CN106467297A - A kind of preparation method of new carbon molecular sieve - Google Patents
A kind of preparation method of new carbon molecular sieve Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of new carbon molecular sieve, as follows including step：(1) by the metal organic framework compound being dried under the protection of atmosphere of inert gases, direct carbonization 24 hours, obtain carbonization material；(2) carbonization material of gained is soaked 8 15 hours in acid solution, then water washing, be dried, obtain final product carbon molecular sieve.The present invention, according to the tactical rule of raw material, repeats preparation, and one-step method is prepared into carbon molecular sieve, has process is simple, the stable feature of product quality.The carbon molecular sieve that the present invention is obtained has excellent property in the field such as separation of nitrogen and oxygen, methane and carbon dioxide, hydrogen and deuterium.
Description
Technical field
The present invention relates to material with carbon element technical field of chemistry, the preparation method of more particularly to a kind of new carbon molecular sieve.
Background technology
Carbon molecular sieve due to having the advantages that all even good stability in duct, in air separation, gas purification, harmful gass
The fields such as removal have a good application prospect.About 3000 tons/year of the production capacity of China's carbon molecular sieve now, adopts phenolic aldehyde more
Resin is raw material, is obtained by high temperature cabonization-activation " multistep processes " adjustment aperture, and its complex manufacturing, energy consumption are big, and produces
Quality is unstable, and quality is relatively low.
Chinese patent document CN 101696006A (application number：200910184952.2) disclose a kind of polyimides again
Close the method that bituminous coal prepares carbon molecular sieve, the raw material bituminous coal of selection heats 2～4 hours in nitrogen atmosphere at 300～600 DEG C；
It is crushed to below 80 mesh by after heating gained coal sample cool drying；Coal sample carbonization 1～4 when 500～1200 DEG C after pulverizing
Hour, or by the coal sample N after pulverizing, mix with polyamic acid solution, during mixing after the infiltration of N '-dimethyl formamide solvent
The mass content of polyamic acid is less than 50%, then by gained mixture grinding and mixing 1～3 hour, and when 500～1200 DEG C
Carbonization 1～4 hour；It is 2: 1～7: 1 addition KOH that carbonization gains are pressed alkali charcoal mass ratio, at 500～800 DEG C after grinding and mixing
When activate 1～4 hour；The acid that activation gains concentration is 0.1mol/L～2mol/L is carried out pickling, then is washed to neutrality
Obtain carbon molecular sieve.
Chinese patent document CN104709893A (application number：201310686410.1) disclose a kind of urging for battery
The manufacture method of the carbon molecular sieve of agent, it comprises the steps：First, carbon compound will be contained containing the polymerizable as carbon precursor
Thing and liquid carrier are mixed and made into the first mixture solution, and using described first mixture solution dipping template, this template is two
Silicon oxide molecular sieve micropore, its micropore that there is mesopore and connect mesopore；Secondly, form the polymerization of carbon precursor in this template micropore
Thing, is completed by being polymerized described carbon precursor in this template micropore；Again, by silicon dioxide oligomer, contain as carbon precursor
Polymerizable carbon compound and liquid carrier be mixed and made into the second mixture solution, using described second mixture solution dipping
The mesopore of this template；Then, in this template, in the hole forms carbon precursor polymer, by being polymerized described carbon in this template mesopore
Precursor completes；Then, using the described carbon precursor polymer in template described in method for pyrolysis carbonization；Finally, using can dissolve
The solution of silicon dioxide removes described template and described silicon dioxide oligomer, that is, obtain carbon molecular sieve.
Chinese patent document CN105460933A (application number：201511007746.6) disclose a kind of system of carbon molecular sieve
Preparation Method, the method adopts agricultural wastes walnut shell, Semen Castaneae shell and Corvic as raw material, and preparation process includes
The steps such as the preparation of raw material powder, molding, carbonization, carbon laydown.
Using different presomas as the raw material preparing carbon molecular sieve in said method, but all there is complex process, life
The shortcoming that production capacity consumption is big, carbon molecular sieve quality is unstable.Especially, tackle in nitrogen/oxygen detached space division molecular sieve, above-mentioned
The aperture of the carbon molecular sieve of method preparation is difficult to accurate adjustment between nitrogen and the kinetic diameter of oxygen, thus can not be fine
Ground meets the detached purpose of nitrogen/oxygen in current industrial.
Content of the invention
For the deficiency in existing carbon molecular sieve technology of preparing, the invention provides a kind of preparation side of new carbon molecular sieve
Method, especially a kind of method with metal-organic framework compound as presoma, carbon molecular sieve being prepared using one step carbonization,
The shortcoming that carbon molecular sieve complicated process of preparation, unstable product quality can be solved.
Technical scheme is as follows：
A kind of preparation method of new carbon molecular sieve is as follows including step：
(1) by the metal-organic framework compound being dried under the protection of atmosphere of inert gases, direct carbonization 2-4 hour,
Obtain carbonization material；
(2) carbonization material of gained is soaked in acid solution 8-15 hour, then water washing, be dried, obtain final product carbon molecule
Sieve.
According to the invention it is preferred to, metal-organic framework compound described in step (1) be organic ligand with metal from
Son is using the metal-organic framework compound being self-assembly of；
It is further preferred that described organic ligand is the Carboxylic acid ligand with rigid structure or the nitrogen with rigid structure
Heterocyclic ligand；The Carboxylic acid ligand of further preferably center phenyl ring and benzamido group substituent group.
It is further preferred that described metal ion is transition metal ionss, more preferably ferrum, cobalt, nickel, copper, zinc ion.
According to the invention it is preferred to, the metal-organic framework compound described in step (1) is:Zn3(L1)(H2O)3、Zn2
(L2)(H2O)2、Co3(L3)(H2O)3、Co3(L1)(H2O)3；Wherein, L1 is：2,4,6- trimethyl -1,3,5- tribenzylamine bases-(1-
Amino -3,5- dioctyl phthalate), L2 is：2,3,5,6- tetramethyls-Isosorbide-5-Nitrae-dibenzyl amido-(1- amino -3,5- dioctyl phthalate), L3 is：1,
3,5- tribenzylamine bases-(1- amino -3,5- dioctyl phthalate).
According to the invention it is preferred to, the noble gases described in step (1) are nitrogen, argon or helium.
According to the invention it is preferred to, in step (1), the temperature of carbonization is 600 DEG C to 800 DEG C.
According to the invention it is preferred to, the acid described in step (2) is hydrochloric acid, sulphuric acid or Fluohydric acid., it is further preferred that
The concentration of hydrochloric acid is 10-37wt%, and the concentration of sulphuric acid or Fluohydric acid. is 10-40wt%.
According to the invention it is preferred to, in step (2), baking temperature is 100-130 DEG C.
According to the present invention, described metal-organic framework compound is commercially available to be obtained, and also can be prepared into by prior art
Arrive；Preferably, it is prepared as follows obtaining：
Organic ligand is stoichiometrically mixed with slaine, adds solvent, be placed in the reactor of sealing, to be mixed
Or after ultrasonic dissolution, put into and be heated to reaction temperature in heating furnace or baking oven and reacted.After completion of the reaction, gained is anti-
Answer product to filter, washed with solvent, be dried, obtain final product.
Beneficial effects of the present invention are as follows：
1 the invention provides a kind of relatively simple method preparing carbon molecular sieve, and the tactical rule of raw material, can
Repeat to prepare, one-step method can be prepared into carbon molecular sieve, there is process is simple, the stable feature of product quality.This is for simplification carbon
The preparation technology of molecular sieve, reduce carbon molecular sieve production cost, lifting carbon molecular sieve quality significant.
2nd, carbonization temperature of the present invention has material impact for the pore structure of molecular sieve, under higher carbonization temperature, can expand
The aperture of big carbon molecular sieve.Therefore, pore size and the pore passage structure of carbon molecular sieve can be adjusted by adjusting calcining heat.
3rd, the carbon molecular sieve that the present invention is obtained is in the separation etc. of nitrogen and oxygen, methane and carbon dioxide, hydrogen and deuterium
Field has excellent property.Its separation principle is molecular sieve principle, specially：Different power using gas with various molecule
Learn diameter so as to there are different diffusion rates in the narrow and small duct of carbon molecular sieve, thus reaching detached effect.
Brief description
Fig. 1 is the schematic diagram before and after carbon molecular sieve carbonization of the present invention.
Fig. 2 is the nitrogen and oxygen adsorption isotherm (25 DEG C) on carbon molecular sieve in application examples 1 of the present invention.
Fig. 3 is the nitrogen and oxygen curve of adsorption kinetics (25 DEG C) on carbon molecular sieve in application examples 1 of the present invention.
Fig. 4 is curve of adsorption kinetics (25 DEG C) on carbon molecular sieve for the methane and carbon dioxide 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 be conventional commercial products, device therefor is conventional equipment.
Embodiment 1
A kind of preparation method of new carbon molecular sieve is as follows including step：
(1) the metal-organic framework compound Zn that will be dried3(L1)(H2O)3Under the protection of nitrogen atmosphere, at 600 DEG C
Direct carbonization 2 hours, obtains carbonization material.Wherein, L1 is：2,4,6- trimethyl -1,3,5- tribenzylamine bases-(1- amino -3,5- bis-
Formic acid).
(2) carbonization material of gained is soaked 8 hours in the hydrochloric acid of 20wt%, then distilled water wash, do for 120 DEG C
Dry, obtain final product carbon molecular sieve.
Metal-organic framework compound described in the present embodiment is prepared as follows obtaining：
Ligand L 1 (0.140 gram) is mixed with zinc nitrate hexahydrate (0.238 gram), adds DMF (20 millis
Rise), deionized water (1 milliliter), after being sufficiently mixed, above-mentioned reactant is placed in 50 milliliters of teflon-lined reactor
In.After reactor is sealed, it is placed in baking oven and to react 24 hours at 90 DEG C, after completion of the reaction, by obtained metal-organic
Framework Compound Filter, is washed with 10 milliliters of DMFs, dries in 100 DEG C, obtains final product.
Embodiment 2
A kind of preparation method of new carbon molecular sieve is as follows including step：
(1) the metal-organic framework compound Zn that will be dried2(L2)(H2O)2Under the protection of argon atmosphere, at 700 DEG C
Direct carbonization 3 hours, obtains carbonization material.Wherein, L2 is：2,3,5,6- tetramethyl -1,4- dibenzyl amido-(1- amino -3,5- two
Formic acid)
(2) carbonization material of gained is soaked 10 hours in the sulphuric acid of 20wt%, then distilled water wash, do for 100 DEG C
Dry, obtain final product carbon molecular sieve.
Metal-organic framework compound described in the present embodiment is prepared as follows obtaining：
Ligand L 2 (0.104 gram) is mixed with zinc nitrate hexahydrate (0.238 gram), adds DMF (6 millis
Rise), ethanol (6 milliliters), deionized water (4 milliliters), after being sufficiently mixed, above-mentioned reactant is placed in 50 milliliters of politef
In the reactor of liner.After reactor is sealed, it is placed in baking oven and reacts 24 hours at 90 DEG C, after completion of the reaction, by gained
The metal-organic framework Compound Filter arriving, is washed with 10 milliliters of DMFs, dries in 100 DEG C.
Embodiment 3
A kind of preparation method of new carbon molecular sieve is as follows including step：
(1) the metal-organic framework compound Co that will be dried3(L3)(H2O)3Under the protection of helium atmosphere, at 800 DEG C
Direct carbonization 4 hours, obtains carbonization material.Wherein, L3 is：1,3,5- tribenzylamine base-(1- amino -3,5- dioctyl phthalate)
(2) carbonization material of gained is soaked 15 hours in the Fluohydric acid. of 20wt%, then distilled water wash, 130 DEG C
It is dried, obtain final product carbon molecular sieve.
Metal-organic framework compound described in the present embodiment is prepared as follows obtaining：
Ligand L 3 (0.131 gram) is mixed with cobalt nitrate hexahydrate (0.175 gram), adds DMF (6 millis
Rise), ethanol (6 milliliters), deionized water (4 milliliters), after being sufficiently mixed, above-mentioned reactant is placed in 50 milliliters of politef
In the reactor of liner.After reactor is sealed, it is placed in baking oven and reacts 24 hours at 100 DEG C, after completion of the reaction, by gained
The metal-organic framework Compound Filter arriving, is washed with 10 milliliters of DMFs, dries in 100 DEG C.
Embodiment 4
A kind of preparation method of new carbon molecular sieve is as follows including step：
(1) the metal-organic framework compound Co that will be dried3(L1)(H2O)3Under the protection of nitrogen atmosphere, at 700 DEG C
Direct carbonization 3 hours, obtains carbonization material.Wherein, L1 is：2,4,6- trimethyl -1,3,5- tribenzylamine bases-(1- amino -3,5- bis-
Formic acid).
(2) carbonization material of gained is soaked 13 hours in the hydrochloric acid of 10wt%, then distilled water wash, do for 110 DEG C
Dry, obtain final product carbon molecular sieve.
Metal-organic framework compound described in the present embodiment is prepared as follows obtaining：
Ligand L 2 (0.140 gram) is mixed with cobalt nitrate hexahydrate (0.175 gram), adds DMF (6 millis
Rise), ethanol (6 milliliters), deionized water (4 milliliters), after being sufficiently mixed, above-mentioned reactant is placed in 50 milliliters of politef
In the reactor of liner.After reactor is sealed, it is placed in baking oven and reacts 24 hours at 100 DEG C, after completion of the reaction, by gained
The metal-organic framework Compound Filter arriving, is washed with 10 milliliters of DMFs, dries in 100 DEG C.
Application examples 1
The carbon molecular sieve that embodiment 1 is obtained is used for the separation of nitrogen and oxygen, and step is as follows：
Take 50mg carbon molecular sieve sample, be placed in the sample basket of weight adsorption instrument (IGA-001).By sample in 200 DEG C with
And activate 12 hours under fine vacuum.It is cooled to after room temperature after sample, control test temperature to be 25 DEG C by water-bath.Set different
Pressure, determination sample oxygen at various pressures and nitrogen adsorption isotherm, as shown in Figure 2.
Measure pressure in the range of 1～1.5bar, the oxygen and nitrogen kinetics diffusion rate on sample, compares two
The difference of the kinetics diffusion rate of person, as shown in Figure 3.
Show, at 25 DEG C, oxygen is on carbon molecular sieve by Fig. 2 nitrogen and oxygen adsorption isotherm on carbon molecular sieve
Equilibrium adsorption capacity be greater than equilibrium adsorption capacity on carbon molecular sieve for the nitrogen, both equilibrium adsorption capacities under 1bar pressure it
Than for 4.29 it is shown that certain adsorptive selectivity.
From the figure 3, it may be seen that with respect to equilibrium adsorption capacity, nitrogen molecule and oxygen molecule show significantly on carbon molecular sieve
Adsorption dynamics adsorption kinetics difference.Oxygen will be significantly faster than that absorption speed on carbon molecular sieve for the nitrogen in the rate of adsorption on carbon molecular sieve
Rate.Nitrogen molecule needs about 14800 seconds (247 minutes) to can be only achieved balance, however, oxygen molecule only need to 1094 seconds (18 points
Clock) just can reach balance.Both adsorbing filament technique are respectively：kO2=5.03 × 10-3S-1, kN2=3.601 × 10-4, inhale
The ratio of attached speed reaches 14, shows excellent dynamic absorption selectivity, has good application in nitrogen/oxygen separates
Prospect.
Application examples 2
The carbon molecular sieve that embodiment 2 is obtained is used for the separation of methane and carbon dioxide, and step is as follows：
Take 50mg carbon molecular sieve sample, be placed in the sample basket of weight adsorption instrument (IGA-001).By sample in 200 DEG C with
And activate 12 hours under fine vacuum.It is cooled to after room temperature after sample, control test temperature to be 25 DEG C by water-bath.Set different
Pressure, determination sample methane at various pressures and carbon dioxide adsorption isothermal line, as shown in Figure 4.
Curve of adsorption kinetics on carbon molecular sieve for the methane and carbon dioxide as shown in Figure 4 shows：Carbon dioxide exists
Certain adsorbance is shown on carbon molecular sieve, however, methane adsorbance on this sample is almost nil.The hole of carbon molecular sieve
Between oxygen and the kinetic diameter of nitrogen, the methane molecule with bigger molecule diameter can not enter carbon molecular sieve in footpath
In the hole, therefore this carbon molecular sieve show obvious kinetics sieve effect to carbon dioxide and methane molecule, show higher
Adsorptive selectivity.
Claims (10)
1. a kind of preparation method of new carbon molecular sieve, as follows including step：
(1) by the metal-organic framework compound being dried under the protection of atmosphere of inert gases, direct carbonization 2-4 hour, obtain carbon
Compound matter；
(2) carbonization material of gained is soaked in acid solution 8-15 hour, then water washing, be dried, obtain final product carbon molecular sieve.
2. the preparation method of new carbon molecular sieve according to claim 1 it is characterised in that metal described in step (1)-
Organic frame compound is for organic ligand and metal ion using the metal-organic framework compound being self-assembly of.
3. the preparation method of new carbon molecular sieve according to claim 2 is it is characterised in that organic described in step (1)
Part is the Carboxylic acid ligand with rigid structure or the n-heterocyclic ligand with rigid structure.
4. the preparation method of new carbon molecular sieve according to claim 2 is it is characterised in that organic described in step (1)
Part is the Carboxylic acid ligand containing center phenyl ring and benzamido group substituent group.
5. the preparation method of new carbon molecular sieve according to claim 2 is it is characterised in that metal described in step (1)
Ion is transition metal ionss.
6. the preparation method of new carbon molecular sieve according to claim 5 is it is characterised in that transition described in step (1)
Metal ion is ferrum, cobalt, nickel, copper, zinc ion.
7. the preparation method of new carbon molecular sieve according to claim 1 it is characterised in that metal described in step (1)-
Organic frame compound is:Zn3(L1)(H2O)3、Zn2(L2)(H2O)2、Co3(L3)(H2O)3Or Co3(L1)(H2O)3；Wherein, L1
For：2,4,6- trimethyl -1,3,5- tribenzylamine bases-(1- amino -3,5- dioctyl phthalate), L2 is：2,3,5,6- tetramethyl -1,4- two
Benzamido group-(1- amino -3,5- dioctyl phthalate), L3 is：1,3,5- tribenzylamine base-(1- amino -3,5- dioctyl phthalate).
8. new carbon molecular sieve according to claim 1 preparation method it is characterised in that in step (1) carbonization temperature
Spend for 600 DEG C to 800 DEG C.
9. the preparation method of new carbon molecular sieve according to claim 1 is it is characterised in that the acid described in step (2)
For hydrochloric acid, sulphuric acid or Fluohydric acid.；Preferably, the concentration of hydrochloric acid is 10-37wt%, and the concentration of sulphuric acid or Fluohydric acid. is 10-
40wt%.
10. the preparation method of new carbon molecular sieve according to claim 1 is it is characterised in that baking temperature in step (2)
For 100-130 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106976859A (en) * | 2017-03-14 | 2017-07-25 | 同济大学 | A kind of method that ultramicropore carbon nano-particles are prepared by presoma of metal organic framework |
| CN106986324A (en) * | 2017-03-10 | 2017-07-28 | 江苏海能动力科技有限公司 | It is a kind of for hollow porous carbon ball electrode material of ultracapacitor and preparation method thereof |
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| CN106986324A (en) * | 2017-03-10 | 2017-07-28 | 江苏海能动力科技有限公司 | It is a kind of for hollow porous carbon ball electrode material of ultracapacitor and preparation method thereof |
| CN106976859A (en) * | 2017-03-14 | 2017-07-25 | 同济大学 | A kind of method that ultramicropore carbon nano-particles are prepared by presoma of metal organic framework |
| CN106976859B (en) * | 2017-03-14 | 2019-01-25 | 同济大学 | A method of using metal organic framework as precursor preparation ultramicropore carbon nano-particles |
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