CN110339811A - 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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- CN110339811A CN110339811A CN201910566902.4A CN201910566902A CN110339811A CN 110339811 A CN110339811 A CN 110339811A CN 201910566902 A CN201910566902 A CN 201910566902A CN 110339811 A CN110339811 A CN 110339811A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 48
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 38
- 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 38
- 230000000813 microbial effect Effects 0.000 title abstract 2
- 238000002360 preparation method Methods 0.000 title description 7
- 244000005700 microbiome Species 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011230 binding agent Substances 0.000 claims abstract description 17
- 230000004913 activation Effects 0.000 claims abstract description 12
- 238000003763 carbonization Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000004898 kneading Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 10
- 241000195649 Chlorella <Chlorellales> Species 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 241000894006 Bacteria Species 0.000 claims description 6
- 239000012620 biological material Substances 0.000 claims description 6
- 230000000243 photosynthetic effect Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 241000192700 Cyanobacteria Species 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 2
- 229920001732 Lignosulfonate Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 239000004021 humic acid Substances 0.000 claims description 2
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 2
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- LCDFWRDNEPDQBV-UHFFFAOYSA-N formaldehyde;phenol;urea Chemical group O=C.NC(N)=O.OC1=CC=CC=C1 LCDFWRDNEPDQBV-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 10
- 239000002028 Biomass Substances 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 2
- 239000012778 molding material Substances 0.000 abstract 2
- 239000002244 precipitate Substances 0.000 abstract 2
- 239000005539 carbonized material Substances 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000003825 pressing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000001404 mediated effect Effects 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229940041514 candida albicans extract Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J20/20—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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
- Y02C20/20—Capture or disposal of greenhouse gases of methane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Carbon And Carbon Compounds (AREA)
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 method comprises the steps of carrying gas, introducing water vapor for activation at the same time, wherein the activation time is 1-4 h, and then cooling to room temperature in an inert atmosphere to obtain a finished productThe prepared carbon molecular sieve can be effectively used for gas separation.
Description
(1) technical field
The present invention relates to a kind of microorganism based carbon molecular sieves and preparation method thereof, and the application in gas separation.
(2) background technique
Carbon molecular sieve (Carbon Molecular Sieves, CMS) is that the one kind to grow up in the phase at the end of the 20th century has
The more carbonaceous adsorbent material of uniform cell structure.Because pore structure is special, gas CMS different to molecular dimension has choosing
The characteristics of selecting property is adsorbed, is widely used in PSA method gas separating-purifying, many aspects such as catalyst carrier.Currently on the market
Most carbon molecular sieves are all with coal, and shell and fruit stone are carbon source, product aperture be mainly suitable for for preparing nitrogen by separating air or
Oxygen processed, and product strength is poor, the easy fluctuation subject to conditions of poor reproducibility, service performance, sieve performance are tight with using the time to increase
The disadvantages of declining again.
The present invention, as primary carbon source, is expanded using common microorganisms of natures such as chlorella, cyanobacteria, photosynthetic bacterias
The raw material sources of carbon molecular sieve.The microstructure of microorganism script helps to obtain the carbon with specific microcellular structure point simultaneously
Son sieve, helps to expand existing application field.By the addition of binder and the activation of vapor, material can be significantly improved
The mechanical strength and adsorption capacity of material.Microorganism based carbon molecular sieve can be the carbon molecular sieve material of more excellent structure more dominance energy
The building of material brings hope.
(3) summary of the invention
The object of the present invention is to provide a kind of microorganisms common using nature as carbon molecules made from primary carbon source
Sieve, raw material sources of the present invention extensively, be easy to get to being easy to industrializing implementation；Preparation process is simple, environmental-friendly；Carbon obtained point
Son sieve being capable of effectively adsorbing separation CO at room temperature2/CH4。
Technical scheme is as follows:
A kind of microorganism based carbon molecular sieve, is prepared as follows to obtain:
(1) biological material pre-processes: by the medium centrifugal of microorganism, washing obtains microorganism precipitating, then by gained
Microorganism precipitating is mixed with alcohol-water mixture, and stirring 12~for 24 hours, it is centrifuged later, washing (first use methanol centrifuge washing 2~3 times,
Deionized water centrifuge washing is used again 2~3 times), drying obtains biological material；
The microorganism is chlorella, photosynthetic bacteria or cyanobacteria；
The alcohol-water mixture is the mixed liquor of methanol and 2~4:1 of deionized water volume ratio；
The volumetric usage of the alcohol-water mixture is calculated as 10~25mL/g with the quality that the microorganism is precipitated；
(2) primary carbonization: biological material obtained by step (1) is calcined 0.5 under 400~550 DEG C, inert atmosphere~
2h is cooled to room temperature (20~30 DEG C), is ground (to 100 mesh), a carbonized stock is obtained, in carbonized stock of gained
Binder, water kneading is added uniformly, is placed in mold and is pressed into molding mass, room temperature naturally dry is stand-by；
Carbonized stock, binder, water mass ratio be 60~80:10~40:0~10, preferably 65~75:15~
25:10；
The binder be selected from phenolic resin, polyvinyl alcohol, polyethylene glycol, starch, cellulose acetate, ligninsulfonate,
Humic acid or hydroxymethyl cellulose；
(3) secondary carbonization: step (2) ready molding mass is placed in tube furnace, and it is secondary to be passed through inert gas progress
Carbonization, 5~10 DEG C/min of heating rate are carbonized 650~1000 DEG C of final temperature, and be carbonized 30~180min of constant temperature time；
(4) it activates: after step (3), 600~850 DEG C is adjusted the temperature to, with N2For carrier gas, while being passed through vapor
It is activated, activation time is 1~4h, is cooled to room temperature under an inert atmosphere later, obtains microorganism based carbon molecular sieve；
The water vapor flow rate is 300~600mL/min, N2Flow rate is 150~300mL/min.
Microorganism based carbon molecular sieve of the present invention can be used for gas-selectively absorption, such as CO2/CH4Adsorbing separation.
Specifically, the method for the application is for example: using static adsorptive method, the expansion system of system is first measured with sky glass tube
Number, then weigh the carbon molecular sieve of 0.5g and be placed in glass tube (1.2 × 6cm of Φ)；Adsorbent equipment vacuumizes first, is subsequently passed
The under test gas of 2bar opens valve by gas free wxpansion to the adsorption tank for being placed with carbon molecular sieve, record after waiting stable systems
Balance pressure after lower stabilization goes out carbon molecular sieve for the adsorbance of tested gas according to correlation data calculation, finally calculates
To CO2/CH4Separation factor.
Compared with prior art, substantial advantage of the invention:
1, carbon is prepared as primary carbon source using common microorganisms of natures such as chlorella, cyanobacteria, photosynthetic bacterias for the first time
Molecular sieve；
2, gained carbon molecular sieve effectively adsorbing separation CO at room temperature2/CH4；
3, it is microbe-derived extensively, be easy to get to being easy to industrializing implementation；Preparation process is simple, no exhaust gas discharge of wastewater, right
It is environmental-friendly.
(4) Detailed description of the invention
Fig. 1 is the carbon molecular sieve powder photo that the chlorella composite material in the embodiment of the present invention 1 is prepared；
Fig. 2 is the carbon molecular sieve powder photo that the photosynthetic bacteria composite material in the embodiment of the present invention 3 is prepared.
(5) specific embodiment
Below by specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited in
This.
Preparation method for cultivating the fluid nutrient medium of microorganism is as follows:
By 0.1g NH4Cl, 0.5g peptone, 0.5g NaCl, 0.5g NaHCO3, 3g sodium acetate, 0.1g MgSO4·
7H2O、0.1g CaCl2、 0.2g K2HPO4, 0.5g yeast extract be placed in a beaker, pure water is added, stirring and dissolving is settled to 1L,
It is placed in refrigerator stand-by.
Embodiment 1: chlorella composite material prepares carbon molecular sieve
1L bead algae culturing liquid is taken, centrifuge washing obtains 3g chlorella sediment.Gained sediment is placed in a beaker, is added
Enter 40ml alcohol-water mixture (methanol: water=4:1) and 12h is stirred at room temperature.Solution uses first alcohol and water centrifuge washing for several times respectively.?
It is placed in baking oven to sample, 90 DEG C of drying 3h.
It takes out above-mentioned sample to be once carbonized, in N2500 DEG C are warming up to 10 DEG C/min under protection, keeps the temperature 2h.To cold
But it is ground to 100 mesh afterwards.With phenolic resin as binder, according to carbonized product, the ratio of binder and water 75:15:10
Example is mediated uniformly, is put into mold (10*5*5mm) and is pressed into molding mass, dries at room temperature.The molding that above-mentioned steps are obtained
Material is placed in tube furnace, is passed through inert gas and is carbonized, 10 DEG C/min of heating rate, is carbonized 900 DEG C of final temperature, and be carbonized constant temperature
Time is 3h.Then activation temperature is adjusted to 700 DEG C, with N2For carrier gas, while being passed through 300ml/min activation vapor, activation
Time is 2h.It is cooled to room temperature to obtain microorganism based carbon molecular sieve (as shown in Figure 1) under an inert atmosphere after the completion of activation.
Comparative example 1: pure microorganism (chlorella) based carbon molecular sieve material
Alcohol solution is substituted for equivalent pure water, the ratio of carbonized product and water is replaced with into 90:10 in kneading process.Its
Remaining operating procedure is as embodiment 1.The chlorella carbon molecular sieve not handled.
Embodiment 2: change binder type
Firstly, a powdered carbonized product is prepared according to the method for embodiment 1.Select starch as binder, according to
The ratio of carbonized product, binder and water 65:25:10 are mediated uniformly, are put into mold and are pressed into molding mass, dry at room temperature.
The molding mass that above-mentioned steps are obtained is placed in tube furnace, is passed through inert gas and is carbonized, 10 DEG C/min of heating rate, carbon
Change 800 DEG C of final temperature, carbonization constant temperature time is 2h.Remaining operating procedure obtains as embodiment 1 using starch as binder system
Standby carbon molecular sieve material.
Embodiment 3: change the type of microorganism
Firstly, selecting photosynthetic bacteria for carbon source, gained sediment is placed in a beaker, 30ml alcohol-water mixture (first is added
Alcohol: water=2:1) it is stirred at room temperature for 24 hours.Solution uses first alcohol and water centrifuge washing for several times respectively.It obtains sample to be placed in baking oven, 80
DEG C drying 3h.
It takes out above-mentioned sample to be once carbonized, in N2550 DEG C are warming up to 10 DEG C/min under protection, keeps the temperature 2h.To cold
But it is ground to 100 mesh afterwards.With phenolic resin as binder, according to carbonized product, the ratio of binder and water 75:15:10
Example is mediated uniformly, is put into mold and is pressed into molding mass, dries at room temperature.The molding mass that above-mentioned steps are obtained is placed in tubular type
It in furnace, is passed through inert gas and is carbonized, 10 DEG C/min of heating rate is carbonized 950 DEG C of final temperature, and carbonization constant temperature time is 3h.It connects
Activation temperature is adjusted to 750 DEG C, with N2For carrier gas, while being passed through 300ml/min activation vapor, activation time 3h.It is living
It is cooled to room temperature (as shown in Figure 2) under an inert atmosphere after the completion of changing.
Embodiment 4: with the carbon molecular sieve prepared in embodiment 1, it is tested to CO2And CH4Absorption property
Using static adsorptive method, the coefficient of expansion of adsorbent equipment first is measured with sky glass tube, then weigh the carbon molecules of 0.5g
Sieve is placed in glass tube (1.2 × 6cm of Φ).Adsorbent equipment vacuumizes first, is subsequently passed the under test gas of 2bar, etc. systems
Valve is opened after stabilization by gas free wxpansion to the adsorption tank for being placed with carbon molecular sieve, records the balance pressure after stablizing, root
The adsorbance for being tested gas for going out carbon molecular sieve according to correlation data calculation, is finally calculated CO2/CH4Separation factor.
As shown in Table 1, the novel porous carbon molecular sieve of microorganism preparation has higher adsorption capacity and adsorptive selectivity.
The performance of porous carbon molecular sieve prepared by 1 embodiment 1,2,3 of table and comparative example 1 compares
Claims (6)
1. a kind of microorganism based carbon molecular sieve, which is characterized in that be prepared as follows to obtain:
(1) biological material pre-processes: by the medium centrifugal of microorganism, washing obtains microorganism precipitating, then by the micro- life of gained
Object precipitating is mixed with alcohol-water mixture, and stirring 12~for 24 hours, it is centrifuged, washs later, drying obtains biological material；
The microorganism is chlorella, photosynthetic bacteria or cyanobacteria；
The alcohol-water mixture is the mixed liquor of methanol and 2~4:1 of deionized water volume ratio；
(2) primary carbonization: calcining 0.5~2h for biological material obtained by step (1) under 400~550 DEG C, inert atmosphere, cold
But it to room temperature, grinds, obtains a carbonized stock, binder, water kneading are added in carbonized stock of gained uniformly, is placed in mold
In be pressed into molding mass, room temperature naturally dry is stand-by；
Carbonized stock, binder, water mass ratio be 60~80:10~40:0~10；
(3) secondary carbonization: step (2) ready molding mass is placed in tube furnace, is passed through inert gas and is carried out secondary carbonization,
5~10 DEG C/min of heating rate is carbonized 650~1000 DEG C of final temperature, and be carbonized 30~180min of constant temperature time；
(4) it activates: after step (3), 600~850 DEG C is adjusted the temperature to, with N2For carrier gas, while being passed through vapor and living
Change, activation time is 1~4h, is cooled to room temperature under an inert atmosphere later, obtains microorganism based carbon molecular sieve.
2. microorganism based carbon molecular sieve as described in claim 1, which is characterized in that in step (1), the alcohol-water mixture
Volumetric usage is calculated as 10~25mL/g with the quality that the microorganism is precipitated.
3. microorganism based carbon molecular sieve as described in claim 1, which is characterized in that in step (2), a carbonized stock,
Binder, water mass ratio be 65~75:15~25:10.
4. microorganism based carbon molecular sieve as described in claim 1, which is characterized in that in step (2), the binder is selected from phenol
Urea formaldehyde, polyvinyl alcohol, polyethylene glycol, starch, cellulose acetate, ligninsulfonate, humic acid or hydroxymethyl cellulose.
5. microorganism based carbon molecular sieve as described in claim 1, which is characterized in that in step (4), the water vapor flow rate is
300~600mL/min, N2Flow rate is 150~300mL/min.
6. application of the microorganism based carbon molecular sieve as described in claim 1 in gas-selectively adsorbing separation.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111871373A (en) * | 2020-07-31 | 2020-11-03 | 宁夏博实科技有限公司 | Adsorbent for separating nitrogen and methane and preparation method and application thereof |
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| 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 |
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