CN104689791B - Preparation and modification methods for solid material Zr-CN for adsorbing CO2 - Google Patents
Preparation and modification methods for solid material Zr-CN for adsorbing CO2 Download PDFInfo
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- CN104689791B CN104689791B CN201510054479.1A CN201510054479A CN104689791B CN 104689791 B CN104689791 B CN 104689791B CN 201510054479 A CN201510054479 A CN 201510054479A CN 104689791 B CN104689791 B CN 104689791B
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- 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
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Abstract
The invention provides a preparation method for a solid material Zr-CN for adsorbing CO2. The preparation method comprises the following steps: dissolving a metal salt A into 80ml of de-ionized water to form a solution A1; adding a metal salt B into the solution A1, and stirring at 30-50 DEG C for 3-5 hours to obtain a first solid product; washing the first solid product with the de-ionized water until the first solid product is neutral; drying the washed first solid product at 30-50 DEG C for 12-24 hours; and putting the product in a vacuum drying box at 80-100 DEG C and drying for 6-8 hours to obtain the solid material Zr-CN. The material has a good adsorption amount to the CO2 under a relatively low temperature and a relatively low CO2 pressure environment.
Description
[technical field]
The present invention relates to co2Sorbing material is and in particular to one kind efficiently can be inhaled in lower temperature and lower pressure environment
Attached co2Solid material zr-cn and its modifier preparation method.
[background technology]
At present, the discharge of industrial waste gas has caused co in air2Concentration sharply increases, thus aggravating greenhouse effects.Therefore,
co2Trapping technique is paid high attention to by various countries.
co2In trapping technique, using ammoniacal liquor and co2Chemical reaction is occurred can significantly to absorb co2Reach efficient trapping co2
Purpose.However, the method power consumption is larger, and the ammoniacal liquor being used is larger to equipment corrosion, therefore higher to equipment requirement,
Relatively costly.In recent years, using all kinds of solid absorbents to co2Carry out absorption to quickly grow.For example utilize hydrotalcite and metal
Oxide carries out co2During absorption, there is larger adsorbance, but adsorption-desorption temperature is higher.Using activated carbon, zeolite or gold
Genus-organic frame (mofs) material carries out co2During absorption, adsorption-desorption temperature is relatively low, and power consumption is relatively low, yet with adsorbing
Journey is physical absorption, and adsorbance is less.Therefore find and there is larger adsorbance, adsorption-desorption temperature is relatively low and has relatively simultaneously
The solid absorbent of good circulation absorption performance is extremely urgent.
In recent years, can be with co using the modified solid absorbent of organic amine2There is chemical reaction, solution on its surface in molecule
Certainly adsorbance is less, the rate of adsorption is less, adsorptive selectivity is relatively low, adsorption-desorption temperature is higher, larger etc. to equipment corrosion
A difficult problem, reaches to co2Carry out the efficient, purpose of high-selectivity adsorption.There is more rich n atom and selected in organic amine molecule
Select as modified material.Organic amine is as co2Adsorption site can be with co2Chemical reaction is occurred to carry out co2Absorption, meanwhile, organic
Amine can should obtain a kind of new material with the matter interaction with lewis acidity as a kind of lewis alkali.Therefore, may be used
To have the acid substance reaction of lewis using organic amine with this, preparation has the solid absorbent of preferable absorption property.
[content of the invention]
It is an object of the invention to provide one kind has efficient co2The solid material zr-cn of absorption property and its modifier
Preparation method.
For achieving the above object, the present invention provides a kind of absorption co2Solid material zr-cn preparation method, including under
State step:
Slaine a is dissolved in 80ml deionized water, forms solution a1；
Slaine b is added to above-mentioned a1 solution, and stirs 3-5h in 30 DEG C -50 DEG C, obtain the first solid product；
First solid matter with deionized water is washed, is in neutrality to solution；
The first solid product after washing is dried after 12h-24h in 30 DEG C -50 DEG C, is placed in 80 DEG C -100 DEG C vacuum drying
6h-8h is dried in case, obtains zr-cn solid material；
Wherein said slaine a is potassium ferrocyanide or six cyanogen close iron () acid potassium；Described slaine b be zirconyl nitrate,
Zirconium nitrate, zirconium-n-propylate, zirconium iso-propoxide, zirconium-n-butylate, zirconium chloride or eight hydration zirconium oxychlorides.
In above-mentioned preparation method, the mol ratio of slaine a and slaine b is [0.5～2]: 1.
The present invention also provides a kind of absorption co by above-mentioned preparation2Solid material zr-cn be modified obtaining am/zr-
The method of cn, comprises the steps:
Take organic amine c to be dissolved in 15g organic solvent, form solution c1；
Absorption co is added in solution c12Zr-cn solid material, obtain turbid solution；
Above-mentioned turbid solution is stirred at room temperature after 3h-6h, is placed in 60 DEG C of -80 DEG C of drying boxes, removes solvent, by gained
Solid product is placed in 100 DEG C of -130 DEG C of drying boxes, keeps 3h-6h, obtains material modified am/zr-cn；
Wherein, described organic amine is selected from ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA or polyethylene
Imines；Described organic solvent is methyl alcohol or absolute ethyl alcohol.
In above-mentioned method of modifying, described organic amine is 1:[10～1 with the mass ratio of zr-cn].
According to experimental result, solid material provided by the present invention, in lower temperature and pressure environment, there is co2Inhale
The features such as attached capacity is larger, adsorption-desorption temperature is relatively low, this method solves common co2Low pressure adsorbent amount is little, desorption temperature
Higher etc. not enough, there is good prospects for commercial application
[brief description]
Fig. 1 show zr-cn in the embodiment of the present invention 1 to co2Adsorbance change over curve map.
Fig. 2 show material modified am/zr-cn in the embodiment of the present invention 13 to co2Adsorbance change over song
Line chart.
[specific embodiment]
The preparation of solid material zr-cn:
Preparation example 1
A. 8mmol potassium ferrocyanide is dissolved in 80ml deionized water, forms solution a1；
B. 4mmol eight is hydrated zirconium oxychloride to add to a1 solution, and stirs 3h in 30 DEG C, obtain the first solid and produce
Thing；
C. gained first solid matter with deionized water is washed, be in neutrality to solution；
D. the first solid product after washing is dried after 12h in 30 DEG C, is placed in 80 DEG C of vacuum drying chambers and 6h is dried, obtain
Solid material zr-cn.
Solid material zr-cn according to obtained by embodiment 1 is to co2Adsorbance change over curve map such as accompanying drawing 1
Shown, as seen from the figure, zr-cn is to co2Absorption increases over and increases, and maximal absorptive capacity 2.35mmol g-1.
Preparation example 2
A. 8mmol potassium ferrocyanide is dissolved in 80ml deionized water, forms solution a1；
B. 8mmol eight is hydrated zirconium oxychloride to add to a1 solution, and stirs 4h in 30 DEG C, obtain the first solid and produce
Thing；
C. gained first solid matter with deionized water is washed, be in neutrality to solution；
D. the first solid product after washing is dried after 18h in 40 DEG C, is placed in 80 DEG C of vacuum drying chambers and 7h is dried, obtain
Solid material zr-cn.
Preparation example 3
A. 8mmol potassium ferrocyanide is dissolved in 80ml deionized water, forms solution a1；
B. 12mmol eight is hydrated zirconium oxychloride to add to a1 solution, and stirs 5h in 30 DEG C, obtain the first solid and produce
Thing；
C. gained first solid matter with deionized water is washed, be in neutrality to solution；
D. the first solid product after washing is dried after 24h in 50 DEG C, is placed in 80 DEG C of vacuum drying chambers and 8h is dried, obtain
Solid material zr-cn.
Preparation example 4
A. 8mmol potassium ferrocyanide is dissolved in 80ml deionized water, forms solution a1；
B. 16mmol eight is hydrated zirconium oxychloride to add to a1 solution, and stirs 3h in 30 DEG C, obtain the first solid and produce
Thing；
C. gained first solid matter with deionized water is washed, be in neutrality to solution；
D. the first solid product after washing is dried after 24h in 40 DEG C, is placed in 80 DEG C of vacuum drying chambers and 8h is dried, obtain
Solid material zr-cn.
Preparation example 5
A. 8mmol potassium ferrocyanide is dissolved in 80ml deionized water, forms solution a1；
B. 4mmol eight is hydrated zirconium oxychloride to add to a1 solution, and stirs 3h in 40 DEG C, obtain the first solid and produce
Thing；
C. gained first solid matter with deionized water is washed, be in neutrality to solution；
D. the first solid product after washing is dried after 12h in 30 DEG C, is placed in 90 DEG C of vacuum drying chambers and 6h is dried, obtain
Solid material zr-cn.
Preparation example 6
A. 8mmol potassium ferrocyanide is dissolved in 80ml deionized water, forms solution a1；
B. 8mmol eight is hydrated zirconium oxychloride to add to a1 solution, and stirs 4h in 40 DEG C, obtain the first solid and produce
Thing；
C. gained first solid matter with deionized water is washed, be in neutrality to solution；
D. the first solid product after washing is dried after 18h in 40 DEG C, is placed in 90 DEG C of vacuum drying chambers and 7h is dried, obtain
Solid material zr-cn.
Preparation example 7
A. 8mmol potassium ferrocyanide is dissolved in 80ml deionized water, forms solution a1；
B. 12mmol eight is hydrated zirconium oxychloride to add to a1 solution, and stirs 5h in 40 DEG C, obtain the first solid and produce
Thing；
C. gained first solid matter with deionized water is washed, be in neutrality to solution；
D. the first solid product after washing is dried after 24h in 50 DEG C, is placed in 90 DEG C of vacuum drying chambers and 8h is dried, obtain
Solid material zr-cn.
Preparation example 8
A. 8mmol potassium ferrocyanide is dissolved in 80ml deionized water, forms solution a1；
B. 16mmol eight is hydrated zirconium oxychloride to add to a1 solution, and stirs 3h in 40 DEG C, obtain the first solid and produce
Thing；
C. gained first solid matter with deionized water is washed, be in neutrality to solution；
D. the first solid product after washing is dried after 24h in 40 DEG C, is placed in 90 DEG C of vacuum drying chambers and 8h is dried, obtain
Solid material zr-cn.
Preparation example 9
A. 8mmol potassium ferrocyanide is dissolved in 80ml deionized water, forms solution a1；
B. 4mmol eight is hydrated zirconium oxychloride to add to a1 solution, and stirs 3h in 50 DEG C, obtain the first solid and produce
Thing；
C. gained first solid matter with deionized water is washed, be in neutrality to solution；
D. the first solid product after washing is dried after 12h in 30 DEG C, is placed in 100 DEG C of vacuum drying chambers and 6h is dried,
Obtain solid material zr-cn.
Preparation example 10
A. 8mmol potassium ferrocyanide is dissolved in 80ml deionized water, forms solution a1；
B. 8mmol eight is hydrated zirconium oxychloride to add to a1 solution, and stirs 4h in 50 DEG C, obtain the first solid and produce
Thing；
C. gained first solid matter with deionized water is washed, be in neutrality to solution；
D. the first solid product after washing is dried after 18h in 40 DEG C, is placed in 100 DEG C of vacuum drying chambers and 7h is dried,
Obtain solid material zr-cn.
Preparation example 11
A. 8mmol potassium ferrocyanide is dissolved in 80ml deionized water, forms solution a1；
B. 12mmol eight is hydrated zirconium oxychloride to add to a1 solution, and stirs 5h in 50 DEG C, obtain the first solid and produce
Thing；
C. gained first solid matter with deionized water is washed, be in neutrality to solution；
D. the first solid product after washing is dried after 24h in 50 DEG C, is placed in 100 DEG C of vacuum drying chambers and 8h is dried,
Obtain solid material zr-cn.
Preparation example 12
A. 8mmol potassium ferrocyanide is dissolved in 80ml deionized water, forms solution a1；
B. 16mmol eight is hydrated zirconium oxychloride to add to a1 solution, and stirs 3h in 50 DEG C, obtain the first solid and produce
Thing；
C. gained first solid matter with deionized water is washed, be in neutrality to solution；
D. the first solid product after washing is dried after 24h in 40 DEG C, is placed in 100 DEG C of vacuum drying chambers and 8h is dried,
Obtain solid material zr-cn.
The preparation of the material modified am/zr-cn of zr-cn:
Preparation example 13
A. ethylenediamine is dissolved in 15g methyl alcohol, forms the alcoholic solution of ethylenediamine.Repeat aforesaid operations
The alcoholic solution of 10 parts of ethylenediamines of preparation.Add 0.5g preparation example 1 in the alcoholic solution of the ethylenediamine of every a preparation
Prepared solid material zr-cn, stirs 3h under room temperature, obtains 10 parts of solid products, wherein added ethylenediamine is with zr-cn's
Mass ratio is respectively 1:10,1:9,1:8,1:7,1:6,1:5,1:4,1:3,1:2 or 1:1.
B. 10 parts of solid products of gained in a step are placed in 80 DEG C of drying boxes, remove solvent, by gained solid product
It is placed in 100 DEG C of drying boxes, keep 3h, obtain material modified am/zr-cn.
Solid material am/zr-cn according to obtained by embodiment 13 is to co2Adsorbance to change over curve map for example attached
Shown in Fig. 2, as seen from the figure, zr-cn is to co2Absorption increases over and increases, and maximal absorptive capacity 3.18mmol g-1.
Preparation example 14
A. ethylenediamine is dissolved in 15g absolute ethyl alcohol, forms the alcoholic solution of ethylenediamine.Repeat aforesaid operations, prepare 10 parts
The alcoholic solution of ethylenediamine.The solid material prepared by 0.5g preparation example 2 is added in the alcoholic solution of the ethylenediamine of every a preparation
Zr-cn, stirs 3h under room temperature, obtains 10 parts of solid products, and the mass ratio of wherein added ethylenediamine and zr-cn is respectively 1:
10th, 1:9,1:8,1:7,1:6,1:5,1:4,1:3,1:2 or 1:1.
B. 10 parts of solid products of gained in a step are placed in 80 DEG C of drying boxes, remove solvent, gained solid product is put
In 100 DEG C of drying boxes, keep 3h, obtain material modified am/zr-cn.
Preparation example 15
A. diethylenetriamine is dissolved in 15g methyl alcohol, forms the alcoholic solution of diethylenetriamine.Repeat aforesaid operations preparation 10
The alcoholic solution of part diethylenetriamine.The alcoholic solution of the diethylenetriamine of every a preparation adds prepared by 0.5g preparation example 3
Solid material zr-cn, stir 3h under room temperature, obtain 10 parts of solid products, the mass ratio of wherein added ethylenediamine and zr-cn
It is respectively 1:10,1:9,1:8,1:7,1:6,1:5,1:4,1:3,1:2 or 1:1.
B. 10 parts of solid products of gained in a step are placed in 80 DEG C of drying boxes, remove solvent, gained solid product is put
In 100 DEG C of drying boxes, keep 3h, obtain material modified am/zr-cn.
Preparation example 16
A. triethylene tetramine is dissolved in 15g absolute ethyl alcohol, forms the alcoholic solution of triethylene tetramine.Repeat aforesaid operations,
The alcoholic solution of 10 parts of triethylene tetramines of preparation.Add 0.5g preparation example 4 in the alcoholic solution of the triethylene tetramine of every a preparation
Prepared solid material zr-cn, stirs 3h under room temperature, obtains 10 parts of solid products, wherein added ethylenediamine is with zr-cn's
Mass ratio is respectively 1:10,1:9,1:8,1:7,1:6,1:5,1:4,1:3,1:2 or 1:1.
B. 10 parts of solid products of gained in a step are placed in 80 DEG C of drying boxes, remove solvent, gained solid product is put
In 100 DEG C of drying boxes, keep 3h, obtain material modified am/zr-cn.
Preparation example 17
A. triethylene tetramine is dissolved in 15g absolute ethyl alcohol, forms the alcoholic solution of triethylene tetramine.Repeat aforesaid operations,
The alcoholic solution of 10 parts of triethylene tetramines of preparation.Add 0.5g preparation example 5 in the alcoholic solution of the triethylene tetramine of every a preparation
Prepared solid material zr-cn, stirs 3h under room temperature, obtains 10 parts of solid products, wherein added ethylenediamine is with zr-cn's
Mass ratio is respectively 1:10,1:9,1:8,1:7,1:6,1:5,1:4,1:3,1:2 or 1:1.
B. 10 parts of solid products of gained in a step are placed in 80 DEG C of drying boxes, remove solvent, gained solid product is put
In 100 DEG C of drying boxes, keep 3h, obtain material modified am/zr-cn.
Preparation example 18
A. triethylene tetramine is dissolved in 15g absolute ethyl alcohol, forms the alcoholic solution of triethylene tetramine.Repeat aforesaid operations,
The alcoholic solution of 10 parts of triethylene tetramines of preparation.Add 0.5g preparation example 6 in the alcoholic solution of the triethylene tetramine of every a preparation
Prepared solid material zr-cn, stirs 3h under room temperature, obtains 10 parts of solid products, wherein added ethylenediamine is with zr-cn's
Mass ratio is respectively 1:10,1:9,1:8,1:7,1:6,1:5,1:4,1:3,1:2 or 1:1.
B. 10 parts of solid products of gained in a step are placed in 80 DEG C of drying boxes, remove solvent, gained solid product is put
In 100 DEG C of drying boxes, keep 3h, obtain material modified am/zr-cn.
Preparation example 19
A. triethylene tetramine is dissolved in 15g absolute ethyl alcohol, forms the alcoholic solution of triethylene tetramine.Repeat aforesaid operations,
The alcoholic solution of 10 parts of triethylene tetramines of preparation.Add 0.5g preparation example 7 in the alcoholic solution of the triethylene tetramine of every a preparation
Prepared solid material zr-cn, stirs 3h under room temperature, obtains 10 parts of solid products, wherein added ethylenediamine is with zr-cn's
Mass ratio is respectively 1:10,1:9,1:8,1:7,1:6,1:5,1:4,1:3,1:2 or 1:1.
B. 10 parts of solid products of gained in a step are placed in 80 DEG C of drying boxes, remove solvent, gained solid product is put
In 100 DEG C of drying boxes, keep 3h, obtain material modified am/zr-cn.
Preparation example 20
A. TEPA is dissolved in 15g absolute ethyl alcohol, forms the alcoholic solution of TEPA.Repeat aforesaid operations,
The alcoholic solution of 10 parts of TEPAs of preparation.Add 0.5g preparation example 8 in the alcoholic solution of the TEPA of every a preparation
Prepared solid material zr-cn, stirs 3h under room temperature, obtains 10 parts of solid products, wherein added ethylenediamine is with zr-cn's
Mass ratio is respectively 1:10,1:9,1:8,1:7,1:6,1:5,1:4,1:3,1:2 or 1:1.
B. 10 parts of solid products of gained in a step are placed in 80 DEG C of drying boxes, remove solvent, gained solid product is put
In 100 DEG C of drying boxes, keep 3h, obtain material modified am/zr-cn.
Preparation example 21
A. TEPA is dissolved in 15g absolute ethyl alcohol, forms the alcoholic solution of TEPA.Repeat aforesaid operations,
The alcoholic solution of 10 parts of TEPAs of preparation.Add 0.5g preparation example 9 in the alcoholic solution of the TEPA of every a preparation
Prepared solid material zr-cn, stirs 3h under room temperature, obtains 10 parts of solid products, wherein added ethylenediamine is with zr-cn's
Mass ratio is respectively 1:10,1:9,1:8,1:7,1:6,1:5,1:4,1:3,1:2 or 1:1.
B. 10 parts of solid products of gained in a step are placed in 80 DEG C of drying boxes, remove solvent, gained solid product is put
In 100 DEG C of drying boxes, keep 3h, obtain material modified am/zr-cn.
Preparation example 22
A. TEPA is dissolved in 15g absolute ethyl alcohol, forms the alcoholic solution of TEPA.Repeat aforesaid operations,
The alcoholic solution of 10 parts of TEPAs of preparation.Add 0.5g preparation example 10 in the alcoholic solution of the TEPA of every a preparation
Prepared solid material zr-cn, stirs 3h under room temperature, obtains 10 parts of solid products, wherein added ethylenediamine is with zr-cn's
Mass ratio is respectively 1:10,1:9,1:8,1:7,1:6,1:5,1:4,1:3,1:2 or 1:1.
B. 10 parts of solid products of gained in a step are placed in 80 DEG C of drying boxes, remove solvent, by gained solid product
It is placed in 100 DEG C of drying boxes, keep 3h, obtain material modified am/zr-cn.
Preparation example 23
A. TEPA is dissolved in 15g absolute ethyl alcohol, forms the alcoholic solution of TEPA.Repeat aforesaid operations,
The alcoholic solution of 10 parts of TEPAs of preparation.Add 0.5g preparation example 11 in the alcoholic solution of the TEPA of every a preparation
Prepared solid material zr-cn, stirs 3h under room temperature, obtains 10 parts of solid products, wherein added ethylenediamine is with zr-cn's
Mass ratio is respectively 1:10,1:9,1:8,1:7,1:6,1:5,1:4,1:3,1:2 or 1:1.
B. 10 parts of solid products of gained in a step are placed in 80 DEG C of drying boxes, remove solvent, gained solid product is put
In 100 DEG C of drying boxes, keep 3h, obtain material modified am/zr-cn.
Preparation example 24
A. polyethyleneimine is dissolved in 15g absolute ethyl alcohol, forms the alcoholic solution of polyethyleneimine.Repeat aforesaid operations,
The alcoholic solution of 10 parts of polyethyleneimines of preparation.Add 0.5g preparation example 12 in the alcoholic solution of the polyethyleneimine of every a preparation
Prepared solid material zr-cn, stirs 3h under room temperature, obtains 10 parts of solid products, wherein added ethylenediamine is with zr-cn's
Mass ratio is respectively 1:10,1:9,1:8,1:7,1:6,1:5,1:4,1:3,1:2 or 1:1.
B. 10 parts of solid products of gained in a step are placed in 80 DEG C of drying boxes, remove solvent, gained solid product is put
In 100 DEG C of drying boxes, keep 3h, obtain material modified am/zr-cn.
Solid material zr-cn and its material modified co
2
Determining adsorption
Embodiment 1
Take the appropriate solid material zr-cn preparing by preparation example 1, be placed in the u-shaped pipe of autochem 2920, lead to
Enter high-purity ar purging solid material zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min, the co of gained zr-cn2Adsorbance changes over
Curve is as shown in Figure 1.
Embodiment 2
Take the appropriate solid material zr-cn preparing by preparation example 2, be placed in the u-shaped pipe of autochem 2920, lead to
Enter high-purity ar purging solid material zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min, the co of gained zr-cn2Adsorbance changes over song
Line is similar with Fig. 1.
Embodiment 3
Take the appropriate solid material zr-cn preparing by preparation example 3, be placed in the u-shaped pipe of autochem 2920, lead to
Enter high-purity ar purging solid material zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min, the co of gained zr-cn2Adsorbance changes over song
Line is similar with Fig. 1.
Embodiment 4
Take the appropriate solid material zr-cn preparing by preparation example 4, be placed in the u-shaped pipe of autochem 2920, lead to
Enter high-purity ar purging solid material zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min, the co of gained zr-cn2Adsorbance changes over song
Line is similar with Fig. 1.
Embodiment 5
Take the appropriate solid material zr-cn preparing by preparation example 5, be placed in the u-shaped pipe of autochem 2920, lead to
Enter high-purity ar purging solid material zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min, the co of gained zr-cn2Adsorbance changes over song
Line is similar with Fig. 1.
Embodiment 6
Take the appropriate solid material zr-cn preparing by preparation example 6, be placed in the u-shaped pipe of autochem 2920, lead to
Enter high-purity ar purging solid material zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min, the co of gained zr-cn2Adsorbance changes over song
Line is similar with Fig. 1.
Embodiment 7
Take the appropriate solid material zr-cn preparing by preparation example 7, be placed in the u-shaped pipe of autochem 2920, lead to
Enter high-purity ar purging solid material zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min, the co of gained zr-cn2Adsorbance changes over song
Line is similar with Fig. 1.
Embodiment 8
Take the appropriate solid material zr-cn preparing by preparation example 8, be placed in the u-shaped pipe of autochem 2920, lead to
Enter high-purity ar purging solid material zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min, the co of gained zr-cn2Adsorbance changes over song
Line is similar with Fig. 1.
Embodiment 9
Take the appropriate solid material zr-cn preparing by preparation example 9, be placed in the u-shaped pipe of autochem 2920, lead to
Enter high-purity ar purging solid material zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min, the co of gained zr-cn2Adsorbance changes over song
Line is similar with Fig. 1.
Embodiment 10
Take the appropriate solid material zr-cn preparing by preparation example 10, be placed in the u-shaped pipe of autochem 2920,
It is passed through high-purity ar purging solid material zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min, the co of gained zr-cn2Adsorbance changes over song
Line is similar with Fig. 1.
Embodiment 11
Take the appropriate solid material zr-cn preparing by preparation example 11, be placed in the u-shaped pipe of autochem 2920,
It is passed through high-purity ar purging solid material zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min, the co of gained zr-cn2Adsorbance changes over song
Line is similar with Fig. 1.
Embodiment 12
Take the appropriate solid material zr-cn preparing by preparation example 12, be placed in the u-shaped pipe of autochem 2920,
It is passed through high-purity ar purging solid material zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min, the co of gained zr-cn2Adsorbance changes over song
Line is similar with Fig. 1.
Embodiment 13
Take the appropriate solid material am/zr-cn preparing by preparation example 13, be placed in the u-shaped pipe of autochem 2920
Interior, it is passed through high-purity ar purging solid material am/zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min.The co of gained zr-cn2Adsorbance changes over song
Line is as shown in Figure 2.
Co with zr-cn solid material in preparation example 12Adsorbance is compared, and this material modified adsorbance significantly increases.
Embodiment 14
Take the appropriate solid material am/zr-cn preparing by preparation example 14, be placed in the u-shaped pipe of autochem 2920
Interior, it is passed through high-purity ar purging solid material am/zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min.The co of gained zr-cn2Adsorbance changes over song
Line is similar with Fig. 2.
Co with zr-cn solid material in preparation example 22Adsorbance is compared, and this material modified adsorbance significantly increases, and is situated between
In 2.5～4mmol g-1Between.
Embodiment 15
Take the appropriate solid material am/zr-cn preparing by preparation example 15, be placed in the u-shaped pipe of autochem 2920
Interior, it is passed through high-purity ar purging solid material am/zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min.The co of gained zr-cn2Adsorbance changes over song
Line is similar with Fig. 2.
Co with zr-cn solid material in preparation example 32Adsorbance is compared, and this material modified adsorbance significantly increases, and is situated between
In 2.5～4mmol g-1Between.
Embodiment 16
Take the appropriate solid material am/zr-cn preparing by preparation example 16, be placed in the u-shaped pipe of autochem 2920
Interior, it is passed through high-purity ar purging solid material am/zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min.The co of gained zr-cn2Adsorbance changes over song
Line is similar with Fig. 2.
Co with zr-cn solid material in preparation example 42Adsorbance is compared, and this material modified adsorbance significantly increases, and is situated between
In 2.5～4mmol g-1Between.
Embodiment 17
Take the appropriate solid material am/zr-cn preparing by preparation example 17, be placed in the u-shaped pipe of autochem 2920
Interior, it is passed through high-purity ar purging solid material am/zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min.The co of gained zr-cn2Adsorbance changes over song
Line is similar with Fig. 2.
Co with zr-cn solid material in preparation example 52Adsorbance is compared, and this material modified adsorbance significantly increases, and is situated between
In 2.5～4mmol g-1Between.
Embodiment 18
Take the appropriate solid material am/zr-cn preparing by preparation example 18, be placed in the u-shaped pipe of autochem 2920
Interior, it is passed through high-purity ar purging solid material am/zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min.The co of gained zr-cn2Adsorbance changes over song
Line is similar with Fig. 2.
Co with zr-cn solid material in preparation example 62Adsorbance is compared, and this material modified adsorbance significantly increases, and is situated between
In 2.5～4mmol g-1Between.
Embodiment 19
Take the appropriate solid material am/zr-cn preparing by preparation example 19, be placed in the u-shaped pipe of autochem 2920
Interior, it is passed through high-purity ar purging solid material am/zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min.The co of gained zr-cn2Adsorbance changes over song
Line is similar with Fig. 2.
Co with zr-cn solid material in preparation example 72Adsorbance is compared, and this material modified adsorbance significantly increases, and is situated between
In 2.5～4mmol g-1Between.
Embodiment 20
Take the appropriate solid material am/zr-cn preparing by preparation example 20, be placed in the u-shaped pipe of autochem 2920
Interior, it is passed through high-purity ar purging solid material am/zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min.The co of gained zr-cn2Adsorbance changes over song
Line is similar with Fig. 2.
Co with zr-cn solid material in preparation example 82Adsorbance is compared, and this material modified adsorbance significantly increases, and is situated between
In 2.5～4mmol g-1Between.
Embodiment 21
Take the appropriate solid material am/zr-cn preparing by preparation example 21, be placed in the u-shaped pipe of autochem 2920
Interior, it is passed through high-purity ar purging solid material am/zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min.The co of gained zr-cn2Adsorbance changes over
Curve is similar with Fig. 2.
Co with zr-cn solid material in preparation example 92Adsorbance is compared, and this material modified adsorbance significantly increases, and is situated between
In 2.5～4mmol g-1Between.
Embodiment 22
Take the appropriate solid material am/zr-cn preparing by preparation example 22, be placed in the u-shaped pipe of autochem 2920
Interior, it is passed through high-purity ar purging solid material am/zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min.The co of gained zr-cn2Adsorbance changes over song
Line is similar with Fig. 2.
Co with zr-cn solid material in preparation example 102Adsorbance is compared, and this material modified adsorbance significantly increases,
Between 2.5～4mmol g-1Between.
Embodiment 23
Take the appropriate solid material am/zr-cn preparing by preparation example 23, be placed in the u-shaped pipe of autochem 2920
Interior, it is passed through high-purity ar purging solid material am/zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min.The co of gained zr-cn2Adsorbance changes over song
Line is similar with Fig. 2.
Co with zr-cn solid material in preparation example 112Adsorbance is compared, and this material modified adsorbance significantly increases,
Between 2.5～4mmol g-1Between.
Embodiment 24
Take the appropriate solid material am/zr-cn preparing by preparation example 24, be placed in the u-shaped pipe of autochem 2920
Interior, it is passed through high-purity ar purging solid material am/zr-cn surface, be warming up to 100 DEG C simultaneously, after keeping 60min, be cooled to 75 DEG C；
It is passed through 5%co2- he gas, gas pressure is 0.2mpa, and gas flow is 50ml min-1, holding 10min, 5%
co2Co in-he gas2Percentage by volume is 5%, he percentage by volume is 95%；
It is passed through high-purity ar, is warming up to 100 DEG C simultaneously, keep 60min.The co of gained zr-cn2Adsorbance changes over song
Line is similar with Fig. 2.
Co with zr-cn solid material in preparation example 122Adsorbance is compared, and this material modified adsorbance significantly increases,
Between 2.5～4mmol g-1Between.
In order to further illustrate the superiority of prepared material in the present invention, from following adsorbent as a comparison case.
Comparative example 1
When 40 DEG C, 80.2g p123 is dissolved in 2000ml deionized water and 400ml concentrated hydrochloric acid, adds the positive silicic acid of 170g four
Ethyl ester (teos), 40 DEG C of stirring 16h.Stop stirring, temperature is increased to 92 DEG C, keep 18h, obtain white solid.By gained
Solid is washed with a large amount of deionized waters, is dried.Gained solid after drying is placed in 550 DEG C of Muffle kiln roasting 6h, obtains molecule
Sieve sba-15.
The sba-15 taking 10g preparation is dissolved in 150ml toluene and the mixed solution of 3.2ml deionized water, stirs 1h.Add
10ml ethylenediamine, heats up, and flow back 4h, adds methyl alcohol and deionized water, is distilled.After distillation finishes, mixed liquor is cooled to
Room temperature, filters, and after gained solid is washed with isopropanol, is dried, and the modified molecular screen material of prepared ethylenediamine is standby.
Co by this ethylenediamine modified molecular screen material2Adsorption experimental results are learnt, temperature is 25 DEG C, co2Concentration is 15%
When, adsorbance is 0.46mmol g-1.Pure co2In environment, co2Pressure is 1atm, when temperature is 295k, co2Adsorbance is about
2mmol·g-1.
Comparative example 2
15g titanium tetraisopropylate is dissolved in 3.41g octylame, obtains supernatant liquid.75ml is added to go in the clarified solution of gained
Ionized water, is stirred vigorously, and produces precipitation.Add, toward in gained precipitation, the hcl solution that 0.2603g concentration is 37%, be stirred overnight
Afterwards, it is placed on 40 DEG C and carries out hydro-thermal process 2 days, then be placed on standing 2 days in 60 DEG C of environment, be finally placed on 80 DEG C
4 days are stood in environment.After products therefrom is filtered, solid product is placed in sealing container and is placed in holding 2 in 100 DEG C of drying boxes
My god, then it is placed on placement 2 days in 120 DEG C of drying boxes, finally it is placed in 140 DEG C of drying boxes and place 2 days.By gained material
Mixed liquor using 375ml methyl alcohol and 125ml ether is washed, then is washed with 500ml methyl alcohol, and gained material is placed in
Keep 2 days in 150 DEG C of drying boxes, standby.
0.5g diethylenetriamine is dissolved in 10g ethanol, stirs 30min, add prepared material in 1g above-mentioned steps,
After 80 DEG C of backflow 2h, it is placed in 80 DEG C of drying boxes and removes solvent, obtain solid absorbent standby.
Co by this diethylenetriamine modified solid material2Adsorption experimental results are learnt, temperature is 75 DEG C, co2Concentration is
When 10%, adsorbance is 2.64mmol g-1.
Claims (4)
1. a kind of absorption co2Zr-cn solid material preparation method, comprise the steps:
Slaine a is dissolved in 80ml deionized water, forms solution a1；
Slaine b is added to above-mentioned a1 solution, and stirs 3-5h in 30 DEG C -50 DEG C, obtain the first solid product；
First solid matter with deionized water is washed, is in neutrality to solution；
The first solid product after washing is dried after 12h-24h in 30 DEG C -50 DEG C, is placed in 80 DEG C of -100 DEG C of vacuum drying chambers
6h-8h is dried, obtains zr-cn solid material；
Wherein, described slaine a is to close iron () acid potassium selected from potassium ferrocyanide or six cyanogen；
Described slaine b is selected from zirconyl nitrate, zirconium nitrate, zirconium-n-propylate, zirconium iso-propoxide, zirconium-n-butylate, zirconium chloride or eight water
Close zirconium oxychloride.
2. absorption co according to claim 12Zr-cn solid material preparation method it is characterised in that described metal
The mol ratio of salt a and slaine b is [0.5～2]: 1.
3. a kind of absorption co prepared to claim 12The method that is modified of zr-cn solid material, comprise the steps:
Take organic amine c to be dissolved in 15g organic solvent, form solution c1；
Absorption co is added in solution c12Zr-cn solid material, obtain turbid solution；
Above-mentioned turbid solution is stirred at room temperature after 3h-6h, is placed in 60 DEG C of -80 DEG C of drying boxes, removes solvent, by gained solid
Product is placed in 100 DEG C of -130 DEG C of drying boxes, keeps 3h-6h, obtains material modified am/zr-cn；
Wherein, described organic amine is selected from ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA or polyethyleneimine；
Described organic solvent is selected from methyl alcohol or absolute ethyl alcohol.
4. method of modifying according to claim 3 is it is characterised in that described organic amine is 1:[10 with the mass ratio of zr-cn
～1].
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| US3639641A (en) * | 1965-08-31 | 1972-02-01 | Shinzoh Satoh | Method for rapid manufacture of nitrided thick layer of super high hardness on ferrous metal articles |
| CN104190367A (en) * | 2014-09-19 | 2014-12-10 | 湖南大学 | Preparation method for organic amine modified material M-NH2 for adsorbing CO2 |
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| US3639641A (en) * | 1965-08-31 | 1972-02-01 | Shinzoh Satoh | Method for rapid manufacture of nitrided thick layer of super high hardness on ferrous metal articles |
| CN104190367A (en) * | 2014-09-19 | 2014-12-10 | 湖南大学 | Preparation method for organic amine modified material M-NH2 for adsorbing CO2 |
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