CN106467297B - A kind of preparation method of carbon molecular sieve - Google Patents
A kind of preparation method of carbon molecular sieve Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of novel carbon molecular sieve, comprise the following steps that dry metal-organic framework compound under the protection of atmosphere of inert gases, direct carbonization 2-4 hours, is obtained carbonization material by (1)；(2) resulting carbonization material is impregnated 8-15 hours in acid solution, then water washing, dry to get carbon molecular sieve.The present invention repeats preparation according to the tactical rule of raw material, and one-step method is prepared into carbon molecular sieve, has the characteristics of simple process, stable product quality.Carbon molecular sieve produced by the present invention has excellent property in fields such as the separation of nitrogen and oxygen, methane and carbon dioxide, hydrogen and deuterium.
Description
Technical field
The present invention relates to carbon material technical field of chemistry, more particularly to a kind of preparation method of novel carbon molecular sieve.
Background technique
Carbon molecular sieve is good due to having many advantages, such as the uniform stability in duct, in air separation, gas purification, pernicious gas
The fields such as removal have a good application prospect.About 3000 tons/year of production capacity of present China carbon molecular sieve, mostly use phenolic aldehyde
Resin is raw material, is made by high temperature cabonization-activation " multistep processes " adjustment aperture, and production technology is complicated, energy consumption is high, and is produced
Quality is unstable, and quality is lower.
Chinese patent document CN 101696006A (it is multiple 200910184952.2) application number: to disclose a kind of polyimides
The method that bituminous coal prepares carbon molecular sieve is closed, the raw material bituminous coal of selection heats 2~4 hours in nitrogen atmosphere at 300~600 DEG C；
The cooling crushed after being dried to 80 mesh of gained coal sample or less will be heated；The charing 1~4 at 500~1200 DEG C by smashed coal sample
Hour, or by smashed coal sample N, mixed after the infiltration of N '-dimethyl formamide solvent with polyamic acid solution, when mixing
The mass content of polyamic acid was no more than 50%, then by gained mixture grinding and mixing 1~3 hour, and at 500~1200 DEG C
Charing 1~4 hour；Charing gains are pressed into alkali charcoal mass ratio for 2: 1~7: 1 addition KOH, at 500~800 DEG C after grinding and mixing
When activate 1~4 hour；Gains will be activated and carry out pickling with the acid that concentration is 0.1mol/L~2mol/L, then be washed to neutrality
Obtain carbon molecular sieve.
Chinese patent document CN104709893A (application number: 201310686410.1) discloses a kind of urging for battery
The manufacturing method of the carbon molecular sieve of agent comprising following steps: firstly, by containing polymerizable containing carbon compound as carbon precursor
Object and liquid carrier are mixed and made into the first mixture solution, impregnate template using first mixture solution, which is two
Silicon oxide molecular sieve micropore, the micropore with mesoporous and connection mesoporous；Secondly, forming carbon precursor polymerization in the template micropore
Object is completed by polymerizeing the carbon precursor in the template micropore；Again, by silica oligomer, containing as carbon precursor
Polymerizable carbon compound and liquid carrier be mixed and made into the second mixture solution, use second mixture solution impregnate
The mesoporous of the template；Then, carbon precursor polymer is formed in the template mesoporous, by polymerizeing the carbon in the template mesoporous
Precursor is completed；Then, the carbon precursor polymer being carbonized in the template using method for pyrolysis；Finally, using that can dissolve
The solution of silica removes the template and the silica oligomer to get carbon molecular sieve is arrived.
Chinese patent document CN105460933A (application number: 201511007746.6) discloses a kind of system of carbon molecular sieve
Preparation Method, using agricultural wastes walnut shell, chestnut shell and Corvic as raw material, preparation process includes this method
The preparation of raw material powder, molding, carbonization, Carbon deposition.
Using different presomas as the raw material for preparing carbon molecular sieve in the above method, but all there is complex process, life
Produce the shortcomings that energy consumption is high, carbon molecular sieve unstable quality.Particularly, the space division molecular sieve separated in nitrogen/oxygen is coped with, it is above-mentioned
The aperture of the carbon molecular sieve of method preparation is difficult accurately to be adjusted between nitrogen and the kinetic diameter of oxygen, thus cannot be fine
Ground meets the purpose that nitrogen/oxygen separates in current industrial.
Summary of the invention
For the deficiency in existing carbon molecular sieve technology of preparing, the present invention provides a kind of preparation sides of novel carbon molecular sieve
Method, especially one kind is using metal-organic framework compound as presoma, the method for preparing carbon molecular sieve using one step carbonization,
It can solve the disadvantage that carbon molecular sieve preparation process complexity, unstable product quality.
Technical scheme is as follows:
A kind of preparation method of carbon molecular sieve, comprises the following steps that
(1) by dry metal-organic framework compound under the protection of atmosphere of inert gases, direct carbonization 2-4 hours,
Obtain carbonization material；
(2) resulting carbonization material is impregnated 8-15 hours in acid solution, then water washing, dry to get carbon molecules
Sieve.
, according to the invention it is preferred to, metal-organic framework compound described in step (1) be organic ligand and metal from
Son is using the metal-organic framework compound being self-assembly of；
It is further preferred that the organic ligand is the Carboxylic acid ligand with rigid structure or the nitrogen with rigid structure
Heterocyclic ligand；The further preferably Carboxylic acid ligand of center phenyl ring and benzamido group substituent group.
It is further preferred that the metal ion is transition metal ions, more preferable iron, cobalt, nickel, copper, zinc ion.
, according to the invention it is preferred to, metal-organic framework compound described in step (1) are as follows: Zn3(L1)(H2O)3、Zn2
(L2)(H2O)2、Co3(L3)(H2O)3、Co3(L1)(H2O)3；Wherein, L1 are as follows: 2,4,6- trimethyls -1,3,5- tribenzylamine base-(1-
Amino -3,5- dioctyl phthalate), L2 are as follows: 2,3,5,6- tetramethyls-Isosorbide-5-Nitrae-dibenzyl amido-(1- amino -3,5- dioctyl phthalate), L3 are as follows: 1,
3,5- tribenzylamine bases-(1- amino -3,5- dioctyl phthalate).
, according to the invention it is preferred to, inert gas described in step (1) is nitrogen, argon gas or helium.
, according to the invention it is preferred to, the temperature carbonized in step (1) is 600 DEG C to 800 DEG C.
, according to the invention it is preferred to, acid described in step (2) be hydrochloric acid, sulfuric acid or hydrofluoric acid, it is further preferred that
The concentration of hydrochloric acid is 10-37wt%, and the concentration of sulfuric acid or hydrofluoric acid is 10-40wt%.
, according to the invention it is preferred to, drying temperature is 100-130 DEG C in step (2).
According to the present invention, the metal-organic framework compound is commercially available obtains, and can also obtain by prior art preparation
It arrives；Preferably, it is prepared as follows to obtain:
Organic ligand is stoichiometrically mixed with metal salt, solvent is added, is placed in the reactor of sealing, it is to be mixed
Or after ultrasonic dissolution, it is put into and is heated to reaction temperature in heating furnace or baking oven and is reacted.It after completion of the reaction, will be resulting anti-
Answer product to filter, washed with solvent, it is dry to get.
Beneficial effects of the present invention are as follows:
1, the method for preparing carbon molecular sieve relatively simple the present invention provides one kind, and the tactical rule of raw material, can
Repeat to prepare, can one-step method be prepared into carbon molecular sieve, there is simple process, the characteristics of stable product quality.This is for simplifying carbon
The preparation process of molecular sieve, the production cost for reducing carbon molecular sieve, the quality for promoting carbon molecular sieve are of great significance.
2, carbonization temperature of the present invention there is great influence can expand under higher carbonization temperature the pore structure of molecular sieve
The aperture of big carbon molecular sieve.It therefore, can be by adjusting calcination temperature, to adjust the pore size and cellular structure of carbon molecular sieve.
3, carbon molecular sieve produced by the present invention is in nitrogen and oxygen, methane and carbon dioxide, hydrogen and the separation of deuterium etc.
Field has excellent property.Its separation principle is molecular sieve principle, specifically: utilize the different power of gas with various molecule
Diameter is learned, makes it that there is different diffusion rates in the narrow duct of carbon molecular sieve, to achieve the effect that separation.
Detailed description of the invention
Fig. 1 is the schematic diagram of carbon molecular sieve of the present invention charing front and back.
Fig. 2 is the adsorption isotherm (25 DEG C) of nitrogen and oxygen on carbon molecular sieve in application examples 1 of the present invention.
Fig. 3 is the curve of adsorption kinetics (25 DEG C) of nitrogen and oxygen on carbon molecular sieve in application examples 1 of the present invention.
Fig. 4 is curve of adsorption kinetics (25 DEG C) of the methane and carbon dioxide on carbon molecular sieve in application examples 2 of the present invention.
Specific embodiment
Below by specific embodiment, the present invention will be further described, but not limited to this.
Raw materials used in embodiment is regular market purchase product, and device therefor is conventional equipment.
Embodiment 1
A kind of preparation method of carbon molecular sieve, comprises the following steps that
(1) by dry metal-organic framework compound Zn3(L1)(H2O)3Under the protection of nitrogen atmosphere, at 600 DEG C
Direct carbonization 2 hours, obtain carbonization material.Wherein, L1 are as follows: 2,4,6- trimethyls -1,3,5- tribenzylamine base-(1- amino -3,5- bis-
Formic acid).
(2) resulting carbonization material is impregnated 8 hours in the hydrochloric acid of 20wt%, then distills water washing, 120 DEG C dry
It is dry to get carbon molecular sieve.
Metal-organic framework compound described in the present embodiment is prepared as follows to obtain:
Ligand L 1 (0.140 gram) is mixed with zinc nitrate hexahydrate (0.238 gram), n,N-Dimethylformamide (20 millis are added
Rise), deionized water (1 milliliter), after being sufficiently mixed, above-mentioned reactant is placed in the reaction kettle of 50 milliliters of polytetrafluoroethyllining lining
In.After reaction kettle is sealed, it is placed in baking oven and is reacted 24 hours at 90 DEG C, it is after completion of the reaction, obtained metal-is organic
Frame Compound Filter is washed with 10 milliliters of n,N-Dimethylformamide, in 100 DEG C drying to get.
Embodiment 2
A kind of preparation method of carbon molecular sieve, comprises the following steps that
(1) by dry metal-organic framework compound Zn2(L2)(H2O)2Under the protection of argon atmosphere, at 700 DEG C
Direct carbonization 3 hours, obtain carbonization material.Wherein, L2 are as follows: 2,3,5,6- tetramethyls-Isosorbide-5-Nitrae-dibenzyl amido-(1- amino -3,5- bis-
Formic acid)
(2) resulting carbonization material is impregnated 10 hours in the sulfuric acid of 20wt%, then distills water washing, 100 DEG C dry
It is dry to get carbon molecular sieve.
Metal-organic framework compound described in the present embodiment is prepared as follows to obtain:
Ligand L 2 (0.104 gram) is mixed with zinc nitrate hexahydrate (0.238 gram), n,N-Dimethylformamide (6 millis are added
Rise), ethyl alcohol (6 milliliters), deionized water (4 milliliters), after being sufficiently mixed, above-mentioned reactant is placed in 50 milliliters of polytetrafluoroethylene (PTFE)
In the reaction kettle of liner.After reaction kettle is sealed, it is placed in baking oven and is reacted 24 hours at 90 DEG C, after completion of the reaction, by gained
The metal-organic framework Compound Filter arrived is washed with 10 milliliters of n,N-Dimethylformamide, is dried in 100 DEG C.
Embodiment 3
A kind of preparation method of carbon molecular sieve, comprises the following steps that
(1) by dry metal-organic framework compound Co3(L3)(H2O)3Under the protection of helium atmosphere, at 800 DEG C
Direct carbonization 4 hours, obtain carbonization material.Wherein, L3 are as follows: 1,3,5- tribenzylamine base-(1- amino -3,5- dioctyl phthalate)
(2) resulting carbonization material is impregnated 15 hours in the hydrofluoric acid of 20wt%, then distills water washing, 130 DEG C
Drying is to get carbon molecular sieve.
Metal-organic framework compound described in the present embodiment is prepared as follows to obtain:
Ligand L 3 (0.131 gram) is mixed with cobalt nitrate hexahydrate (0.175 gram), n,N-Dimethylformamide (6 millis are added
Rise), ethyl alcohol (6 milliliters), deionized water (4 milliliters), after being sufficiently mixed, above-mentioned reactant is placed in 50 milliliters of polytetrafluoroethylene (PTFE)
In the reaction kettle of liner.After reaction kettle is sealed, it is placed in baking oven and is reacted 24 hours at 100 DEG C, after completion of the reaction, by gained
The metal-organic framework Compound Filter arrived is washed with 10 milliliters of n,N-Dimethylformamide, is dried in 100 DEG C.
Embodiment 4
A kind of preparation method of carbon molecular sieve, comprises the following steps that
(1) by dry metal-organic framework compound Co3(L1)(H2O)3Under the protection of nitrogen atmosphere, at 700 DEG C
Direct carbonization 3 hours, obtain carbonization material.Wherein, L1 are as follows: 2,4,6- trimethyls -1,3,5- tribenzylamine base-(1- amino -3,5- bis-
Formic acid).
(2) resulting carbonization material is impregnated 13 hours in the hydrochloric acid of 10wt%, then distills water washing, 110 DEG C dry
It is dry to get carbon molecular sieve.
Metal-organic framework compound described in the present embodiment is prepared as follows to obtain:
Ligand L 2 (0.140 gram) is mixed with cobalt nitrate hexahydrate (0.175 gram), n,N-Dimethylformamide (6 millis are added
Rise), ethyl alcohol (6 milliliters), deionized water (4 milliliters), after being sufficiently mixed, above-mentioned reactant is placed in 50 milliliters of polytetrafluoroethylene (PTFE)
In the reaction kettle of liner.After reaction kettle is sealed, it is placed in baking oven and is reacted 24 hours at 100 DEG C, after completion of the reaction, by gained
The metal-organic framework Compound Filter arrived is washed with 10 milliliters of n,N-Dimethylformamide, is dried in 100 DEG C.
Application examples 1
Carbon molecular sieve made from embodiment 1 is used for the separation of nitrogen and oxygen, steps are as follows:
50mg carbon molecular sieve sample is taken, is placed in the sample basket of weight adsorption instrument (IGA-001).By sample in 200 DEG C with
And it is activated 12 hours under high vacuum.After sample is cooled to room temperature, controlling test temperature by water-bath is 25 DEG C.It sets different
Pressure, measurement sample oxygen at various pressures and nitrogen adsorption isotherm, as shown in Figure 2.
Pressure is measured out of 1~1.5bar, the dynamics diffusion rate of oxygen and nitrogen on sample compares two
The difference of the dynamics diffusion rate of person, as shown in Figure 3.
Show that at 25 DEG C, oxygen is on carbon molecular sieve by the adsorption isotherm of Fig. 2 nitrogen and oxygen on carbon molecular sieve
Equilibrium adsorption capacity be greater than equilibrium adsorption capacity of the nitrogen on carbon molecular sieve, equilibrium adsorption capacity of the two under 1bar pressure it
Than being 4.29, it is shown that certain adsorptive selectivity.
From the figure 3, it may be seen that nitrogen molecule and oxygen molecule are shown significantly on carbon molecular sieve relative to equilibrium adsorption capacity
Adsorption dynamics adsorption kinetics difference.The rate of adsorption of the oxygen on carbon molecular sieve will be significantly faster than that absorption speed of the nitrogen on carbon molecular sieve
Rate.Nitrogen molecule needs about 14800 seconds (247 minutes) to can be only achieved balance, however, oxygen molecule only need 1094 seconds (18 points
Clock) balance can be reached.The adsorbing filament technique of the two is respectively as follows: kO2=5.03 × 10-3S-1, kN2=3.601 × 10-4, inhale
The ratio between attached rate reaches 14, shows excellent dynamic absorption selectivity, has good application in nitrogen/oxygen separation
Prospect.
Application examples 2
Carbon molecular sieve made from embodiment 2 is used for the separation of methane and carbon dioxide, steps are as follows:
50mg carbon molecular sieve sample is taken, is placed in the sample basket of weight adsorption instrument (IGA-001).By sample in 200 DEG C with
And it is activated 12 hours under high vacuum.After sample is cooled to room temperature, controlling test temperature by water-bath is 25 DEG C.It sets different
Pressure, the methane and carbon dioxide adsorption thermoisopleth of measurement sample at various pressures, as shown in Figure 4.
Curve of adsorption kinetics of the methane and carbon dioxide as shown in Figure 4 on carbon molecular sieve is shown: carbon dioxide exists
Certain adsorbance is shown on carbon molecular sieve, however, the adsorbance of methane on this sample is almost nil.The hole of carbon molecular sieve
For diameter between oxygen and the kinetic diameter of nitrogen, the methane molecule with bigger molecule diameter not can enter carbon molecular sieve
In hole, therefore the carbon molecular sieve shows apparent dynamics sieve effect to carbon dioxide and methane molecule, shows higher
Adsorptive selectivity.
Claims (3)
1. a kind of preparation method of carbon molecular sieve, comprises the following steps that
(1) by dry metal-organic framework compound under the protection of atmosphere of inert gases, direct carbonization 2-4 hours, carbon
The temperature of change is 600 DEG C to 800 DEG C, obtains carbonization material；
The metal-organic framework compound is that organic ligand and metal ion use the metal-being self-assembly of to have machine frame
Frame compound；
The organic ligand is the Carboxylic acid ligand containing center phenyl ring and benzamido group substituent group；
The metal ion is iron, cobalt, nickel, copper or zinc ion；
(2) resulting carbonization material is impregnated 8-15 hours in acid solution, then water washing, dry to get carbon molecular sieve.
2. the preparation method of carbon molecular sieve according to claim 1, which is characterized in that acid described in step (2) is salt
Acid, sulfuric acid or hydrofluoric acid；
The concentration of hydrochloric acid is 10-37 wt%, and the concentration of sulfuric acid or hydrofluoric acid is 10-40 wt%.
3. the preparation method of carbon molecular sieve according to claim 1, which is characterized in that drying temperature is in step (2)
100-130℃。
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| CN101885485A (en) * | 2010-07-08 | 2010-11-17 | 深圳市普迈达科技有限公司 | Method for preparing carbon material with high specific surface area by using metallic organic framework material as template |
| CN104418315A (en) * | 2013-08-22 | 2015-03-18 | 苏州奥索特新材料有限公司 | Preparation method of ordered mesoporous carbon material with high specific surface area by using metal organic skeleton |
| CN104710965A (en) * | 2015-04-02 | 2015-06-17 | 北京科技大学 | Method for preparing multilevel porous carbon base composite phase change material |
| CN105481043A (en) * | 2016-01-07 | 2016-04-13 | 大连理工大学 | Method for adsorbing organic pollutants in water environment with porous carbon obtained by carbonizing metal organic framework material as adsorbent |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885485A (en) * | 2010-07-08 | 2010-11-17 | 深圳市普迈达科技有限公司 | Method for preparing carbon material with high specific surface area by using metallic organic framework material as template |
| CN104418315A (en) * | 2013-08-22 | 2015-03-18 | 苏州奥索特新材料有限公司 | Preparation method of ordered mesoporous carbon material with high specific surface area by using metal organic skeleton |
| CN104710965A (en) * | 2015-04-02 | 2015-06-17 | 北京科技大学 | Method for preparing multilevel porous carbon base composite phase change material |
| CN105481043A (en) * | 2016-01-07 | 2016-04-13 | 大连理工大学 | Method for adsorbing organic pollutants in water environment with porous carbon obtained by carbonizing metal organic framework material as adsorbent |
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