sieve are wide in source, easy to obtain and easy to implement industrially; the preparation process is simple and environment-friendly; the prepared carbon molecular sieve can effectively adsorb and separate CO at room temperature2/CH4。
The technical scheme of the invention is as follows:
a microbial-based carbon molecular sieve is prepared by the following steps:
(1) pretreatment of biomass material: centrifuging a culture solution of microorganisms, washing with water to obtain a microorganism precipitate, mixing the obtained microorganism precipitate with an alcohol-water mixed solution, stirring for 12-24 h, centrifuging, washing (firstly centrifuging and washing with methanol for 2-3 times, then centrifuging and washing with deionized water for 2-3 times), and drying to obtain a biomass material;
the microorganism is chlorella, photosynthetic bacteria or blue algae;
the alcohol-water mixed solution is prepared by mixing methanol and deionized water in a volume ratio of 2-4: 1;
the volume consumption of the alcohol-water mixed solution is 10-25 mL/g based on the mass of the microbial precipitate;
(2) primary carbonization: calcining the biomass material obtained in the step (1) at 400-550 ℃ under an inert atmosphere for 0.5-2 h, cooling to room temperature (20-30 ℃), grinding (below 100 meshes) to obtain a primary carbonized material, adding a binder and water into the primary carbonized material, uniformly kneading, placing in a mold, pressing to obtain a molding material, and naturally airing at room temperature for later use;
the mass ratio of the primary carbonized material to the binder to the water is 60-80: 10-40: 0-10, preferably 65-75: 15-25: 10;
the binder is selected from phenolic resin, polyvinyl alcohol, polyethylene glycol, starch, cellulose acetate, lignin sulfonate, humic acid or hydroxymethyl cellulose;
(3) secondary carbonization: placing the molding material prepared in the step (2) in a tubular furnace, introducing inert gas for secondary carbonization, wherein the temperature rise speed is 5-10 ℃/min, the final carbonization temperature is 650-1000 ℃, and the carbonization constant temperature time is 30-180 min;
(4) and (3) activation: after the step (3), adjusting the temperature to 600-850 ℃ by N2Simultaneously introducing water vapor as carrier gas for activation for 1-4 h, and then cooling to room temperature under inert atmosphere to obtain the microbial-based carbon molecular sieve;
the flow rate of the steam is 300-600 mL/min, N2The flow rate is 150 to 300 mL/min.
The microbial-based carbon molecular sieve can be used for gas selective adsorption, such as CO2/CH4The adsorption separation of (3).
Specifically, the application method includes: adopting a static adsorption method, firstly measuring the expansion coefficient of a system by using an empty glass tube, and then weighing 0.5g of carbon molecular sieve to be placed in a glass tube (phi 1.2 multiplied by 6 cm); the adsorption device is firstly vacuumized, then 2bar of gas to be detected is introduced, after the system is stabilized, a valve is opened to allow the gas to freely expand to an adsorption tank containing a carbon molecular sieve,recording the stabilized equilibrium pressure, calculating the adsorption capacity of the carbon molecular sieve to the gas to be detected according to related data, and finally calculating to obtain CO2/CH4The separation factor of (1).
Compared with the prior art, the invention has the substantial advantages that:
1. the carbon molecular sieve is prepared by taking common microorganisms in nature such as chlorella, blue algae, photosynthetic bacteria and the like as main carbon sources for the first time;
2. the obtained carbon molecular sieve can effectively adsorb and separate CO at room temperature2/CH4；
3. The microorganism source is wide and easy to obtain, and the industrial implementation is easy; the preparation process is simple, no waste gas and waste water is discharged, and the method is environment-friendly.
(IV) description of the drawings
FIG. 1 is a photograph of a carbon molecular sieve powder prepared from a chlorella composite in example 1 of the present invention;
FIG. 2 is a photograph of carbon molecular sieve powder prepared from the photosynthetic bacteria composite material in example 3 of the present invention.
(V) detailed description of the preferred embodiments
The present invention is further illustrated by the following specific examples, but the scope of the invention is not limited thereto.
The preparation method of the liquid culture medium for culturing the microorganisms comprises the following steps:
0.1g of NH4Cl, peptone 0.5g, NaCl 0.5g, NaHCO 0.5g33g of sodium acetate, 0.1g of MgSO4·7H2O、0.1g CaCl2、0.2g K2HPO4And 0.5g of yeast extract is placed in a beaker, pure water is added, the mixture is stirred and dissolved, the volume is determined to be 1L, and the mixture is placed in a refrigerator for standby.
Example 1: preparation of carbon molecular sieve from chlorella composite material
Collecting 1L Chlorella culture solution, centrifuging, and washing to obtain 3g Chlorella precipitate. The resulting precipitate was placed in a beaker, and 40ml of an alcohol-water mixture (methanol: water ═ 4: 1) was added and stirred at room temperature for 12 hours. The solution was washed several times with methanol and water, respectively, by centrifugation. The obtained sample is placed in an oven and dried for 3h at 90 ℃.
Taking out the sample, carbonizing the sample at N2Raising the temperature to 500 ℃ at a speed of 10 ℃/min under protection, and preserving the temperature for 2 h. After cooling, grinding the mixture to be below 100 meshes. Using phenolic resin as a binder, and mixing the carbonized product, the binder and water in a ratio of 75: 15: 10, putting the mixture into a mold (10 x 5mm), pressing the mixture into a molding material, and airing the molding material at room temperature. And (3) placing the molding material obtained in the step into a tubular furnace, introducing inert gas for carbonization, wherein the temperature rise speed is 10 ℃/min, the final carbonization temperature is 900 ℃, and the constant carbonization temperature time is 3 h. Then the activation temperature is adjusted to 700 ℃ and N is added2As carrier gas, 300ml/min of activation water vapor is simultaneously introduced, and the activation time is 2 h. And after the activation is finished, cooling to room temperature under an inert atmosphere to obtain the microbial-based carbon molecular sieve (shown in figure 1).
Comparative example 1: pure microorganism (chlorella) -based carbon molecular sieve material
The alcohol aqueous solution was replaced with an equal amount of pure water, and the ratio of the carbonized product to water during kneading was replaced with 90: 10. the remaining procedure was the same as in example 1. Obtaining the carbon molecular sieve of the chlorella without treatment.
Example 2: changing the type of binder
First, a powdery primary carbonized product was prepared according to the method of example 1. Starch was chosen as binder, according to the carbonization product, binder and water 65: 25: 10, putting the mixture into a mold to be pressed into a molding material, and airing the molding material at room temperature. And (3) placing the molding material obtained in the step into a tubular furnace, introducing inert gas for carbonization, wherein the temperature rise speed is 10 ℃/min, the final carbonization temperature is 800 ℃, and the constant carbonization temperature time is 2 h. The rest of the operation steps are the same as the example 1, and the carbon molecular sieve material prepared by using the starch as the binder is obtained.
Example 3: changing the kind of microorganism
First, photosynthetic bacteria were selected as a carbon source, and the obtained precipitate was placed in a beaker, and 30ml of an alcohol-water mixture (methanol: water ═ 2: 1) was added and stirred at room temperature for 24 hours. The solution was washed several times with methanol and water, respectively, by centrifugation. The obtained sample is placed in an oven and dried for 3h at the temperature of 80 ℃.
Taking out the sample, carbonizing the sample at N2Raising the temperature to 550 ℃ at a speed of 10 ℃/min under protection, and preserving the temperature for 2 h. After cooling, grinding the mixture to be below 100 meshes. Using phenolic resin as a binder, and mixing the carbonized product, the binder and water in a ratio of 75: 15: 10, putting the mixture into a mold to be pressed into a molding material, and airing the molding material at room temperature. And (3) placing the molding material obtained in the step into a tubular furnace, introducing inert gas for carbonization, wherein the temperature rise speed is 10 ℃/min, the final temperature of carbonization is 950 ℃, and the constant temperature time of carbonization is 3 h. Then the activation temperature is adjusted to 750 ℃ and N is added2As carrier gas, 300ml/min of activation water vapor is introduced at the same time, and the activation time is 3 h. After activation was completed, the reaction mixture was cooled to room temperature under an inert atmosphere (as shown in FIG. 2).
Example 4: the carbon molecular sieve prepared in example 1 was tested for CO2And CH4Adsorption performance of
By adopting a static adsorption method, the expansion coefficient of the adsorption device is firstly measured by using an empty glass tube, and then 0.5g of carbon molecular sieve is weighed and placed in the glass tube (phi 1.2 multiplied by 6 cm). Firstly vacuumizing an adsorption device, then introducing 2bar of gas to be detected, opening a valve after a system is stable to allow the gas to freely expand to an adsorption tank containing a carbon molecular sieve, recording the stable equilibrium pressure, calculating the adsorption quantity of the carbon molecular sieve to the gas to be detected according to related data, and finally calculating to obtain CO2/CH4The separation factor of (1).
As shown in Table 1, the novel porous carbon molecular sieve prepared by the microorganism has higher adsorption capacity and adsorption selectivity.
Table 1 comparison of properties of porous carbon molecular sieves prepared in examples 1, 2 and 3 and comparative example 1
Claims (6)
1. A microbial-based carbon molecular sieve is characterized by being prepared by the following method:
(1) pretreatment of biomass material: centrifuging a culture solution of microorganisms, washing with water to obtain a microorganism precipitate, mixing the obtained microorganism precipitate with an alcohol-water mixed solution, stirring for 12-24 h, centrifuging, washing, and drying to obtain a biomass material;
the microorganism is chlorella, photosynthetic bacteria or blue algae;
the alcohol-water mixed solution is prepared by mixing methanol and deionized water in a volume ratio of 2-4: 1;
(2) primary carbonization: calcining the biomass material obtained in the step (1) at 400-550 ℃ for 0.5-2 h in an inert atmosphere, cooling to room temperature, grinding to obtain a primary carbonized material, adding a binder and water into the primary carbonized material, uniformly kneading, placing in a mold, pressing to prepare a molding material, and naturally airing at room temperature for later use;
the mass ratio of the primary carbonized material to the binder to the water is 60-80: 10-40: 0 to 10;
(3) secondary carbonization: placing the molding material prepared in the step (2) in a tubular furnace, introducing inert gas for secondary carbonization, wherein the temperature rise speed is 5-10 ℃/min, the final carbonization temperature is 650-1000 ℃, and the carbonization constant temperature time is 30-180 min;
(4) and (3) activation: after the step (3), adjusting the temperature to 600-850 ℃ by N2And (3) carrying gas, introducing water vapor for activation, wherein the activation time is 1-4 h, and then cooling to room temperature under an inert atmosphere to obtain the microbial-based carbon molecular sieve.
2. The microbial-based carbon molecular sieve of claim 1, wherein in the step (1), the volume usage amount of the alcohol-water mixed solution is 10-25 mL/g based on the mass of the microbial precipitate.
3. The microbial-based carbon molecular sieve of claim 1, wherein in the step (2), the mass ratio of the primary carbonized material to the binder to water is 65-75: 15-25: 10.
4. the microbial-based carbon molecular sieve of claim 1, wherein in step (2), the binder is selected from the group consisting of phenolic resin, polyvinyl alcohol, polyethylene glycol, starch, cellulose acetate, lignin sulfonate, humic acid, and hydroxymethyl cellulose.
5. The microbial-based carbon molecular sieve of claim 1, wherein in step (4), the water vapor flow rate is 300-600 mL/min, N2The flow rate is 150 to 300 mL/min.
6. The microbial-based carbon molecular sieve of claim 1 in gaseous CO2/CH4Application in selective adsorption separation.
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| CN111871373B (en) * | 2020-07-31 | 2022-06-21 | 宁夏博实科技有限公司 | Adsorbent for separating nitrogen and methane and preparation method and application thereof |
| CN114682233B (en) * | 2022-03-17 | 2024-02-13 | 青岛华世洁环保科技有限公司 | Core-shell type carbon molecular sieve and preparation method and application thereof |
| CN114956074A (en) * | 2022-06-17 | 2022-08-30 | 西安交通大学 | Seaweed-based three-dimensional porous carbon sieve and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11106751A (en) * | 1997-10-06 | 1999-04-20 | Mokushitsu Fukugou Zairyo Gijutsu Kenkyu Kumiai | Soil conditioner and sox adsorbent |
| CN1568290A (en) * | 2001-08-23 | 2005-01-19 | 宝洁公司 | Manufacturing method of water filter |
| CN105056879A (en) * | 2015-07-13 | 2015-11-18 | 安徽成方新材料科技有限公司 | Composite spherical activated carbon added with polyester fibers and capable of improving mechanical strength as well as preparation method of composite spherical activated carbon |
| WO2016144248A1 (en) * | 2015-03-12 | 2016-09-15 | Provtagaren Ab | Method for active or passive sampling of particles and gas phase organic and non-organic components in a fluid flow |
| CN106006631A (en) * | 2016-05-26 | 2016-10-12 | 湖州民强炭业有限公司 | Biologically-modified eulaliopsis binata fiber CMSCH4 concentrated methane carbon molecular sieve |
| WO2017049090A1 (en) * | 2015-09-16 | 2017-03-23 | Sweetwater Energy, Inc. | Specialized activated carbon derived from pretreated biomass |
| CN107115845A (en) * | 2017-06-21 | 2017-09-01 | 北京金隅琉水环保科技有限公司 | Carbon dioxide absorber, carbon dioxide adsorption tower and carbon dioxide recovery system, in accordance |
| CN109603565A (en) * | 2018-12-12 | 2019-04-12 | 浙江工业大学 | The method of catechol assistant depositing synthesis metal organic framework composite membrane |
-
2019
- 2019-06-27 CN CN201910566902.4A patent/CN110339811B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11106751A (en) * | 1997-10-06 | 1999-04-20 | Mokushitsu Fukugou Zairyo Gijutsu Kenkyu Kumiai | Soil conditioner and sox adsorbent |
| CN1568290A (en) * | 2001-08-23 | 2005-01-19 | 宝洁公司 | Manufacturing method of water filter |
| WO2016144248A1 (en) * | 2015-03-12 | 2016-09-15 | Provtagaren Ab | Method for active or passive sampling of particles and gas phase organic and non-organic components in a fluid flow |
| CN105056879A (en) * | 2015-07-13 | 2015-11-18 | 安徽成方新材料科技有限公司 | Composite spherical activated carbon added with polyester fibers and capable of improving mechanical strength as well as preparation method of composite spherical activated carbon |
| WO2017049090A1 (en) * | 2015-09-16 | 2017-03-23 | Sweetwater Energy, Inc. | Specialized activated carbon derived from pretreated biomass |
| CN106006631A (en) * | 2016-05-26 | 2016-10-12 | 湖州民强炭业有限公司 | Biologically-modified eulaliopsis binata fiber CMSCH4 concentrated methane carbon molecular sieve |
| CN107115845A (en) * | 2017-06-21 | 2017-09-01 | 北京金隅琉水环保科技有限公司 | Carbon dioxide absorber, carbon dioxide adsorption tower and carbon dioxide recovery system, in accordance |
| CN109603565A (en) * | 2018-12-12 | 2019-04-12 | 浙江工业大学 | The method of catechol assistant depositing synthesis metal organic framework composite membrane |
Non-Patent Citations (5)
| Title |
|---|
| Comparison of performance and ionic concentration gradient of two-chamber microbial fuel cell using ceramic membrane (CM) and cation exchange membrane (CEM) as separators;Daud Siti Mariam et al.;《ELECTROCHIMICA ACTA》;20180101;365-376 * |
| Sustainable activated carbons of macroalgae waste from the Agar-Agar industry. Prospects as adsorbent for gas storage at high pressures;Ferrera-Lorenzo N. et al.;《CHEMICAL ENGINEERING JOURNAL》;20140815;128-136 * |
| Sustainable Growth and Lipid Production from Chlorella pyrenoidosa Using N-Doped Carbon Nanosheets: Unravelling the Role of Graphitic Nitrogen;Khanra Anwesha et al.;《ACS SUSTAINABLE CHEMISTRY & ENGINEERING》;20180131;774-780 * |
| 改性生物质基活性炭的制备及其CO2/CH4的选择性吸附性能研究;高俊;《万方数据库》;20181218;全文 * |
| 碳分子筛的制备与应用研究进展;赵海华等;《安徽化工》;20150228;9-11 * |
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