CN108970590A - Utilize the method and its application of carbon dioxide in active material or modified active material capture and enriched air - Google Patents
Utilize the method and its application of carbon dioxide in active material or modified active material capture and enriched air Download PDFInfo
- Publication number
- CN108970590A CN108970590A CN201810489846.4A CN201810489846A CN108970590A CN 108970590 A CN108970590 A CN 108970590A CN 201810489846 A CN201810489846 A CN 201810489846A CN 108970590 A CN108970590 A CN 108970590A
- Authority
- CN
- China
- Prior art keywords
- modified
- active material
- carbon dioxide
- carbon
- type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B01J20/26—Synthetic macromolecular compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G33/00—Cultivation of seaweed or algae
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
Abstract
The invention discloses a kind of method and its application using carbon dioxide in active material or modified active material capture and enriched air, belong to environmental protection technical field.The present invention is long-term in order to realize, carbon dioxide in efficient absorption air, provide a kind of method using carbon dioxide in active material or modified active material capture and enriched air, wherein active material is ion exchange resin, zeolite molecular sieve, activated alumina or active carbon, modified active material is modified zeolite molecular sieve, modified activated aluminum oxide or modified activated carbon, this method can efficient absorption Carbon Dioxide in Air in normal temperature and pressure, and the carbon dioxide of absorption is come out, it can also be as carbon-dioxide gasfertilizer, for promoting the growth of biology, growth including promoting microalgae, take full advantage of carbon dioxide, and reduce the carbon dioxide content in air.
Description
Technical field
The invention belongs to environmental protection technical fields, and in particular to a method of carbon dioxide in capture and enriched air
And its application.
Background technique
With the development of human society, gas concentration lwevel in air from the 280ppm in 1750 before the industrial revolution by
Gradually rise to 367ppm in 1999, when in 2005 rapidly rises to 379ppm.Quickling increase for gas concentration lwevel results in
Serious greenhouse effects.How to reduce the gas concentration lwevel in air and make full use of carbon dioxide, is academia and industry
The hot spot on boundary.
Due to very low, the industry with respect to for the carbon dioxide in industrial waste gas and natural gas of the gas concentration lwevel in air
The pretreated method and technology of upper processing waste and natural gas is not suitable for that it is captured and is enriched at normal temperatures and pressures, room temperature
Under normal pressure capture and enriched air in carbon dioxide be always a very big challenge.Current feasible methods and techniques are also not
It is more, mainly have: 1, alkaline solution, although the process cost of its absorbing carbon dioxide is low, regeneration i.e. desorption carbon dioxide cost
It is high；2, amine-modified oxide, although its adsorption capacity and stability are preferable, adsorption time is often up to a few hours,
Cause working efficiency relatively low；3, amine-modified metal-organic framework materials, there are many this kind of material literature report, but its cost is high
It is expensive, it yet there are no the product sale for large-scale application；4, cryogenic separation, using the method for two stages compression condensation titanium dioxide
Carbon liquid is solidified into dry ice, then in the method for distillation, carbon dioxide is separated from liquefaction or cured impurity, this
Technology energy consumption is high, needs special equipment, is unsuitable for domestic applications；5, membrane separation technique, this technology is also in conceptual phase, cost
Height, temporarily can not large-scale application.
On the whole, the conventional method disadvantage for the carbon dioxide in air being captured and being enriched at normal temperatures and pressures is bright
It is aobvious, and large-scale application is unable to get in a short time also in developing stage to the research and development of new material, new method.Therefore, anxious at present
Need a kind of method for capableing of the carbon dioxide in efficient absorption air at normal temperatures and pressures.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of sides for capableing of carbon dioxide long-term, in efficient absorption air
Method.
The present invention solves technological means used by above-mentioned technical problem, and there is provided in a kind of capture and enriched air two
The method of carbonoxide, this method using active material capture at normal temperatures and pressures and enriched air in carbon dioxide；The activity
Material is ion exchange resin, zeolite molecular sieve, activated alumina or active carbon.
Wherein, in the method described above using carbon dioxide in active material capture and enriched air, the capture
And the time of carbon dioxide is no less than 30min in enriched air.
Wherein, in the method described above using carbon dioxide in active material capture and enriched air, the ion
Exchanger resin is hydrogen-oxygen type strong basic type anion-exchange resin or hydrogen-oxygen type weak base type anion exchange resin.
Wherein, in the method described above using carbon dioxide in active material capture and enriched air, the ion
The partial size of exchanger resin is 0.1~5.0mm.
Wherein, in the method described above using carbon dioxide in active material capture and enriched air, the zeolite
Molecular sieve is at least one of X-type, Y type, A type, β type or ZSM type.
Wherein, in the method described above using carbon dioxide in active material capture and enriched air, the zeolite
The partial size of molecular sieve is 1~10mm.
Wherein, in the method described above using carbon dioxide in active material capture and enriched air, the activity
Aluminium oxide is at least one of γ type, ρ type, η type, χ type or χ-ρ type.
Wherein, in the method described above using carbon dioxide in active material capture and enriched air, the activity
The partial size of aluminium oxide is 1~10mm.
Wherein, in the method described above using carbon dioxide in active material capture and enriched air, the activity
Charcoal is at least one of wood activated charcoal, active fruit shell carbon, cocoanut active charcoal or coaly activated carbon.
Wherein, in the method described above using carbon dioxide in active material capture and enriched air, the activity
The partial size of charcoal is 1~10mm.
Wherein, in the method described above using carbon dioxide in active material capture and enriched air, when active material
When material is ion exchange resin, the condition of carbon dioxide further includes relative humidity not higher than 80% in capture and enriched air.
The present invention in order to solve the above technical problems, additionally provide another kind can more effectively capture and enriched air in dioxy
Change carbon method, this method using modified active material capture at normal temperatures and pressures and enriched air in carbon dioxide；It is described to change
Property active material be modified zeolite molecular sieve, modified activated aluminum oxide or modified activated carbon.
Wherein, described in the method described above using carbon dioxide in modified active material capture and enriched air
The time of carbon dioxide is no less than 30min in capture and enriched air.
Wherein, described in the method described above using carbon dioxide in modified active material capture and enriched air
Modified zeolite molecular sieve is to be reacted using metal salt with zeolite molecular sieve, the zeolite molecular sieve by Metal Ions Modification of formation.
Preferably, in the method described above using carbon dioxide in modified active material capture and enriched air, institute
It states modified zeolite molecular sieve to be prepared by following methods: zeolite molecular sieve is fitted into reaction vessel, under inert gas shielding,
By concentration be 0.1~2.0M metal salt solution be added in reaction vessel, adjust metal salt solution the rate of outflow be 0.5~
Stop that metal salt solution is added after 15mL/s, 30~300min, it is washed, dry, obtain modified zeolite molecular sieve.
Wherein, described in the method described above using carbon dioxide in modified active material capture and enriched air
Modified activated aluminum oxide is at least one of modified activated aluminum oxide A, modified activated aluminum oxide B or modified activated aluminum oxide C.
Wherein, described in the method described above using carbon dioxide in modified active material capture and enriched air
Modified activated aluminum oxide A is to handle activated alumina, the active oxygen with new construction of formation using metal hydroxide solutions
Change aluminium.
Preferably, in the method described above using carbon dioxide in modified active material capture and enriched air, institute
It states modified activated aluminum oxide A to be prepared by following methods: activated alumina being encased in reaction vessel, is then by concentration
Circulation 0.5 in reaction vessel~for 24 hours is added in the metal hydroxide solutions of 0.1~3.0M, is filtered, washed, is dried, obtains modification
Activated alumina A；Wherein, activated alumina and the mass volume ratio of metal hydroxide solutions are 1:0.5~10.
Wherein, described in the method described above using carbon dioxide in modified active material capture and enriched air
Modified activated aluminum oxide B be to use carbonate solution or bicarbonate solution to handle activated alumina after, formation contains carbon
The activated alumina compound of hydrochlorate or bicarbonate.
Preferably, in the method described above using carbon dioxide in modified active material capture and enriched air, institute
It states modified activated aluminum oxide B to be prepared by following methods: activated alumina being encased in reaction vessel, is then by concentration
The carbonate solution or bicarbonate solution of 0.1~5.0M, which is added in reaction vessel, recycles 0.5~48h, is filtered, washed, is done
It is dry, obtain modified activated aluminum oxide B；Wherein, the mass volume ratio of activated alumina and carbonate solution or bicarbonate solution is
1:0.5~10.
Wherein, described in the method described above using carbon dioxide in modified active material capture and enriched air
After modified activated aluminum oxide C is first handles activated alumina using metal hydroxide solutions, then through carbonate solution or carbonic acid
The processing of hydrogen salt solution, the activated alumina compound containing carbonate or bicarbonate of formation.
Preferably, in the method described above using carbon dioxide in modified active material capture and enriched air, institute
It states modified activated aluminum oxide C to be prepared by following methods: activated alumina being encased in reaction vessel, is then by concentration
Circulation 0.5 in reaction vessel~for 24 hours is added in the metal hydroxide solutions of 0.1~5.0M, is filtered, washed, is dried, by gained
Solid is encased in reaction vessel, then reaction is added in carbonate solution or bicarbonate solution that concentration is 0.1~5.0M and is held
0.5~48h is recycled in device, is filtered, washed, is dried, obtains modified activated aluminum oxide C；Wherein, activated alumina and metal hydrogen-oxygen
The mass volume ratio of compound solution is 1:0.5~10；The mass body of activated alumina and carbonate solution or bicarbonate solution
Product is than being 1:0.5~10.
Wherein, described in the method described above using carbon dioxide in modified active material capture and enriched air
Modified activated carbon is that active carbon is handled using carbonate solution or bicarbonate solution, and formation contains carbonate or bicarbonate
Active Carbon composites.
Preferably, in the method described above using carbon dioxide in modified active material capture and enriched air, institute
It states modified activated carbon to be prepared by following methods: active carbon is encased in reaction vessel, be then 0.1~5.0M by concentration
Carbonate solution or bicarbonate solution be added reaction vessel in recycle 0.5~48h, be filtered, washed, dried, obtain modification
Active carbon；Wherein, the mass volume ratio of active carbon and carbonate solution or bicarbonate solution is 1:0.5~10.
Preferably, in the method described above using carbon dioxide in modified active material capture and enriched air, institute
Stating metal salt is at least one of calcium chloride, lithium chloride, potassium chloride, calcium nitrate, potassium nitrate, potassium sulfate or potassium carbonate.
Preferably, in the method described above using carbon dioxide in modified active material capture and enriched air, institute
Stating metal hydroxides is at least one of lithium hydroxide, potassium hydroxide, sodium hydroxide or calcium hydroxide.
Preferably, in the method described above using carbon dioxide in modified active material capture and enriched air, institute
Stating carbonate is at least one of sodium carbonate or potassium carbonate.
Preferably, in the method described above using carbon dioxide in modified active material capture and enriched air, institute
Stating bicarbonate is at least one of sodium bicarbonate or saleratus.
The present invention also answers the above-mentioned carbon dioxide using in active material or modified active material capture and enriched air
For in plant growth, after the carbon dioxide in active material or modified active material capture and enriched air, by active material
Or the carbon dioxide adsorbed in modified active material comes out, and as carbon-dioxide gasfertilizer, can be used to the life for promoting biology
It is long, such as the growth for promoting microalgae.
Described above will utilize the Carbon Dioxide Application in active material or modified active material capture and enriched air
When in both culturing microalgae, when active material is ion exchange resin, the condition of desorption is that relative humidity is higher than 40%, the time 5
~120min；When material be zeolite molecular sieve, activated alumina, active carbon, modified zeolite molecular sieve, modified activated aluminum oxide or
When modified activated carbon, the condition of desorption is 300~500 DEG C of 0.5~5h of heating.
In the present invention, the meaning of the mass volume ratio are as follows: solid in mass, solution by volume, in identical quantity
Ratio under grade unit, such as active carbon described above and the mass volume ratio of carbonate solution or bicarbonate solution are 1:
0.5~10, it can be active carbon as unit of g, carbonate solution or bicarbonate solution are as unit of mL.
The present invention is also to utilize zeolite molecular sieve, activated alumina, active carbon, modified zeolite molecular sieve, modified active oxygen
Change aluminium or modified activated carbon capture and the carbon dioxide in enriched air, desorption carbon dioxide provide a kind of desorption box, wraps
Include box body (1), heating element (3) and upper cover (4)；Wherein, box body (1) at least one end has opening, and heating element (3) is mounted on
In box body (1), it is open at one end that upper cover (4) is mounted on box body (1).
The present invention also for using ion exchange resin capture and enriched air in carbon dioxide, desorption carbon dioxide provide
A kind of desorption box comprising box body (1), heating element (3), upper cover (4) and humidifier (5)；Wherein, box body (1) at least one
End has opening, and heating element (3) is mounted in box body (1), and it is open at one end that upper cover (4) is mounted on box body (1), humidifier (5)
It is connected to box body (1) inside.
It preferably, further include fan (2) in above-mentioned desorption box, box body (1) both ends have opening, and upper cover (4) is mounted on box
Body (1) is open at one end, and fan (2) is mounted on the opening of box body (1) other end.
The beneficial effects of the present invention are:
The present invention is using the carbon dioxide in active material and modified active material capture and enriched air, by carbon dioxide
It is used for both culturing microalgae after desorption, reduces the carbon dioxide content in air, and take full advantage of carbon dioxide；Through the present invention
Active material after method of modifying is modified is captured from air and the ability of carbon dioxide-enriched has a distinct increment, and through too long
After the adsorption-desorption cycle use of phase, the more stable absorption to carbon dioxide and desorption ability are still kept；It is used herein
Carbon dioxide be air in existing substance, not will cause carbon dioxide generate and greenhouse effects, have good application before
Scape；Using in air carbon dioxide carry out both culturing microalgae, not only environmental protection and also can make full use of the resource for seeming useless, produce
Raw a large amount of fronds have good utility value, the industrialization potential with height.
Detailed description of the invention
Fig. 1 is strong basic type anion-exchange resin (hydrogen-oxygen type) and weak base type anion exchange resin (hydrogen-oxygen type) desorption two
Carbonoxide is used for both culturing microalgae, the biomass variety situation map of microalgae.
Fig. 2 is that 10X type zeolite molecular sieve and its modified active material desorb carbon dioxide and be used for both culturing microalgae, microalgae
Biomass variety situation map.
Fig. 3 is that 13X type zeolite molecular sieve and its modified active material desorb carbon dioxide and be used for both culturing microalgae, microalgae
Biomass variety situation map.
Fig. 4 is that Y-type zeolite molecular sieve and its modified active material desorb carbon dioxide and be used for both culturing microalgae, the life of microalgae
Object amount figure of changing.
Fig. 5 is that 4A type zeolite molecular sieve and its modified active material desorb carbon dioxide and be used for both culturing microalgae, microalgae
Biomass variety situation map.
Fig. 6 is that 5A type zeolite molecular sieve and its modified active material desorb carbon dioxide and be used for both culturing microalgae, microalgae
Biomass variety situation map.
Fig. 7 is that ZSM-5 type zeolite molecular sieve and its modified active material desorb carbon dioxide and be used for both culturing microalgae, microalgae
Biomass variety situation map.
Fig. 8 is that γ type activated alumina and its modified active material desorb carbon dioxide and be used for both culturing microalgae, microalgae
Biomass variety situation map.
Fig. 9 is that ρ type activated alumina and its modified active material desorb carbon dioxide and be used for both culturing microalgae, the life of microalgae
Object amount figure of changing.
Figure 10 is that η type activated alumina and its modified active material desorb carbon dioxide and be used for both culturing microalgae, microalgae
Biomass variety situation map.
Figure 11 is that χ type activated alumina and its modified active material desorb carbon dioxide and be used for both culturing microalgae, microalgae
Biomass variety situation map.
Figure 12 is that χ-ρ type activated alumina and its modified active material desorb carbon dioxide and be used for both culturing microalgae, microalgae
Biomass variety situation map.
Figure 13 is that wood activated charcoal and its modified active material desorb carbon dioxide and be used for both culturing microalgae, the biology of microalgae
Measure figure of changing.
Figure 14 is that active fruit shell carbon and its modified active material desorb carbon dioxide and be used for both culturing microalgae, the biology of microalgae
Measure figure of changing.
Figure 15 is that cocoanut active charcoal and its modified active material desorb carbon dioxide and be used for both culturing microalgae, the biology of microalgae
Measure figure of changing.
Figure 16 is that coaly activated carbon and its modified active material desorb carbon dioxide and be used for both culturing microalgae, the biology of microalgae
Measure situation of change.
Figure 17 is the decomposition texture schematic diagram of carbon dioxide adsorption-desorption apparatus of the present invention, wherein 1 being box body, 2 being wind
Fan, 3 be heating element, 4 be upper cover, 5 be humidifier.
Figure 18 is the decomposition texture schematic diagram of carbon dioxide adsorption-desorption apparatus of the present invention, wherein 1 being box body, 2 being wind
Fan, 3 be heating element, 4 be upper cover.
Specific embodiment
The present invention provides the methods of carbon dioxide in two kinds of captures and enriched air；Specifically, one of method is
Using active material normal temperature and pressure capture and enriched air in carbon dioxide；The active material is ion exchange resin, boiling
Stone molecular sieve, activated alumina or active carbon.
Ion exchange resin is with functional group, has reticular structure, insoluble high-molecular compound, is widely used in
The industries such as water process, food industry, pharmaceutical industry, environmental protection；Zeolite molecular sieve (Zeolite) is that one kind is widely used in gas
Body isolates and purifies, ion exchange, is catalyzed the inorganic crystal material reacted；Activated alumina (ActivatedAlumina) is a kind of
The solid material of porosity, high degree of dispersion has very big surface area, is widely used as catalyst, catalyst carrier；Active carbon
(Activated Carbon) is a kind of specially treated charcoal, has countless tiny holes, and surface area is huge, is had very strong
Physical absorption and chemical adsorption capacity.
Ion exchange resin (hydrogen-oxygen type), zeolite molecular sieve, activated alumina and active carbon of the present invention can adsorb simultaneously
Desorb carbon dioxide；The ion exchange resin is hydrogen-oxygen type strong basic type anion-exchange resin or hydrogen-oxygen type weak base type anion
Exchanger resin；The zeolite molecular sieve is at least one of X-type, Y type, A type, β type or ZSM type；The activated alumina is
At least one of γ type, ρ type, η type, χ type or χ-ρ type；The active carbon is wood activated charcoal, active fruit shell carbon, coconut husk are living
Property at least one of charcoal or coaly activated carbon.
Active material anion exchange resin (hydrogen-oxygen type) adsorbs carbon dioxide under low relative humidity (being not higher than 80%),
Carbon dioxide is desorbed under high relative humidity (being higher than 40%), that is, requires to adsorb the opposite of carbon dioxide in a specific experiment
Humidity is lower than the relative humidity of desorption；Zeolite molecular sieve, activated alumina or active carbon adsorb air at normal temperatures and pressures
In carbon dioxide after, can be substantially by the carbon dioxide of absorption in 300~500 DEG C of 0.5~5h of heating.It is produced to improve
Product working efficiency carbon dioxide-enriched as far as possible simultaneously, the time of carbon dioxide is no less than in active material capture and enriched air
30min。
Specifically, it is another can more effectively capture and enriched air in the method for carbon dioxide be to utilize modified active material
Material carbon dioxide in normal temperature and pressure capture and enriched air；The modified active material is modified zeolite molecular sieve, modified work
Zeolite molecular sieve described above, activated alumina and active carbon, i.e., be modified by property aluminium oxide or modified activated carbon.
In order to improve product working efficiency while as far as possible carbon dioxide-enriched, modified active material capture and enriched air
The time of middle carbon dioxide is no less than 30min；Modified zeolite molecular sieve, modified activated aluminum oxide or modified activated carbon are normal in room temperature
It, can be substantially by the carbon dioxide solution of absorption in 300~500 DEG C of 0.5~5h of heating after carbon dioxide in pressure absorption air
It inhales.
In the present invention, the modified zeolite molecular sieve is to use metal salt (such as calcium chloride, lithium chloride, potassium chloride, nitric acid
Calcium, potassium nitrate, potassium sulfate or potassium carbonate) it is reacted with zeolite molecular sieve, in the cation replacement zeolite molecular sieve in metal salt
Cation, the zeolite molecular sieve by Metal Ions Modification of formation, makes the absorption property of zeolite molecular sieve change；It can be by
Following methods are prepared: zeolite molecular sieve being fitted into reaction vessel, is 0.1~2.0M by concentration under inert gas shielding
Metal salt solution be added in reaction vessel, adjust metal salt solution the rate of outflow be 0.5~15mL/s, 30~300min
Stop that metal salt solution is added afterwards, it is washed, dry, obtain modified zeolite molecular sieve.
Modified activated aluminum oxide can be obtained by the way that three kinds of methods are modified to activated alumina in the present invention, modified active oxidation
Aluminium is at least one of modified activated aluminum oxide A, modified activated aluminum oxide B or modified activated aluminum oxide C.
Wherein, the modified activated aluminum oxide A is to use metal hydroxides (such as lithium hydroxide, potassium hydroxide, hydroxide
Sodium or calcium hydroxide) solution processing activated alumina, the activated alumina with new construction of formation；Metal hydroxides and work
Property aluminium oxide chemically react, metal hydroxides corrosion activity aluminium oxide internal gutter, make activated alumina Kong Rong, ratio
Surface area etc. changes, so that activated alumina be made to form new structure；It can be prepared by following methods: by active oxygen
Change aluminium to be encased in reaction vessel, then the metal hydroxide solutions that concentration is 0.1~3.0M are added in reaction vessel and follow
Ring 0.5~for 24 hours, it is filtered, washed, dried, obtain modified activated aluminum oxide A；Wherein, activated alumina and metal hydroxides are molten
The mass volume ratio of liquid is 1:0.5~10.
Wherein, the modified activated aluminum oxide B is to use carbonate (such as sodium carbonate or potassium carbonate) solution or bicarbonate
After salt (such as sodium bicarbonate or saleratus) solution handles activated alumina, carbonate or bicarbonate enter activated alumina
In internal gutter, with activated alumina physical bond, the activated alumina compound containing carbonate or bicarbonate of formation；
It can be prepared by following methods: activated alumina be encased in reaction vessel, the carbon for being then 0.1~5.0M by concentration
Acid salt solution or bicarbonate solution, which are added in reaction vessel, recycles 0.5~48h, is filtered, washed, is dried, obtains modified active
Aluminium oxide B；Wherein, the mass volume ratio of activated alumina and carbonate solution or bicarbonate solution is 1:0.5~10.
Wherein, it after the modified activated aluminum oxide C is first handles activated alumina using metal hydroxide solutions, then passes through
Carbonate solution or bicarbonate solution processing, the activated alumina compound containing carbonate or bicarbonate of formation；Its
It can be prepared by following methods: activated alumina is encased in reaction vessel, the metal for being then 0.1~5.0M by concentration
Hydroxide solution be added reaction vessel in circulation 0.5~for 24 hours, be filtered, washed, dried, obtained solid is encased in reaction
In container, then by concentration be 0.1~5.0M carbonate solution or bicarbonate solution be added reaction vessel in circulation 0.5~
48h is filtered, washed, is dried, and modified activated aluminum oxide C is obtained；Wherein, the matter of activated alumina and metal hydroxide solutions
Amount volume ratio is 1:0.5~10；The mass volume ratio of activated alumina and carbonate solution or bicarbonate solution be 1:0.5~
10。
Modified activated carbon is to handle active carbon, carbonate or carbon using carbonate solution or bicarbonate solution in the present invention
Sour hydrogen salt enters in active carbon internal gutter, with active carbon physical bond, the work containing carbonate or bicarbonate of formation
Property Carbon composites；It can be prepared by following methods: active carbon is encased in reaction vessel, then by concentration be 0.1~
The carbonate solution or bicarbonate solution of 5.0M, which is added in reaction vessel, recycles 0.5~48h, is filtered, washed, is dried, obtained
Modified activated carbon；Wherein, the mass volume ratio of active carbon and carbonate solution or bicarbonate solution is 1:0.5~10.
It when the present invention prepares modified active material, requires to be washed in post-processing and be dried, prepare modified zeolite point
When son sieve, in post-processing, washing generally uses 3~6 times of volumes (multiple of volume is for the quality of active material)
Deionized water is cleaned 3~5 times, then in 250~500 DEG C of 24~36h of vacuum drying, then it is logical with the speed of 50~500mL/min
Enter 1~4h of inert gas, prevents oxygen in air by material oxidation.
When preparing modified activated aluminum oxide or modified activated carbon, in post-processing, washing generally using 1-6 times of volume go from
Sub- water cleans 1~5 time, then 50~300 DEG C dry 1~for 24 hours, 400~500 DEG C of vacuum drying are then warming up in 1~2h
24~36h is handled, prevents oxidation reaction under high temperature from occurring.
It, will since the present invention is using the carbon dioxide in active material or modified active material capture and enriched air
After the carbon dioxide adsorbed in active material or modified active material comes out, it can be used as carbon-dioxide gasfertilizer, be applied to
Promote using carbon dioxide as the growth of the biology of growth nutrient, such as promoting micro algae growth.In addition, inventor points out, it is living
Property material includes but is not limited to ion exchange resin, zeolite molecular sieve, activated alumina or active carbon, and modified active material includes
But it is not limited to modified zeolite molecular sieve, modified activated aluminum oxide or modified activated carbon, as long as material has absorption carbon dioxide
Ability can be used for biological growth.
Zeolite molecular sieve in the present invention after metal ion-modified, the active oxidation through metal hydroxide solutions modification
Aluminium is modified through the modified activated alumina of carbonate solution or bicarbonate solution, first through metal hydroxide solutions again through carbon
Acid salt solution or the activated alumina of bicarbonate solution modification, the active carbon through carbonate solution or bicarbonate solution modification
It can still be maintained after relatively surely with stronger carbon dioxide adsorption ability, and by long-term adsorption-desorption cycle
Fixed carbon dioxide adsorption and desorption ability.Therefore, modified active material is more suitable in promoting biological growth in the present invention
It is applied.
Microalgae is that have photosynthetic rate height using the biology that carbon dioxide is most in nature, breed fast, environmental suitability
By force, treatment effeciency it is high, it is controllable and easily with Other Engineering Integration ofTechnology the advantages that, and can get efficiently, it is three-dimensional, highdensity
Culture technique, while a large amount of frond is generated after carbon sequestration with good utility value, therefore the industrialization potential with height.
As shown in figure 17, according to an embodiment of the invention, the desorption box A includes carbon dioxide box 1, fan 2, adds
Thermal element 3, upper cover 4 and humidifier 5.
Specifically, 1 both ends of box body have opening, and heating element 3 is mounted in box body 1, and upper cover 4 is mounted on 1 one end of box body
Opening, fan 2 are mounted on another end opening of box body 1, are connected to inside humidifier 5 and box body 1.Ion exchange resin is loaded into box body
Inside 1, fan 2 blows air into desorption box 1, and heating element 3 heats the air being blown into, and hot-air makes ion exchange resin
Humidity reduces, and ion exchange resin is to adsorb the carbon dioxide in air, after a certain period of time, closes fan 2 and heating element
3, start humidifier 5, humidifier 5 vaporizes water by microwave, and the water of vaporization is blown into desorption box 1, ion exchange resin
Humidity increases, and the carbon dioxide of absorption is discharged, is escaped by upper cover 4.
As shown in figure 18, according to an embodiment of the invention, the desorption box B includes carbon dioxide box 1, fan 2, adds
Thermal element 3 and upper cover 4.
Specifically, 1 both ends of box body have opening, and heating element 3 is mounted in box body 1, and upper cover 4 is mounted on 1 one end of box body
Opening, fan 2 are mounted on another end opening of box body 1.Active material or modified active material are loaded into inside desorption box 1, fan 2
It blows air into and desorbs box 1, the active material of active material or modification is to adsorb the carbon dioxide in air, certain time
Afterwards, after the active material of closing fan 2, starting heating element 3, active material or modification is heated, by the carbon dioxide of absorption
Release, is escaped by upper cover 4.
In above-mentioned desorption box A and B, installation fan be in order to make large quantity of air flow through active material or modified active material,
More carbon dioxide are adsorbed convenient for material, accelerate the speed of absorption or desorption, can decide whether that wind is installed according to actual needs
Fan, when not installing fan, box body is at least open at one end.
Below by embodiment, invention is further described in detail, but does not therefore limit the scope of the present invention
Among the embodiment described range.
Carbon dioxide detection device employed in the embodiment of the present invention is the production of Shenzhen Yuan Te Science and Technology Ltd.
The portable carbon dioxide detector of model SKY2000-CO2-M.
In the embodiment of the present invention, the partial size of used ion exchange resin is 0.1~5.0mm；The zeolite molecular sieve
Partial size be 1~10mm；The partial size of the activated alumina is 1~10mm；The partial size of the active carbon is 1~10mm.
The embodiment of the present invention 1~14 is parallel simultaneously to be carried out 3 times, as a result takes 3 average value, and calculate standard deviation.
In embodiment 1~14 in table 1~13 " gas concentration lwevel " column " X ± S ", " X " indicates the average value of parallel test,
" S " is the standard deviation of 3 parallel laboratory tests.
In embodiment 1~12 in the subscript of table 1~12 " gas concentration lwevel " column gas concentration lwevel data, " * " is indicated
Modified active material is compared with active material before modified, p < 0.05, significant difference；" * * " indicates modified active material and changes
Active material is compared before property, p < 0.01, and difference is extremely significant；" ## " indicates active material or modified active material and empty desorption box A
Or empty desorption box B is compared, p < 0.01, difference is extremely significant.
In 15 Fig. 1~16 of embodiment, " * " indicates active material or modified active material compared with air, and p < 0.05 is poor
It is different significant；" * * " indicates active material or modified active material compared with air, and p < 0.01, difference is extremely significant；" # " indicates
Modified active material is compared with active material before modified, p < 0.05, significant difference；" ## " indicates modified active material and modification
Preceding active material is compared, and p < 0.01, difference is extremely significant.
Embodiment 1: ion exchange resin adsorbs the carbon dioxide in simultaneously desorption air under normal temperature and pressure
(1), respectively by 150g strong basic type anion-exchange resin (hydrogen-oxygen type) and weak base type anion exchange resin (hydrogen-oxygen
Type) it is loaded into two desorption box A；
(2), relative humidity 50% under room temperature, to desorption box A in be passed through air 10min；
(3), desorption box A is put into the closed container of volume 1.5L, vapor is passed through into container, make to desorb in box A
Relative humidity rise to 70%, maintain 50min, it is dense using carbon dioxide in portable carbon dioxide detector record closed container
Degree；
(4), above-mentioned adsorption-desorption operation is repeated, gas concentration lwevel when recording the 100th time and the 500th time the results are shown in Table
1。
Carbon dioxide result data in the absorption of 1 ion exchange resin of table and desorption air
Embodiment 2: zeolite molecular sieve adsorbs the carbon dioxide in simultaneously desorption air under normal temperature and pressure
(1), the 10X type of 150g, 13X type, Y type, 4A type, 5A type and ZSM-5 type zeolite molecular sieve are loaded into six respectively
In a desorption box B；
(2), relative humidity 70% under room temperature, to desorption box B in be passed through air 90min；
(3), desorption box B is put into the closed container of volume 1.5L, the zeolite molecules in heating desorption box B are sieved to 350
DEG C, 2.5h is maintained, gas concentration lwevel in portable carbon dioxide detector record closed container is used；
(4), above-mentioned adsorption-desorption operation is repeated, gas concentration lwevel when recording the 100th time and the 500th time the results are shown in Table
2。
Carbon dioxide result data in the absorption of 2 zeolite molecular sieve of table and desorption air
Embodiment 3: potassium chloride modified zeolite molecular sieve, and the titanium dioxide in absorption at normal temperatures and pressures and desorption air
Carbon
(1), the 10X type of 500g, 13X type, Y type, 4A type, 5A type and ZSM-5 type zeolite molecular sieve are packed into six respectively
In ion exchange column, helium 1.5h is passed through with the speed of 430mL/min；
(2), by potassium chloride deionized water dissolving, the Klorvess Liquid that concentration is 0.5M is obtained；
(3), Klorvess Liquid is added in ion exchange column, control valve makes Klorvess Liquid with the speed of 1mL/s
Outflow；
(4), stop that Klorvess Liquid is added after 50min, rinsed zeolite molecular sieve 3 times with the deionized water of 5 times of volumes；
(5), the zeolite molecular sieve rinsed with deionized water is taken out, be warming up to 450 DEG C in 1h and be dried under vacuum
Zeolite molecular sieve after drying is passed through helium 2h with the speed of 100mL/min by 36h, obtains metallic potassium ion modification zeolite point
Son sieve；Wherein, after modified, quality is respectively as follows: for 10X type, 13X type, Y type, 4A type, 5A type and ZSM-5 type zeolite molecular sieve
530g, 517g, 543g, 524g, 527g and 511g；
(6), the metallic potassium ion modification zeolite molecular sieve 150g of above-mentioned different model is loaded into six desorption box B respectively
In；
(7), relative humidity 70% under room temperature, to desorption box B in be passed through air 90min；
(8), desorption box B is put into the closed container of volume 1.5L, the modified zeolite molecular sieve in heating desorption box B is extremely
350 DEG C, 2.5h is maintained, uses gas concentration lwevel in portable carbon dioxide detector record closed container；
(9), above-mentioned adsorption-desorption operation is repeated, gas concentration lwevel when recording the 100th time and the 500th time the results are shown in Table
3。
Carbon dioxide result data in the absorption of 3 potassium chloride modified zeolite molecular sieve of table and desorption air
Embodiment 4: activated alumina adsorbs the carbon dioxide in simultaneously desorption air under normal temperature and pressure
(1), the γ type of 150g, ρ type, η type, χ type and χ-ρ type are loaded into five desorption box B respectively；
(2) relative humidity 70% under room temperature, to desorption box B in be passed through air 90min；
(3) desorption box B is put into the closed container of volume 1.5L, the activated alumina in heating desorption box B to 500
DEG C, 3h is maintained, gas concentration lwevel in portable carbon dioxide detector record closed container is used；
(4), above-mentioned adsorption-desorption operation is repeated, gas concentration lwevel when recording the 100th time and the 500th time the results are shown in Table
4。
Carbon dioxide result data in the absorption of 4 activated alumina of table and desorption air
Embodiment 5: potassium carbonate modified activated alumina, and the titanium dioxide in absorption at normal temperatures and pressures and desorption air
Carbon
(1), by potassium carbonate deionized water dissolving, the solution of potassium carbonate that concentration is 0.2M is obtained；
(2), the γ type of 200g, ρ type, η type, χ type and χ-ρ type activated alumina are encased in five reaction columns respectively,
800mL solution of potassium carbonate is added, solution is made to recycle 1h in reaction column；
(3), liquid is discarded, activated alumina is collected, is cleaned 3 times with the deionized water of 5 times of volumes, is handled later in 90 DEG C
Then 16h is warming up to 500 DEG C of vacuum drying treatment 36h, obtains potassium carbonate modified activated alumina in 2h；Wherein, γ type, ρ
Type, η type, χ type and χ-ρ type activated alumina after modified, quality be respectively as follows: 236g, 232g, 223g, 221g, 208g and
211g；
(4), the potassium carbonate modified activated alumina 150g of above-mentioned different model is loaded into five desorption box B respectively；
(5), relative humidity 70% under room temperature, to desorption box B in be passed through air 90min；
(6), desorption box B is put into the closed container of volume 1.5L, the modified activated aluminum oxide in heating desorption box B is extremely
500 DEG C, 3h is maintained, uses gas concentration lwevel in portable carbon dioxide detector record closed container；
(7), above-mentioned adsorption-desorption operation is repeated, gas concentration lwevel when recording the 100th time and the 500th time the results are shown in Table
5。
Carbon dioxide result data in the absorption of the potassium carbonate modified activated alumina of table 5 and desorption air
Embodiment 6: saleratus modified activated aluminum oxide, and the dioxy in absorption at normal temperatures and pressures and desorption air
Change carbon
(1), by saleratus deionized water dissolving, the potassium bicarbonate solution that concentration is 0.5M is obtained；
(2), the γ type of 200g, ρ type, η type, χ type and χ-ρ type activated alumina are encased in five reaction columns respectively,
800mL potassium bicarbonate solution is added, solution is made to recycle 2h in reaction column；
(3), liquid is discarded, activated alumina is collected, is cleaned 5 times with the deionized water of 5 times of volumes, later at 200 DEG C
Reason for 24 hours, is then warming up to 500 DEG C of vacuum drying treatment 36h, obtains saleratus modified activated aluminum oxide in 2h；Wherein, γ
After modified, quality is respectively as follows: 231g, 245g, 239g, 218g and 215g for type, ρ type, η type, χ type and χ-ρ type activated alumina；
(4), the saleratus modified activated aluminum oxide 150g of above-mentioned different model is loaded into five desorption box B；
(5), relative humidity 70% under room temperature, to desorption box B in be passed through air 90min；
(6), desorption box B is put into the closed container of volume 1.5L, the modified activated aluminum oxide in heating desorption box B is extremely
500 DEG C, 3h is maintained, uses gas concentration lwevel in portable carbon dioxide detector record closed container；
(7), above-mentioned adsorption-desorption operation is repeated, gas concentration lwevel when recording the 100th time and the 500th time the results are shown in Table
6。
Carbon dioxide result data in the absorption of 6 saleratus modified activated aluminum oxide of table and desorption air
Embodiment 7: sodium hydroxide modified activated aluminum oxide, and the dioxy in absorption at normal temperatures and pressures and desorption air
Change carbon
(1), by sodium hydroxide deionized water dissolving, the sodium hydroxide solution that concentration is 2.5M is obtained；
(2), the γ type of 100g, ρ type, η type, χ type and χ-ρ type activated alumina are encased in five reaction columns respectively,
500mL sodium hydroxide solution is added, recycles solution for 24 hours in reaction column；
(3), liquid is discarded, activated alumina is collected, is cleaned 2 times with the deionized water of 1 times of volume, is handled later in 90 DEG C
Then 12h is warming up to 400 DEG C of vacuum drying treatments for 24 hours, obtains sodium hydroxide modified activated aluminum oxide in 2h；Wherein, γ type, ρ
After modified, quality is respectively as follows: 92g, 89g, 97g, 92g and 91g for type, η type, χ type and χ-ρ type activated alumina；
(4), 150g sodium hydroxide modified activated aluminum oxide is loaded into desorption box B；
(5), relative humidity 70% under room temperature, to desorption box B in be passed through air 90min；
(6), desorption box B is put into the closed container of volume 1.5L, the modified activated aluminum oxide in heating desorption box B is extremely
500 DEG C, 3h is maintained, uses gas concentration lwevel in portable carbon dioxide detector record closed container；
(7), above-mentioned adsorption-desorption operation is repeated, gas concentration lwevel when recording the 100th time and the 500th time the results are shown in Table
7。
Carbon dioxide result data in the absorption of 7 sodium hydroxide modified activated aluminum oxide of table and desorption air
Embodiment 8: it is first modified through sodium hydroxide, then inhaled through potassium carbonate modified activated alumina, and at normal temperatures and pressures
Carbon dioxide in attached and desorption air
(1), by sodium hydroxide deionized water dissolving, the sodium hydroxide solution that concentration is 2M is obtained；
(2), the γ type of 500g, ρ type, η type, χ type and χ-ρ type activated alumina are encased in five reaction columns respectively,
2500mL sodium hydroxide solution is added, recycles solution for 24 hours in reaction column；
(3), liquid is discarded, activated alumina is collected, is cleaned 2 times with the deionized water of 1 times of volume, is handled later in 90 DEG C
For 24 hours, it is then warming up to 500 DEG C of vacuum drying treatments in 1h for 24 hours, obtains sodium hydroxide modified activated aluminum oxide；
(4), by potassium carbonate deionized water dissolving, the solution of potassium carbonate that concentration is 0.5M is obtained；
(5), the sodium hydroxide modified activated aluminum oxide for the different model that step (3) obtains is encased in five reactions respectively
In column, 2500mL solution of potassium carbonate is added, recycles solution for 24 hours in reaction column；
(6), liquid is discarded, activated alumina is collected, is cleaned 5 times with the deionized water of 5 times of volumes, is handled later in 90 DEG C
Then 16h is warming up to 500 DEG C of vacuum drying treatments for 24 hours in 1h, obtain first through sodium hydroxide modification, again through potassium carbonate modified work
Property aluminium oxide；Wherein, γ type, ρ type, η type, χ type and χ-ρ type activated alumina after modified, quality be respectively as follows: 510g, 525g,
513g, 501g and 491g；
(7), the modified activated aluminum oxide 150g for the different model that step (6) obtains is loaded into five desorption box B respectively
In；
(8), relative humidity 70% under room temperature, to desorption box B in be passed through air 90min；
(9), desorption box B is put into the closed container of volume 1.5L, the modified activated aluminum oxide in heating desorption box B is extremely
500 DEG C, 3h is maintained, uses gas concentration lwevel in portable carbon dioxide detector record closed container；
(10), above-mentioned adsorption-desorption operation is repeated, as a result gas concentration lwevel when recording the 100th time and the 500th time is shown in
Table 8.
Table 8 is first through sodium hydroxide modification, again through the titanium dioxide in the absorption of potassium carbonate modified activated alumina and desorption air
Carbon result
Data
Embodiment 9: it is first modified through sodium hydroxide, then through saleratus modified activated aluminum oxide, and at normal temperatures and pressures
Adsorb the carbon dioxide in simultaneously desorption air
(1), by sodium hydroxide deionized water dissolving, the sodium hydroxide solution that concentration is 2M is obtained；
(2), the γ type of 500g, ρ type, η type or χ type and χ-ρ type activated alumina are encased in five reaction columns respectively
In, 2500mL sodium hydroxide solution is added, solution is made to recycle 20h in reaction column；
(3), liquid is discarded, activated alumina is collected, is cleaned 2 times with the deionized water of 1 times of volume, is handled later in 90 DEG C
For 24 hours, it is then warming up to 500 DEG C of vacuum drying treatments in 1h for 24 hours, obtains sodium hydroxide modified activated aluminum oxide；
(4), by saleratus deionized water dissolving, the potassium bicarbonate solution that concentration is 0.8M is obtained；
(5), the sodium hydroxide modified activated aluminum oxide for the different model that step (3) obtains is encased in five reactions respectively
In column, 3000mL potassium bicarbonate solution is added, solution is made to recycle 2h in reaction column；
(6), liquid is discarded, activated alumina is collected, is cleaned 5 times with the deionized water of 5 times of volumes, is handled later in 90 DEG C
Then 16h is warming up to 500 DEG C of vacuum drying treatments for 24 hours in 1h, obtain first modified through sodium hydroxide, modified through saleratus again
Activated alumina；Wherein, γ type, ρ type, η type, χ type and χ-ρ type activated alumina after modified, quality be respectively as follows: 514g,
522g, 507g, 492g and 488g；
(7), the modified activated aluminum oxide 150g for the different model that step (6) obtains is loaded into five desorption box B respectively
In；
(8), relative humidity 70% under room temperature, to desorption box B in be passed through air 90min；
(9), desorption box B is put into the closed container of volume 1.5L, the modified activated aluminum oxide in heating desorption box B is extremely
500 DEG C, 3h is maintained, uses gas concentration lwevel in portable carbon dioxide detector record closed container；
(10), above-mentioned adsorption-desorption operation is repeated, as a result gas concentration lwevel when recording the 100th time and the 500th time is shown in
Table 9.
Table 9 is first by sodium hydroxide modification, again through the dioxy in the absorption of saleratus modified activated aluminum oxide and desorption air
Change carbon knot
Fruit data
Embodiment 10: the carbon dioxide under normal temperature and pressure in activated carbon adsorption and desorption air
(1), 150g wood activated charcoal, active fruit shell carbon, cocoanut active charcoal and coaly activated carbon are loaded into four respectively
It desorbs in box B；
(2), relative humidity 70% under room temperature, to desorption box B in be passed through air 60min；
(3), desorption box B is put into the closed container of volume 1.5L, the active carbon in heating desorption box B is to 250 DEG C, dimension
2h is held, gas concentration lwevel in portable carbon dioxide detector record closed container is used；
(4), above-mentioned adsorption-desorption operation is repeated, gas concentration lwevel when recording the 100th time and the 500th time the results are shown in Table
10。
Carbon dioxide result data in 10 activated carbon adsorption of table and desorption air
Embodiment 11: potassium carbonate modified active carbon, and the carbon dioxide in absorption at normal temperatures and pressures and desorption air
(1), by potassium carbonate deionized water dissolving, the solution of potassium carbonate that concentration is 0.2M is obtained；
(2), 2000g wood activated charcoal, active fruit shell carbon, cocoanut active charcoal and coaly activated carbon are encased in four respectively
In reaction column, 5000mL solution of potassium carbonate is added, solution is made to recycle 2h in reaction column；
(3), it discards liquid, collects active carbon, clean 3 times with the deionized water of 5 times of volumes, later in 90 DEG C of processing 16h,
Then it is warming up to 450 DEG C of vacuum drying treatment 36h in 1h, obtains potassium carbonate modified active carbon；Wherein, wood activated charcoal, shell
After modified, quality is respectively as follows: 2274g, 2531g, 2527g and 2257g for active carbon, cocoanut active charcoal and coaly activated carbon；
(4), the different types of potassium carbonate modified active carbon 150g for respectively obtaining step (3) is loaded into four desorption boxes
In B；
(5), relative humidity 70% under room temperature, to desorption box B in be passed through air 60min；
(6), desorption box B is put into the closed container of volume 1.5L, the modified activated carbon in heating desorption box B to 250
DEG C, 2h is maintained, gas concentration lwevel in portable carbon dioxide detector record closed container is used；
(7), above-mentioned adsorption-desorption operation is repeated, gas concentration lwevel when recording the 100th time and the 500th time the results are shown in Table
11。
Carbon dioxide result data in the potassium carbonate modified activated carbon adsorption of table 11 and desorption air
Embodiment 12: saleratus modified activated carbon, and the titanium dioxide in absorption at normal temperatures and pressures and desorption air
Carbon
(1), by saleratus deionized water dissolving, the potassium bicarbonate solution that concentration is 4M is obtained；
(2), 2000g wood activated charcoal, active fruit shell carbon, cocoanut active charcoal and coaly activated carbon are encased in four respectively
In reaction column, 4000mL potassium bicarbonate solution is added, solution is made to recycle 45h in reaction column；
(3), it discards liquid, collects active carbon, clean 3 times with the deionized water of 5 times of volumes, later in 90 DEG C of processing 16h,
Then it is warming up to 450 DEG C of vacuum drying treatment 36h in 1h, obtains saleratus modified activated carbon；Wherein, wood activated charcoal, fruit
After modified, quality is respectively as follows: 2155g, 2137g, 2323g and 2052g for shell active carbon, cocoanut active charcoal and coaly activated carbon；
(4), the different types of saleratus modified activated carbon 150g for respectively obtaining step (3) is loaded into four desorptions
In box B；
(5), relative humidity 70% under room temperature, to desorption box B in be passed through air 60min；
(6), desorption box B is put into the closed container of volume 1.5L, the modified activated carbon in heating desorption box B to 250
DEG C, 2h is maintained, gas concentration lwevel in portable carbon dioxide detector record closed container is used；
(7), above-mentioned adsorption-desorption operation is repeated, gas concentration lwevel when recording the 100th time and the 500th time the results are shown in Table
12。
Carbon dioxide result data in the absorption of 12 saleratus modified activated carbon of table and desorption air
Embodiment 13: desorbing under normal temperature and pressure and do not load any active material in box A, and the carbon dioxide tested in air is dense
Degree
(1), relative humidity 50% under room temperature, to desorption box A in be passed through air 10min；
(2), desorption box A is put into the closed container of volume 1.5L, vapor is passed through into container, make to desorb in box A
Relative humidity rise to 70%, maintain 50min, carbon dioxide is dense during recording this using portable carbon dioxide detector
Degree；
(3), above-mentioned adsorption-desorption operation is repeated, gas concentration lwevel when recording the 100th time and the 500th time the results are shown in Table
13。
Embodiment 14: desorbing the active material for not loading any active material or modification in box B under normal temperature and pressure, test is empty
Gas concentration lwevel in gas
(1), relative humidity 70% under room temperature, to desorption box B in be passed through air 90min；
(2), desorption box B is put into the closed container of volume 1.5L, heating desorption box B to 500 DEG C, maintains 2h, used
Portable carbon dioxide detector records the concentration of carbon dioxide during this；
(3), above-mentioned adsorption-desorption operation is repeated, gas concentration lwevel when recording the 100th time and the 500th time the results are shown in Table
13。
Carbon dioxide result data in 13 blank test of table absorption and desorption air
Embodiment 15: the application effect of active material and the active material of modification test
Air is adsorbed according to corresponding operating using the active material of active material or modification in 5kg embodiment 1~12
In carbon dioxide be introduced into microdisk electrode device with the rich carbonated air of pump continuous drawing after desorption.Microalgae algae
For scenedesmus Scenedesmus sp., incubator is the column Photoreactor of long 60cm, internal diameter 3cm.Every group three parallel, air-flow
Amount is 200mL/min.Initial inoculation concentration A680=0.2, cultivation cycle 18 days.Take within every 3 days after inoculation 5mL algae solution measurement biology
Measure concentration.It is compared with air.Experimental result is as shown in Fig. 1-Figure 16, it is seen that the setting of active material or modified active material mentions
The high growth efficiency of microalgae, and the effect of modified active material in the present embodiment is better than unmodified active material, changes
Property front and back data have statistical significance.
In conclusion the present invention utilizes the carbon dioxide in active material and modified active material capture and enriched air,
It will be used for both culturing microalgae after carbon dioxide, reduces the carbon dioxide content in air, and take full advantage of titanium dioxide
Carbon.Active material after method modified by this invention is modified is captured from air and the ability of carbon dioxide-enriched has larger mention
It rises, and after long-term adsorption-desorption cycle use, still keeps the more stable absorption to carbon dioxide and desorption ability.
Carbon dioxide used in the present invention is existing substance in air, not will cause carbon dioxide generation and greenhouse effects, has
Good application prospect.
The invention is not limited to specific embodiments above-mentioned.The present invention, which expands to, any in the present specification to be disclosed
New feature or any new combination, and disclose any new method or process the step of or any new combination.
Claims (10)
1. the method for carbon dioxide in capture and enriched air, it is characterised in that: existed using active material or modified active material
Under normal temperature and pressure capture and enriched air in carbon dioxide；The active material is ion exchange resin, zeolite molecular sieve, activity
Aluminium oxide or active carbon；The modified active material is modified zeolite molecular sieve, modified activated aluminum oxide or modified activated carbon.
2. the method for carbon dioxide in capture according to claim 1 and enriched air, it is characterised in that: work as active material
When for ion exchange resin, the condition of carbon dioxide further includes relative humidity not higher than 80% in capture and enriched air.
3. according to claim 1 utilize carbon dioxide in active material or modified active material capture and enriched air
Method, it is characterised in that: at least meet following one:
The ion exchange resin is hydrogen-oxygen type strong basic type anion-exchange resin or hydrogen-oxygen type weak base type anion exchange resin；
The zeolite molecular sieve is at least one of X-type, Y type, A type, β type or ZSM type；
The activated alumina is at least one of γ type, ρ type, η type, χ type or χ-ρ type；
The active carbon is at least one of wood activated charcoal, active fruit shell carbon, cocoanut active charcoal or coaly activated carbon.
4. the method for carbon dioxide in capture according to claim 1 and enriched air, it is characterised in that: under at least meeting
Column one:
The modified zeolite molecular sieve is to be reacted using metal salt with zeolite molecular sieve, the zeolite by Metal Ions Modification of formation
Molecular sieve；
The modified activated aluminum oxide is in modified activated aluminum oxide A, modified activated aluminum oxide B or modified activated aluminum oxide C
It is at least one；Wherein, modified activated aluminum oxide A is to handle activated alumina using metal hydroxide solutions, and formation has
The activated alumina of new construction；The modified activated aluminum oxide B is to use carbonate solution or bicarbonate solution to handle and living
After property aluminium oxide, the activated alumina compound containing carbonate or bicarbonate of formation；The modified activated aluminum oxide C is
After first handling activated alumina using metal hydroxide solutions, then through carbonate solution or bicarbonate solution processing, formed
The activated alumina compound containing carbonate or bicarbonate；
The modified activated carbon is that active carbon is handled using carbonate solution or bicarbonate solution, formation containing carbonate or
The active Carbon composites of bicarbonate.
5. the method for carbon dioxide in capture according to claim 4 and enriched air, it is characterised in that: under at least meeting
Column one:
The modified zeolite molecular sieve is prepared by following methods: zeolite molecular sieve being fitted into reaction vessel, inert gas
Under protection, the metal salt solution that concentration is 0.1~2.0M is added in reaction vessel, the rate of outflow of metal salt solution is adjusted
Stop that metal salt solution is added for 0.5~15mL/s, after 30~300min, it is washed, dry, obtain modified zeolite molecular sieve；
The modified activated aluminum oxide A is prepared by following methods: activated alumina being encased in reaction vessel, then will
Concentration be 0.1~3.0M metal hydroxide solutions be added reaction vessel in circulation 0.5~for 24 hours, be filtered, washed, dried,
Obtain modified activated aluminum oxide A；Wherein, activated alumina and the mass volume ratio of metal hydroxide solutions are 1:0.5~10；
The modified activated aluminum oxide B is prepared by following methods: activated alumina being encased in reaction vessel, then will
The carbonate solution or bicarbonate solution that concentration is 0.1~5.0M, which are added in reaction vessel, recycles 0.5~48h, is filtered, is washed
It washs, dry, obtain modified activated aluminum oxide B；Wherein, the quality volume of activated alumina and carbonate solution or bicarbonate solution
Than for 1:0.5~10；
The modified activated aluminum oxide C is prepared by following methods: activated alumina being encased in reaction vessel, then will
Concentration be 0.1~5.0M metal hydroxide solutions be added reaction vessel in circulation 0.5~for 24 hours, be filtered, washed, dried,
Obtained solid is encased in reaction vessel, then the carbonate solution or bicarbonate solution that concentration is 0.1~5.0M are added
0.5~48h is recycled in reaction vessel, is filtered, washed, is dried, obtains modified activated aluminum oxide C；Wherein, activated alumina and gold
The mass volume ratio for belonging to hydroxide solution is 1:0.5~10；Activated alumina and carbonate solution or bicarbonate solution
Mass volume ratio is 1:0.5~10；
The modified activated carbon is prepared by following methods: active carbon being encased in reaction vessel, is then 0.1 by concentration
The carbonate solution or bicarbonate solution of~5.0M, which is added in reaction vessel, recycles 0.5~48h, is filtered, washed, is dried,
Obtain modified activated carbon；Wherein, the mass volume ratio of active carbon and carbonate solution or bicarbonate solution is 1:0.5~10.
6. the application of active material or modified active material in the growth for promoting biology, it is characterised in that: by active material or
After the carbon dioxide adsorbed in modified active material, as carbon-dioxide gasfertilizer, for promoting the growth of biology, including rush
Into the growth of microalgae.
7. desorbing box, it is characterised in that: including box body (1), heating element (3) and upper cover (4)；Wherein, box body (1) at least one end
With opening, heating element (3) is mounted in box body (1), and it is open at one end that upper cover (4) is mounted on box body (1).
8. desorption box according to claim 7, it is characterised in that: it further include humidifier (5), the humidifier (5) and box
Connection inside body (1).
9. desorption box according to claim 7 or 8, it is characterised in that: further include fan (2), box body (1) both ends, which have, opens
Mouthful, upper cover (4) is mounted on that box body (1) is open at one end, and fan (2) is mounted on the opening of box body (1) other end.
10. according to the described in any item desorption boxes of claim 7~9, it is characterised in that: be provided with active material in box body or change
Property active material.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810489846.4A CN108970590A (en) | 2018-05-21 | 2018-05-21 | Utilize the method and its application of carbon dioxide in active material or modified active material capture and enriched air |
| PCT/CN2018/098362 WO2019223113A1 (en) | 2018-05-21 | 2018-08-02 | Method of capturing and enriching carbon dioxide from air by using active material or modified active material and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810489846.4A CN108970590A (en) | 2018-05-21 | 2018-05-21 | Utilize the method and its application of carbon dioxide in active material or modified active material capture and enriched air |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108970590A true CN108970590A (en) | 2018-12-11 |
Family
ID=64542060
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810489846.4A Pending CN108970590A (en) | 2018-05-21 | 2018-05-21 | Utilize the method and its application of carbon dioxide in active material or modified active material capture and enriched air |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN108970590A (en) |
| WO (1) | WO2019223113A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113385141A (en) * | 2021-06-23 | 2021-09-14 | 浙江大学 | Facility CO for improving plant cultivation by applying ZSM-5 molecular sieve2Concentration and method of crop growth |
| CN113424717A (en) * | 2021-07-15 | 2021-09-24 | 浙江大学 | Method for promoting photosynthetic efficiency of facility horticultural crops by using zeolite molecular sieve |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112657478A (en) * | 2020-12-17 | 2021-04-16 | 国网陕西省电力公司电力科学研究院 | Ce modified carbon dioxide adsorbing material in closed semi-closed space and preparation method and application thereof |
| AU2021441253A1 (en) * | 2021-04-14 | 2023-11-23 | William Marsh Rice University | Porous polymeric carbon sorbents and methods of making and using same |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2232191Y (en) * | 1995-08-25 | 1996-08-07 | 侯见丁 | Carbon dioxide gas fertilizer collection apparatus |
| CN101998876A (en) * | 2006-10-02 | 2011-03-30 | 环球研究技术有限公司 | Method and apparatus for extracting carbon dioxide from air |
| CN102350303A (en) * | 2011-07-18 | 2012-02-15 | 中国科学院宁波材料技术与工程研究所 | Zeolite molecular sieve material which has high-efficiency CO2 capturing function and preparation method thereof |
| CN103194375A (en) * | 2013-04-09 | 2013-07-10 | 浙江大学 | Device and method for concentrating and recovering carbon dioxide in air for culturing microalgae |
| CA2878664A1 (en) * | 2012-07-17 | 2014-01-23 | Antecy B.V. | Materials and process for reversible adsorption of carbon dioxide |
| CN106804555A (en) * | 2017-01-20 | 2017-06-09 | 唐成康 | Application and its method of modifying of the metal ion-modified zeolite molecular sieve in mosquito is caught |
| CN108031238A (en) * | 2018-01-18 | 2018-05-15 | 上海孙桥农业科技股份有限公司 | Capture device and application method that carbon dioxide in air is used for industrialized agriculture |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05161843A (en) * | 1991-12-16 | 1993-06-29 | Osaka Gas Co Ltd | Carbon dioxide adsorbent |
| CN101721972B (en) * | 2009-12-08 | 2011-11-09 | 华东理工大学 | Method for preparing spherical activated carbon with large CO2 absorption capacity |
| CN101745365B (en) * | 2009-12-30 | 2012-07-25 | 郑州雪山实业有限公司 | Preparation method of 13X molecular sieve with high adsorption property |
| CN101745285B (en) * | 2010-01-29 | 2012-06-13 | 南京大学 | Method for removing carbon dioxide from air by adsorption |
| CN108579706A (en) * | 2011-05-17 | 2018-09-28 | 恩弗里德系统公司 | Sorbent for reducing carbon dioxide from room air |
-
2018
- 2018-05-21 CN CN201810489846.4A patent/CN108970590A/en active Pending
- 2018-08-02 WO PCT/CN2018/098362 patent/WO2019223113A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2232191Y (en) * | 1995-08-25 | 1996-08-07 | 侯见丁 | Carbon dioxide gas fertilizer collection apparatus |
| CN101998876A (en) * | 2006-10-02 | 2011-03-30 | 环球研究技术有限公司 | Method and apparatus for extracting carbon dioxide from air |
| CN102350303A (en) * | 2011-07-18 | 2012-02-15 | 中国科学院宁波材料技术与工程研究所 | Zeolite molecular sieve material which has high-efficiency CO2 capturing function and preparation method thereof |
| CA2878664A1 (en) * | 2012-07-17 | 2014-01-23 | Antecy B.V. | Materials and process for reversible adsorption of carbon dioxide |
| CN103194375A (en) * | 2013-04-09 | 2013-07-10 | 浙江大学 | Device and method for concentrating and recovering carbon dioxide in air for culturing microalgae |
| CN106804555A (en) * | 2017-01-20 | 2017-06-09 | 唐成康 | Application and its method of modifying of the metal ion-modified zeolite molecular sieve in mosquito is caught |
| CN108031238A (en) * | 2018-01-18 | 2018-05-15 | 上海孙桥农业科技股份有限公司 | Capture device and application method that carbon dioxide in air is used for industrialized agriculture |
Non-Patent Citations (3)
| Title |
|---|
| 周安宁等编: "《吸附法》", 《洁净煤技术》 * |
| 肖钢等编: "《吸附法分离CO2技术》", 《大能源二氧化碳》 * |
| 骆仲泱等编: "《CO2吸附剂》", 《二氧化碳捕集封存和利用技术》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113385141A (en) * | 2021-06-23 | 2021-09-14 | 浙江大学 | Facility CO for improving plant cultivation by applying ZSM-5 molecular sieve2Concentration and method of crop growth |
| CN113385141B (en) * | 2021-06-23 | 2022-05-31 | 浙江大学 | Facility CO for improving plant cultivation by applying ZSM-5 molecular sieve2Concentration and method of crop growth |
| CN113424717A (en) * | 2021-07-15 | 2021-09-24 | 浙江大学 | Method for promoting photosynthetic efficiency of facility horticultural crops by using zeolite molecular sieve |
| CN113424717B (en) * | 2021-07-15 | 2022-05-31 | 浙江大学 | Method for promoting photosynthetic efficiency of facility horticultural crops by using zeolite molecular sieve |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019223113A1 (en) | 2019-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108970590A (en) | Utilize the method and its application of carbon dioxide in active material or modified active material capture and enriched air | |
| CN106082193B (en) | A kind of method that multilevel hierarchy carbon material is prepared using algae as carbon source | |
| Zhao et al. | Synthesis of MIL-101 (Cr) and its water adsorption performance | |
| CN110218721B (en) | High-stability immobilized carbonic anhydrase as well as preparation method and application thereof | |
| CN107321317A (en) | A kind of solid amine carbon dioxide absorbing material, preparation method and application | |
| CN106390928A (en) | Preparation method of active carbon based on cellulose aerogel, and applications thereof | |
| CN103111262B (en) | Porous material of metal-organic framework and preparation method of material | |
| CN105032113B (en) | Process for capturing carbon dioxide in flue gas based on wet reclamation technology | |
| CN106829914A (en) | A kind of three-dimensional porous carbon negative pole material of lithium ion battery | |
| CN108714429A (en) | A kind of rodlike CoP/CoP2The preparation method of nano-complex elctro-catalyst | |
| CN210410106U (en) | Fertile collection device of circulated formula carbon dioxide gas | |
| CN103120927A (en) | Amino functional silica-gel adsorbing material, and preparation method and application thereof | |
| CN110193350A (en) | Load the biomass carbon aerogel adsorbent and the preparation method and application thereof of titanate | |
| CN104829430B (en) | A kind of method of liquid phase ethylene glycol deep dehydration | |
| CN101822929A (en) | Method for capturing carbon dioxide by utilizing electrical desorption technology | |
| CN113318697A (en) | For CO desorption of amine solutions2Is loaded with SO42Filler of metal oxide and process for its preparation | |
| CN108821283A (en) | A method of utilizing Chinese fir bark microwave assisted aqueous extraction hot preparation active carbon | |
| CN104039423B (en) | Control freezing ammonia process is used to remove CO from flue gas2 | |
| CN102728320B (en) | Preparation method for modified porous bamboo charcoal materials used for separating carbon dioxide and methane | |
| CN102338278A (en) | Method for increasing natural gas adsorption storage capability | |
| CN107840334A (en) | A kind of atomic hole porous carbon materials and preparation method thereof | |
| CN110193349A (en) | The biomass carbon aerogel adsorbent and its preparation method of load titan silicate and application | |
| CN102764629B (en) | Method for preparing absorbing agent for medium-temperature gas desulfurization | |
| CN100336588C (en) | Process for regenerating sulfur loading active carbon | |
| CN105080470A (en) | Methane/carbon dioxide separating absorbent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20230712 Address after: No. 1026, 10th Floor, Building 2, No. 533 Jinyun Road, High tech Zone, Chengdu, Sichuan, 610000 Applicant after: Sichuan Xinyicheng Technology Co.,Ltd. Address before: No. 1710, 17th Floor, Building 8, No. 388, North Section of Yizhou Avenue, High tech Zone, Chengdu City, Sichuan Province, 610000 Applicant before: CHENGDU VALENS MEDICAL TECHNOLOGY Co.,Ltd. Applicant before: Tang Chengkang |
|
| TA01 | Transfer of patent application right |