CN108187628A - A kind of activating coal gangue prepares CO2The method of sorbing material - Google Patents
A kind of activating coal gangue prepares CO2The method of sorbing material Download PDFInfo
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- CN108187628A CN108187628A CN201810242827.1A CN201810242827A CN108187628A CN 108187628 A CN108187628 A CN 108187628A CN 201810242827 A CN201810242827 A CN 201810242827A CN 108187628 A CN108187628 A CN 108187628A
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- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/25—Coated, impregnated or composite adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The invention discloses a kind of activating coal gangues to prepare CO2The method of sorbing material is directed to comprehensive utilization and the CO of gangue2The preparation method of sorbing material.This method handles to obtain efficient CO by microwave-heating, alkali process, impregnation, first supercritical processing and grafting using gangue as raw material2Material for trapping, then by CO2Material for trapping is placed in fixed bed reactors, for trapping CO2.The present invention is used as CO2Material for trapping has many advantages, such as that trapping capacity is big, adsorption rate is fast, manufacturing cost is cheap, and favorable regeneration effect, while the comprehensive utilization for gangue provides a new way.
Description
Technical field
The present invention relates to a kind of activating coal gangues to prepare CO2The method of sorbing material is directed to the comprehensive profit of gangue
With and CO2The preparation method of sorbing material.
Background technology
With the increase of mankind's activity, global CO2Discharge capacity is growing day by day, leads to global warning, and temperature is upper
It rises and brings a series of environmental problem, such as sea-level rise, glacial recession, frozen soil thawing, lake（River）Ice freeze late with it is early melt,
Animals and plants distribution is reduced to polar region and Diagnostic predictor extension, certain animals and plants quantity, some plant blossom times in advance etc..Work
The production of industry metaplasia is as CO2The major source of discharge, by the CO in industrial processes2Detached, trapped and concentrated storage for
Alleviate CO2It is largely effective to discharge the environmental problem brought.Therefore, it has been started in global range for CO2Trapping and storing technology are ground
The upsurge of hair.
CO2Trapping technique is broadly divided into chemical absorbing and physical absorption two ways, and wherein chemical absorbing is CO2Passing through
It learns reaction and generates new substance, and physical absorption is then by CO by adsorption2It is fixed.In MODEL OF CHEMICAL ABSORPTION PROCESS
Absorbent mainly has calcium carbonate, aminated compounds, ammonium hydroxide etc., such as carbonic acid calcium uptake CO2After generate calcium bicarbonate, calcium bicarbonate
It splits the carbon dioxide off, can be recycled under the high temperature conditions.And physical absorption focuses primarily upon micropore/mesoporous inorganic molecule
On sieve, porous metal organic frameworks, metal oxide and carbon-based sorbing material, but since alkalinity is relatively weak, absorption speed
Degree and capacity are more low, greatly limit its commercial Application.More popular modified molecular screen material, the organic bone of porous metals
Frame material etc. has larger promotion in terms of adsorption capacity and capacity, but preparation process is relative complex, and cost is higher, unfavorable
In industrial use.
Chinese patent CN101804332B disclose and it is a kind of develop new material technology for raw material using gangue, load is poly-
The method that aziridine prepares carbon dioxide capture material.Gangue crushes, and then high-temperature roasting adds in acid solution, be sufficiently stirred,
Alundum (Al2O3) ingredient in gangue has aluminium chloride with hydrochloric acid reaction product solution, filters silica and aluminium ion point
It opens, obtains the filtrate of aluminium chloride, further aluminium polychloride is made in reaction to filtrate.It filters to contain titanium dioxide in remaining solid object
Silicon, high alkali liquid heating prepare silicate solutions, then with containing polyethyleneimine and acid solution precipitation process, polyethyleneimine are made to sink
Product obtains mesoporous particles on silica dioxide granule.And there is high cold compression strength.But the patent makes in preparation process
With a large amount of acid solution, if carrying out industrialized production, acid pickle may be caused to handle the problems such as difficult.
Chinese patent CN104907045B discloses a kind of formula of high-efficiency carbon dioxide material for trapping and corresponding preparation
Technique.The material characteristics are using graininess, column, spherical or cellular active carbon with high specific surface area as carrier；Dipping
Activated silica aluminium glue containing one or more of alkali metal/alkali salts is active transition layer, secondary after separation of solid and liquid, drying and roasting
Organic compounds containing nitrogen is impregnated, is made after redrying.The material for trapping used in preparation process graininess, column,
Spherical or cellular active carbon with high specific surface area, so manufacturing cost is higher.
Chinese patent CN101890340B, which is disclosed, to be related to trapping CO2With globular mesoporous carbon composite material and preparation method thereof
And application, the material include following components and parts by weight content：Organic precursor 5-20, surfactant 0.1-3, catalyst 1-
2nd, inorganic template agent 50, polyethyleneimine 5-30 by organic precursor, catalyst and inorganic template agent mixing prepolymerization, are added in
Aging after surfactant after drying, charing process, inorganic template agent remove and support polyethyleneimine, obtains trapping two
The material is placed in ADSORPTION IN A FIXED BED tower by carbonoxide globular mesoporous carbon composite material, for trapping carbon dioxide.The patent
Preparation process is more complicated.
Gangue is the solid fertilizer of generation during coal production, is one of solid waste of world today's maximum.
Gangue mainly mixes a small amount of organic matter by a large amount of inanimate matters and forms, and is a kind of carbon containing with coal seam association in coalification course
Measure black and gray rock relatively low, harder than coal.Gangue is applied to CO2It, not only can be real in the preparation process of material for trapping
The comprehensive utilization of existing Coal Gangue Resource, and cheap CO can be made2Material for trapping.At present, Chinese patent
CN101804332B is disclosed and a kind of utilization gangue develops CO for raw material2The technology of new material is trapped, but the technology will
Aluminium element in gangue is by sour dissolution filter, but aluminium oxide has certain absorption property for carbon dioxide.
Invention content
Present invention aims at providing, a kind of trapping capacity is big, adsorptive selectivity is high, cheap, preparation process is simple
CO2Material for trapping preparation method, while solve the Utilizing question of gangue.
The present invention provides a kind of activating coal gangues to prepare CO2The method of sorbing material, the method be using gangue as
Raw material, by microwave-heating, alkali process, impregnation and first supercritical processing and etc. obtain CO2Material for trapping, specific method are
Follow these steps what is carried out：
1）Microwave-heating
Gangue, calcium carbonate and zinc chloride by quality for 80 ~ 90g, 1 ~ 5g and 1 ~ 5g are uniformly mixed, are placed in microwave-heating stove
In, water vapour is passed through, reactor microwave power is then set as 300 ~ 400W, final temperature is 700 ~ 850 DEG C, the reaction time 10
~ 25min, cooling obtain sample A；
2）Alkali process
Sample A is placed in 1.2 ~ 2.5mol/L aqueous slkalis, temperature is that 2.5 ~ 3h is stirred at 60 ~ 70 DEG C, and filtering, drying obtains sample
Product B；
3）Impregnation
Sample B dippings are ultrasonically treated with being used in the mixed aqueous solution of calcium nitrate and nickel nitrate, in dipping process, processing time
For 40min, ultrasonic power 700W, filtering, dry, calcining obtain sample C to dipping after the completion；
4）First supercritical processing
Sample C is placed in reaction kettle, reaction kettle is warming up to 374.3 DEG C, is then passed through water and nitrogen to reaction kettle with 3:1 matter
For amount than the reaction medium mixed, the pressure for controlling reaction kettle is 22.05MPa, reaction medium is made to reach supercriticality, instead
After answering 20 ~ 25min, sample D is obtained；
5）Grafting is handled
Organic amine with alcohol solution is mixed, sample D is then added in, handles 30min, ultrasonic power 700W under ultrasound condition, so
Heating removes alcohols solvent afterwards, and CO is dried to obtain at 100 ~ 115 DEG C2Material for trapping, wherein organic amine are triethylenediamine, two
Ethylenetriamine, hexa, hexamethylene imine, triethylenediamine, polyethyleneimine, diethanol amine, three ethyl alcohol
One kind or arbitrary several mixture in amine.
In above-mentioned preparation method, the step 1）The flow of middle water vapour is 30cm3/min。
In above-mentioned preparation method, the step 2）Middle aqueous slkali is calcium acetate aqueous solution.
In above-mentioned preparation method, the step 3）A concentration of 1.02 ~ 1.35mol/L of middle calcium nitrate solution, nickel nitrate are molten
A concentration of 0.1 ~ 0.3mol/L of liquid, and two kinds of solution are 1 by volume：2 mixing.
In above-mentioned preparation method, the step 3）Middle calcination temperature is 850 ~ 900 DEG C, time 50min.
In above-mentioned preparation method, alcohols is a kind of in methanol, ethyl alcohol and normal propyl alcohol or arbitrary several in the step 5)
Mixture.
Microwave-heating processing：Gangue with calcium carbonate and zinc chloride is mixed, then passes to water vapour, wherein carbonate exists
Have under hot conditions and corrode by hole effect, and silicate, aluminate and inclined aluminium can be generated with the sial compound in gangue
The compounds such as hydrochlorate；Zinc chloride has catalytic dehydration under high temperature action, make in gangue the hydrogen of carbon compound, oxygen with
The form of water is separated, and more carbon is made to retain in the feed, and form carbon compound skeleton, the carbon after over cleaning
Surface is exposed, and forms the active centre with adsorption capacity, while the presence of zinc chloride can be used as microwave absorption, increase
Absorption of the coal spoil for microwave；Water vapour is passed through on the one hand as microwave absorption, increases the suction of microwave in reaction process
It receives, on the other hand can be that the hole of gangue occlusion opens and reacts to form new sky in active site as activator
Cave, and increase the hardness of sorbing material, while water vapour can take away the exhaust gas generated in reaction process as flow regime
And extra heat.
Alkali process：Material is handled using calcium acetate aqueous slkali, the part metals oxygen contained in material can be dissolved out
Compound, can also react zeolite of the generation with big specific surface area with alumino-silicate, while can increase golden in material
Belong to the amount of calcium.
Impregnation：Using the mixed aqueous solution of calcium nitrate and nickel nitrate in dipping process, and under ultrasonication into
Row, wherein calcium, nickel can increase material C O2Adsorption activity position, and be ultrasonically treated increase the distributing homogeneity of active sites.
First supercritical processing：At supercritical conditions, material is handled, material surface metal can be made quickly to form gold
Belong to oxide, such as the formation of calcium oxide, nickel oxide, iron oxide.
Grafting is handled：The introducing of organic compounds containing nitrogen can further enhance material for CO2Trapping capacity and speed
Degree, and can recycling with reinforcing material.
Compared with prior art, the present invention has the following advantages：
1）CO provided by the invention2Material for trapping preparation process is simple, pollution-free, and the use of gangue is raw material, is bastard coal
The comprehensive utilization of stone provides a new way, while can reduce CO2The manufacturing cost of material for trapping；
2）CO provided by the invention2Material for trapping adsorption effect is good, by bastard coal stone material by microwave-heating in preparation process
Reason, alkali process, impregnation, first supercritical processing and grafting processing, not only increase the specific surface area of material for trapping, while make material
The adsorbing metals active sites such as calcium oxide, nickel oxide and iron oxide, the especially increase pair of calcium oxide active sites are uniform-distribution on material
It is improved in the effect of material for trapping most apparent.It is handled simultaneously by grafting, increases the nitrogenous compound of material surface, further
Material is enhanced for CO2Trapping effect；
3）CO provided by the invention2Material for trapping favorable regeneration effect.
Description of the drawings
Fig. 1 prepares CO for a kind of activating coal gangue2The method process flow chart of sorbing material；
Fig. 2 is CO prepared by embodiment 12Adsorption isotherm at 75 DEG C of sorbing material；
Fig. 3 is CO prepared by embodiment 12Sorbing material electron-microscope scanning figure.
Specific embodiment
The specific embodiment of the present invention is further illustrated below.
The present invention provides a kind of activating coal gangues to prepare CO2The method of sorbing material, the method be using gangue as
Raw material, by microwave-heating, alkali process, impregnation and first supercritical processing and etc. obtain CO2Material for trapping, specific method are
Follow these steps what is carried out：
1）Microwave-heating
Gangue, calcium carbonate and zinc chloride by quality for 80 ~ 90g, 1 ~ 5g and 1 ~ 5g are uniformly mixed, are placed in microwave-heating stove
In, water vapour is passed through, reactor microwave power is then set as 300 ~ 400W, final temperature is 700 ~ 850 DEG C, the reaction time 10
~ 25min, cooling obtain sample A；
2）Alkali process
Sample A is placed in 1.2 ~ 2.5mol/L aqueous slkalis, temperature is that 2.5 ~ 3h is stirred at 60 ~ 70 DEG C, and filtering, drying obtains sample
Product B；
3）Impregnation
Sample B dippings are ultrasonically treated with being used in the mixed aqueous solution of calcium nitrate and nickel nitrate, in dipping process, processing time
For 40min, ultrasonic power 700W, filtering, dry, calcining obtain sample C to dipping after the completion；
4）First supercritical processing
Sample C is placed in reaction kettle, reaction kettle is warming up to 374.3 DEG C, is then passed through water and nitrogen to reaction kettle with 3:1 matter
For amount than the reaction medium mixed, the pressure for controlling reaction kettle is 22.05MPa, reaction medium is made to reach supercriticality, instead
After answering 20 ~ 25min, sample D is obtained；
5）Grafting is handled
Organic amine with alcohol solution is mixed, sample D is then added in, handles 30min, ultrasonic power 700W under ultrasound condition, so
Heating removes alcohols solvent afterwards, and CO is dried to obtain at 100 ~ 115 DEG C2Material for trapping, wherein organic amine are triethylenediamine, two
Ethylenetriamine, hexa, hexamethylene imine, triethylenediamine, polyethyleneimine, diethanol amine, three ethyl alcohol
One kind or arbitrary several mixture in amine.
Microwave-heating processing of the present invention：Gangue with calcium carbonate and zinc chloride is mixed, then passes to water vapour, wherein carbon
Hydrochlorate has under the high temperature conditions to be corroded by hole effect, and can generate silicate, aluminate with the sial compound in gangue
With the compounds such as meta-aluminate；Zinc chloride has catalytic dehydration under high temperature action, makes carbon compound in gangue
Hydrogen, oxygen are separated in the form of water, more carbon are made to retain in the feed, and form carbon compound skeleton, by clear
The surface for washing rear carbon is exposed, and forms the active centre with adsorption capacity, while the presence of zinc chloride can be used as microwave
Absorbent increases absorption of the gangue for microwave；Water vapour is passed through on the one hand as microwave absorption, is increased in reaction process
On the other hand the absorption of microwave can be that the hole of gangue occlusion opens and reacts shape in active site as activator
The hole of Cheng Xin, and increase the hardness of sorbing material, while water vapour can be taken away raw in reaction process as flow regime
Into exhaust gas and extra heat.
Alkali process of the present invention：Material is handled using calcium acetate aqueous slkali, the part contained in material can be dissolved out
Metal oxide, can also react zeolite of the generation with big specific surface area with alumino-silicate, while can increase material
The amount of calcium metal in material.
Impregnation of the present invention：Using calcium nitrate and the mixed aqueous solution of nickel nitrate in dipping process, and make in ultrasound
It is carried out under, wherein calcium, nickel can increase material C O2Adsorption activity position, and be ultrasonically treated make being evenly distributed for active sites
Property increase.
First supercritical processing of the present invention：At supercritical conditions, material is handled, material surface metal can be made quick
Metal oxide is formed, such as the formation of calcium oxide, nickel oxide, iron oxide.
Grafting processing of the present invention：The introducing of organic compounds containing nitrogen can further enhance material for CO2Trapping capacity
And speed, and can recycling with reinforcing material.
Below by specific embodiment, the present invention is further described, but is not limited to following embodiment.
Embodiment 1
1）Microwave-heating
Gangue, calcium carbonate and zinc chloride by quality for 90g, 5g and 5g are uniformly mixed, is placed in microwave-heating stove, is passed through
30cm3Then reactor microwave power is set as 400W by/min water vapours, final temperature is 850 DEG C, reaction time 10min, cold
But sample A is obtained；
2）Alkali process
Sample A is placed in 1.2mol/L calcium acetate aqueous slkalis, temperature is to stir 2.5h at 70 DEG C, is filtered, drying obtains sample
B；
3）Impregnation
By sample B dippings in the mixed aqueous solution of 1.02mol/L calcium nitrate and 0.15mol/L nickel nitrates, being adopted in dipping process
With supersound process, processing time 40min, ultrasonic power 700W, dipping filters, is dry after the completion, 900 DEG C of calcining 50min
Obtain sample C；
4）First supercritical processing
Sample C is placed in reaction kettle, reaction kettle is warming up to 374.3 DEG C, is then passed through water and nitrogen to reaction kettle with 3:1 matter
For amount than the reaction medium mixed, the pressure for controlling reaction kettle is 22.05MPa, reaction medium is made to reach supercriticality, instead
After answering 20min, sample D is obtained；
5）Grafting is handled
Diethylenetriamines with ethanol solution is mixed, sample D is then added in, 30min, ultrasonic power is handled under ultrasound condition
700W, then heating remove alcohols solvent, 70.3gCO are dried to obtain at 115 DEG C2Material for trapping.
The CO that will be obtained2Material for trapping is filled in fixed bed trap, and control trapping temperature is 75 DEG C, and trapping pressure is
Normal pressure controls CO2Air speed be 800h-1By fixed bed, the CO in fixed bed2Material for trapping completes trapping.To embodiment 1 ~ 3
And activated carbon in the market and molecular sieve are to CO2Adsorbance be compared, adsorption time 100min, adsorbate dosage is
2g, the results are shown in Table 1.
Table 1
| Adsorbent | Adsorption temp | Adsorbance（mg CO2/ g adsorbents） |
| Embodiment 1 | 75℃ | 276 |
| Embodiment 2 | 75℃ | 240 |
| Embodiment 3 | 75℃ | 281 |
| Activated carbon | 30 | 50 |
| Molecular sieve | 30 | 130 |
Embodiment 2
1）Microwave-heating
Gangue, calcium carbonate and zinc chloride by quality for 80g, 1g and 5g are uniformly mixed, is placed in microwave-heating stove, is passed through
30cm3Then reactor microwave power is set as 400W by/min water vapours, final temperature is 850 DEG C, reaction time 10min, cold
But sample A is obtained；
2）Alkali process
Sample A is placed in 1.2mol/L calcium acetate aqueous slkalis, temperature is to stir 2.5h at 70 DEG C, is filtered, drying obtains sample
B；
3）Impregnation
By sample B dippings in the mixed aqueous solution of 1.35mol/L calcium nitrate and 0.15mol/L nickel nitrates, being adopted in dipping process
With supersound process, processing time 40min, ultrasonic power 700W, dipping filters, is dry after the completion, 900 DEG C of calcining 50min
Obtain sample C；
4）First supercritical processing
Sample C is placed in reaction kettle, reaction kettle is warming up to 374.3 DEG C, is then passed through water and nitrogen to reaction kettle with 3:1 matter
For amount than the reaction medium mixed, the pressure for controlling reaction kettle is 22.05MPa, reaction medium is made to reach supercriticality, instead
After answering 20min, sample D is obtained；
5）Grafting is handled
Polyethyleneimine with ethanol solution is mixed, sample D is then added in, 30min, ultrasonic power is handled under ultrasound condition
700W, then heating remove alcohols solvent, 59.8gCO are dried to obtain at 115 DEG C2Material for trapping.
The CO that will be obtained2Material for trapping is filled in fixed bed trap, and control trapping temperature is 75 DEG C, and trapping pressure is
Normal pressure controls CO2Air speed be 800h-1By fixed bed, the CO in fixed bed2Material for trapping completes trapping.
Embodiment 3
1）Microwave-heating
Gangue, calcium carbonate and zinc chloride by quality for 80g, 1g and 5g are uniformly mixed, is placed in microwave-heating stove, is passed through
30cm3Then reactor microwave power is set as 400W by/min water vapours, final temperature is 850 DEG C, reaction time 10min, cold
But sample A is obtained；
2）Alkali process
Sample A is placed in 2.5mol/L calcium acetate aqueous slkalis, temperature is to stir 2.5h at 70 DEG C, is filtered, drying obtains sample
B；
3）Impregnation
By sample B dippings in the mixed aqueous solution of 1.35mol/L calcium nitrate and 0.30mol/L nickel nitrates, being adopted in dipping process
With supersound process, processing time 40min, ultrasonic power 700W, dipping filters, is dry after the completion, 900 DEG C of calcining 50min
Obtain sample C；
4）First supercritical processing
Sample C is placed in reaction kettle, reaction kettle is warming up to 374.3 DEG C, is then passed through water and nitrogen to reaction kettle with 3:1 matter
For amount than the reaction medium mixed, the pressure for controlling reaction kettle is 22.05MPa, reaction medium is made to reach supercriticality, instead
After answering 20min, sample D is obtained；
5）Grafting is handled
Polyethyleneimine with ethanol solution is mixed, sample D is then added in, 30min, ultrasonic power is handled under ultrasound condition
700W, then heating remove alcohols solvent, 61.3gCO are dried to obtain at 115 DEG C2Material for trapping.
The CO that will be obtained2Material for trapping is filled in fixed bed trap, and control trapping temperature is 75 DEG C, and trapping pressure is
Normal pressure controls CO2Air speed be 800h-1By fixed bed, the CO in fixed bed2Material for trapping completes trapping.
Claims (6)
1. a kind of activating coal gangue prepares CO2The method of sorbing material, the method are using gangue as raw material, by microwave thermal
Solution, alkali process, impregnation and first supercritical processing and etc. obtain CO2Material for trapping, specific method are to follow these steps to carry out
's：
1）Microwave-heating
Gangue, calcium carbonate and zinc chloride by quality for 80 ~ 90g, 1 ~ 5g and 1 ~ 5g are uniformly mixed, are placed in microwave-heating stove
In, water vapour is passed through, reactor microwave power is then set as 300 ~ 400W, final temperature is 700 ~ 850 DEG C, the reaction time 10
~ 25min, cooling obtain sample A；
2）Alkali process
Sample A is placed in 1.2 ~ 2.5mol/L aqueous slkalis, temperature is that 2.5 ~ 3h is stirred at 60 ~ 70 DEG C, and filtering, drying obtains sample
Product B；
3）Impregnation
Sample B dippings are ultrasonically treated with being used in the mixed aqueous solution of calcium nitrate and nickel nitrate, in dipping process, processing time
For 40min, ultrasonic power 700W, filtering, dry, calcining obtain sample C to dipping after the completion；
4）First supercritical processing
Sample C is placed in reaction kettle, reaction kettle is warming up to 374.3 DEG C, is then passed through water and nitrogen to reaction kettle with 3:1 matter
For amount than the reaction medium mixed, the pressure for controlling reaction kettle is 22.05MPa, reaction medium is made to reach supercriticality, instead
After answering 20 ~ 25min, sample D is obtained；
5）Grafting is handled
Organic amine with alcohol solution is mixed, sample D is then added in, handles 30min, ultrasonic power 700W under ultrasound condition, so
Heating removes alcohols solvent afterwards, and CO is dried to obtain at 100 ~ 115 DEG C2Material for trapping, wherein organic amine are triethylenediamine, two
Ethylenetriamine, hexa, hexamethylene imine, triethylenediamine, polyethyleneimine, diethanol amine, three ethyl alcohol
One kind or arbitrary several mixture in amine.
2. a kind of activating coal gangue prepares CO according to claims 12The method of sorbing material, it is characterised in that the step
Rapid 1）The flow of middle water vapour is 30cm3/min。
3. a kind of activating coal gangue prepares CO according to claims 12The method of sorbing material, it is characterised in that the step
Rapid 2）Middle aqueous slkali is calcium acetate aqueous solution.
4. a kind of activating coal gangue prepares CO according to claims 12The method of sorbing material, it is characterised in that the step
Rapid 3）A concentration of 1.02 ~ 1.35mol/L of middle calcium nitrate solution, a concentration of 0.1 ~ 0.3mol/L of nickel nitrate solution, and two
Kind solution is 1 by volume：2 mixing.
5. a kind of activating coal gangue prepares CO according to claims 12The method of sorbing material, it is characterised in that the step
Rapid 3）Middle calcination temperature is 850 ~ 900 DEG C, time 50min.
6. a kind of activating coal gangue prepares CO according to claims 12The method of sorbing material, it is characterised in that the step
It is rapid 5) in alcohols be a kind of in methanol, ethyl alcohol and normal propyl alcohol or arbitrary several mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN112717973A (en) * | 2020-11-16 | 2021-04-30 | 中北大学 | Preparation of rod-like g-C by microwave hydrothermal method3N4Method and application of nanosheet |
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| CN112915990A (en) * | 2021-01-26 | 2021-06-08 | 中国矿业大学(北京) | Coal gangue in-situ carbon activation material and preparation method and application thereof |
| CN112915990B (en) * | 2021-01-26 | 2022-02-15 | 中国矿业大学(北京) | Coal gangue in-situ carbon activation material and preparation method and application thereof |
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