CN113332948B - Method for reducing composite molten salt in adsorbent by adding alkaline ion blocker - Google Patents

Method for reducing composite molten salt in adsorbent by adding alkaline ion blocker Download PDF

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CN113332948B
CN113332948B CN202110114762.4A CN202110114762A CN113332948B CN 113332948 B CN113332948 B CN 113332948B CN 202110114762 A CN202110114762 A CN 202110114762A CN 113332948 B CN113332948 B CN 113332948B
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adsorbent
alkali metal
calcium
cooling
salt
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CN113332948A (en
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罗聪
蔡国秋
幸文婷
张立麒
李小姗
邬凡
柳朝晖
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Huazhong University of Science and Technology
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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
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • 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
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
    • 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
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • 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

Abstract

The invention discloses a method for reducing compound molten salt in an adsorbent by adding an alkaline ion blocking agent, which comprises the steps of calcining quicklime and alkali metal salt in the presence of the alkaline ion blocking agent, and then performing step cooling to obtain a calcium-based adsorbent; the method for reducing the composite molten salt in the adsorbent by adding the alkaline ion blocking agent effectively reduces the alkali metal-alkaline earth metal composite molten carbonate in the obtained calcium-based adsorbent, thereby greatly improving the CO of the calcium-based adsorbent 2 Adsorption capacity; the method has the advantages of no complicated steps and easy operation.

Description

Method for reducing composite molten salt in adsorbent by adding alkaline ion blocker
Technical Field
The invention belongs to the technical field of chemistry, and particularly relates to a method for reducing composite molten salt in an adsorbent by adding an alkaline ion blocker.
Background
The calcium cycling technology is a novel CO which is mainly recommended to develop in the world in order to cope with global climate change 2 /SO 2 One of the trapping techniques. The method has been widely used in China, the United states, the European Union, australia, canada and the like, and is widely focused by the mainstream scientific research institutions at home and abroad.
The common method for preparing the calcium adsorbent in the prior art is an impregnation method, which is to impregnate the surface of the calcium-based adsorbent with high-activity salt, wherein the high-activity salt accounts for 0.1-2.0% of the mass of the adsorbent. Because alkali metal has better high-temperature activity, alkali metal salt is generally used for impregnation, so that the ion diffusion capacity of the surface of the adsorbent is improved, and the CO of the adsorbent is enhanced 2 Capture Capacity.
The professor Anthony Canada, 2003, early on proposed impregnating limestone with trace amounts of NaCl or Na 2 CO 3 Multiple times of itRecycled CO 2 The adsorption capacity can be increased by about 40%, from 0.10 (gCO 2 /g adsorbent) to 0.14 (gCO) 2 /g adsorbent). Basic researches on alkali metal salt impregnation modified calcium-based adsorbents are also carried out by university of east and Shandong, and KMnO is respectively researched 4 、KCl、K 2 CO 3 NaCl and Na 2 CO 3 Impregnating pure CaCO with various pure alkali metal salts 3 The experiments of (2) show that most of the alkali metal salts have obvious modification effect, and CO after multiple times of circulation 2 The adsorption capacity can be improved by about 100%. In addition, mn (NO) 3 ) 2 The dipping modification of the calcium-based adsorbent by the salts such as calcium lignosulfonate and the like also finds a better lifting effect. From the above studies, it was found that impregnating an alkali metal salt into a calcium-based adsorbent can increase CO of the adsorbent 2 The trapping capacity and the lifting range are mostly between 40 and 100 percent.
Whether the dipping method can be further utilized to obtain a larger lifting effect on the basis of 40-100% lifting amplitude is a major concern. Through scientific experiments, the applicant previously proposed an improved impregnation method to make calcium-based CO 2 The performance of the adsorbent is improved by 150-200%. The improvement method is now already granted to national invention patent (Xu Yongqing, luo Cong, etc., a calcium-based carbon dioxide/sulfur dioxide absorbent and a preparation method thereof, national intellectual property agency, cn105903317 b.2018, granted: china.), the main difference between the improvement method and the common method is that limestone is added with a calcination-hydration process before being mixed with alkali metal salt for soaking.
Those skilled in the art have focused on developing a method for reducing complex molten salts in adsorbents to further increase calcium-based CO 2 /SO 2 Adsorption performance of the adsorbent.
Disclosure of Invention
The present invention has been made in view of the above problems, and aims to provide a method for modifying calcium-based CO in alkali metal salts to overcome or at least partially solve the above problems 2 /SO 2 In the preparation process of the adsorbent, the alkali ion blocking agent is added for subtractionA method for compounding molten salt in a small amount of adsorbent.
In order to achieve the above object, the present invention provides a method for reducing complex molten salt in an adsorbent by adding a basic ion blocking agent, comprising calcining quicklime and an alkali metal salt in the presence of the basic ion blocking agent, and then performing stepwise cooling to obtain a calcium-based adsorbent;
further, the alkali metal salt includes an alkali metal sodium salt and an alkali metal potassium salt;
further, the alkali metal sodium salt is NaCl, naBr, na 2 CO 3 、NaHCO 3 One or more of (a) and (b); the alkali metal potassium salt is KCl, KBr, KHCO 3 、K 2 CO 3 One or more of the following;
further, the temperature of the calcination is not less than 850 ℃;
further, the calcination time is 0.5-2 hours;
further, the alkaline ion blocker is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide and magnesium hydroxide;
further, the step cooling comprises two stages of cooling, wherein the first stage cooling is in the absence of CO 2 Cooling to 100-400 ℃ in the gas environment; the second stage of cooling is to cool to room temperature in air;
further, the catalyst does not contain CO 2 The gas environment of (1) is one or more of a water vapor gas environment, a nitrogen gas environment, an argon gas environment and an oxygen gas environment;
further, the calcining temperature is 850-1000 ℃;
further, the method for reducing the composite molten salt in the adsorbent by adding the alkaline ion blocker comprises the following specific steps:
step 1, calcining limestone in air at 700-1100 ℃ for 0.5-2 hours to obtain quicklime;
step 2, adding the quicklime obtained in the step 1 into an alkali metal salt solution, then adding an alkaline ion blocker, mixing and stirring to form paste, and airing to obtain a salt-doped lime solid;
step 3, calcining the salt-doped lime solid obtained in the step 2 at 850-1000 ℃ for 0.5-2 hours;
step 4, calcining the solid obtained in the step 3 until the solid does not contain CO 2 In the first stage of cooling to 100-400 deg.c;
step 5, placing the solid cooled in the step 4 in air to continue the second stage of cooling, and cooling to room temperature to obtain the calcium-based adsorbent;
further, in the step 2, the percentage content of the alkali metal salt solution is 1% -3%;
further, in the step 2, the weight ratio of the quicklime to the alkali metal salt compound in the alkali metal salt solution is 100:1-30:1;
further, in the step 2, the weight ratio of the quicklime to the alkaline ion blocker is 1000:1-300:1;
in a preferred embodiment of the present invention, the alkali metal salt is potassium carbonate by a method of reducing complex molten salts in an adsorbent by adding a basic ion blocker;
in a preferred embodiment of the present invention, the method for reducing complex molten salt in an adsorbent by adding a basic ion blocker, in step 1, the limestone calcination temperature is 700 ℃;
in another preferred embodiment of the present invention, the method for reducing complex molten salt in an adsorbent by adding a basic ion blocker, in step 1, the limestone calcination temperature is 950 ℃;
in another preferred embodiment of the present invention, the method for reducing complex molten salt in an adsorbent by adding a basic ion blocker, in step 1, the limestone calcination temperature is 1100 ℃;
in a preferred embodiment of the present invention, in the method for reducing composite molten salt in an adsorbent by adding a basic ion blocker, in step 1, the limestone calcination time is 0.5 hours;
in another preferred embodiment of the present invention, in the method for reducing composite molten salt in an adsorbent by adding a basic ion blocker, in step 1, the limestone calcination time is 1 hour;
in another preferred embodiment of the present invention, in the method for reducing composite molten salt in an adsorbent by adding a basic ion blocker, in step 1, the limestone calcination time is 2 hours;
in a preferred embodiment of the present invention, the method for reducing complex molten salt in an adsorbent by adding a basic ion blocker comprises the step 2 of adding 1% of alkali metal salt solution;
in another preferred embodiment of the present invention, the method for reducing complex molten salt in an adsorbent by adding a basic ion blocker comprises 2% of alkali metal salt solution in step 2;
in another preferred embodiment of the present invention, the method for reducing complex molten salt in an adsorbent by adding a basic ion blocker comprises the step 2 of adding an alkali metal salt solution in an amount of 3%;
in the preferred embodiment of the invention, the method for reducing the composite molten salt in the adsorbent by adding the alkaline ion blocker comprises the following steps of 2, wherein the weight ratio of quicklime to alkali metal salt compound in the alkali metal salt solution is 100:1;
in another preferred embodiment of the present invention, the method for reducing the composite molten salt in the adsorbent by adding the alkali ion blocking agent comprises the following steps of 2, wherein the weight ratio of quicklime to alkali metal salt compound in the alkali metal salt solution is 50:1;
in another preferred embodiment of the present invention, the method for reducing the composite molten salt in the adsorbent by adding the alkali ion blocking agent comprises the following steps of 2, wherein the weight ratio of quicklime to alkali metal salt compound in the alkali metal salt solution is 30:1;
in the preferred embodiment of the invention, the method for reducing the composite molten salt in the adsorbent by adding the alkaline ion blocking agent comprises the following steps of (2) setting the weight ratio of quicklime to the alkaline ion blocking agent to be 1000:1;
in another preferred embodiment of the present invention, in the method for reducing composite molten salt in an adsorbent by adding a basic ion blocking agent, in step 2, the weight ratio of quicklime to the basic ion blocking agent is 500:1;
in another preferred embodiment of the present invention, in the method for reducing composite molten salt in an adsorbent by adding a basic ion blocking agent, in step 2, the weight ratio of quicklime to the basic ion blocking agent is 300:1;
in a preferred embodiment of the present invention, the method for reducing composite molten salt in an adsorbent by adding a basic ion blocker, in step 3, the calcination temperature of the salt-doped lime solid is 850 ℃;
in another preferred embodiment of the present invention, the method for reducing composite molten salt in an adsorbent by adding a basic ion blocker, in step 3, the calcination temperature of the salt-doped lime solid is 900 ℃;
in another preferred embodiment of the present invention, the method for reducing composite molten salt in an adsorbent by adding a basic ion blocker, in step 3, the calcination temperature of the salt-doped lime solid is 1000 ℃;
in a preferred embodiment of the invention, the method for reducing composite molten salt in the adsorbent by adding alkaline ion blocker comprises the following steps of (3) calcining the salt-doped lime solid for 0.5 hours;
in another preferred embodiment of the present invention, the method for reducing composite molten salt in an adsorbent by adding a basic ion blocker, in step 3, the calcination time of the salt-doped lime solid is 1 hour;
in another preferred embodiment of the present invention, the method for reducing composite molten salt in an adsorbent by adding a basic ion blocker, in step 3, the calcination time of the salt-doped lime solid is 2 hours;
in a preferred embodiment of the present invention, the method for reducing complex molten salts in an adsorbent by adding a basic ion blocker, step 4, is free of CO 2 The gas environment of (2) is a vapor gas environment;
in another preferred embodiment of the present invention, the throughMethod for reducing composite molten salt in adsorbent by adding alkaline ion blocker, and step 4, method does not contain CO 2 The gas environment of (2) is nitrogen gas environment;
in a preferred embodiment of the present invention, the method for reducing complex molten salt in an adsorbent by adding a basic ion blocker, in step 4, the cooling temperature of the first stage cooling is 100 ℃;
in another preferred embodiment of the present invention, the method for reducing complex molten salt in an adsorbent by adding a basic ion blocker, in step 4, the cooling temperature of the first stage cooling is 300 ℃;
in another preferred embodiment of the present invention, the method for reducing complex molten salt in an adsorbent by adding a basic ion blocker, in step 4, the cooling temperature of the first stage cooling is 400 ℃;
in the preferred embodiment of the invention, the raw material of the alkali metal sodium salt or the alkali metal potassium salt is one or more of sea salt and lake salt;
in a preferred embodiment of the present invention, the calcium-based adsorbent is further subjected to grinding treatment, wherein the calcium-based adsorbent is obtained by continuously grinding the solid cooled to room temperature in the step 5, and the particle size of the ground calcium-based adsorbent is not more than 0.3mm;
the invention also provides the calcium-based adsorbent prepared by the method according to any one of the above steps, wherein the calcium-based adsorbent internally comprises a macroporous structure with the diameter of 100-200 nm;
one or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
the method for reducing the composite molten salt in the adsorbent adopts the addition of the alkaline ion blocking agent and adopts the method without CO during cooling 2 The gas environment of the calcium-based adsorbent is cooled in stages, and the calcination temperature is optimally adjusted and optimized, so that the alkali metal-alkaline earth metal composite molten carbonate in the obtained calcium-based adsorbent is effectively reduced, thereby greatly improving the CO of the calcium-based adsorbent 2 Adsorption capacity;
according to the method for reducing the composite molten salt in the adsorbent, sodium hydroxide, potassium hydroxide or magnesium hydroxide is used as a blocking agent, the addition amount of the sodium hydroxide, the potassium hydroxide or the magnesium hydroxide is optimized to be 0.1-0.3%, and if the content of alkaline substances is too low, the blocking agent effect cannot be achieved; if the content of the alkaline substance is too high, the sintering of the calcium-based adsorbent under the high-temperature condition is accelerated, the microstructure of the adsorbent is destroyed, and in the high-temperature calcination process, hydroxide ions effectively inhibit alkali metal-alkaline earth metal in the mixture from forming composite acidic molten salt;
the method for reducing the composite molten salt in the adsorbent has the advantages of less complicated steps and easy operation.
The foregoing description is only an overview of the present invention, and is intended to be implemented in accordance with the teachings of the present invention in order that the same may be more clearly understood and to make the same and other objects, features and advantages of the present invention more readily apparent.
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In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are drawings in some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of the method of example 1 of the present invention;
FIG. 2 is a schematic diagram of an adsorbent prepared by a conventional impregnation method and a conventional modified impregnation method.
Detailed Description
The advantages and various effects of the present invention will be more clearly apparent from the following detailed description and examples. It will be understood by those skilled in the art that these specific embodiments and examples are intended to illustrate the invention, not to limit the invention.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification will control.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
From 2018 to date, the applicant is searching for the root cause of improving the performance of the calcium-based adsorbent by an improved impregnation method, searching for the improvement of the calcium-based CO on the basis of 150-200% of the improvement range 2 The method for the performance of the adsorbent. The applicant has found through a great deal of experiments and analytical researches that the mixture of alkali metal salt and calcium can generate alkali metal-alkaline earth metal composite molten carbonate K under certain conditions 2 Ca(CO 3 ) 2 And Na (Na) 2 Ca(CO 3 ) 2 The composite molten carbonate remains in the calcium-based adsorbent, occupies the surface space of the adsorbent, reduces the ion diffusion capacity of the surface of the adsorbent, and has obvious inhibition effect on the performance of the adsorbent. The research on the adsorbents prepared by the common impregnation method and the modified impregnation method shows that the adsorbent prepared by the common impregnation method contains a large amount of composite molten carbonate, so that the modification effect is poor; even in the modified impregnation method, there are some such complex molten carbonates, and thus there is still room for further improvement in the modified impregnation method.
Therefore, through detailed scientific research, the patent provides a method for adding the alkaline ion blocker, which reduces the generation of alkali metal-alkaline earth metal composite molten carbonate, thereby greatly improving the CO of the calcium-based adsorbent 2 Adsorption capacity.
The method of reducing composite molten salt in the adsorbent of the present application will be described in detail with reference to examples.
Example 1 preparation of calcium-based adsorbent
Calcining limestone in air at 950 ℃ for 0.5 hour to obtain quicklime;
adding 50 g of quicklime into 50 g (2% of potassium chloride solution), adding 0.1 g of magnesium hydroxide, fully mixing and stirring to obtain a pasty mixture, and airing to obtain a salt-doped lime solid;
calcining the salt-doped lime solid at 900 ℃ for 1 hour;
cooling the calcined solid in the first stage in the water vapor gas environment to 400 ℃;
then cooling to room temperature in the second stage in air;
and finally, grinding the cooled solid into powder with the particle size not exceeding 0.3mm to obtain the calcium-based adsorbent product.
Example 2 preparation of calcium-based adsorbent
Calcining limestone in the air at 850 ℃ for 2 hours to obtain quicklime;
adding 50 g of quicklime into 50 g (2% of potassium carbonate solution), adding 0.2 g of magnesium hydroxide, fully mixing and stirring to obtain a pasty mixture, and airing to obtain a salt-doped lime solid;
calcining the salt-doped lime solid at 850 ℃ for 2 hours;
cooling the calcined solid in the first stage in a nitrogen gas environment to 300 ℃;
then cooling to room temperature in the second stage in air;
and finally, grinding the cooled solid into powder with the particle size not exceeding 0.3mm to obtain the calcium-based adsorbent product.
Example 3 preparation of calcium-based adsorbent
Calcining limestone in air at 950 ℃ for 1 hour to obtain quicklime;
adding 50 g of quicklime into 100 g (1% of) chloridizing solution, adding 0.1 g of sodium hydroxide, fully mixing and stirring to obtain pasty mixture, and airing to obtain salt-doped lime solid;
calcining the salt-doped lime solid at 950 ℃ for 0.5 hour;
cooling the calcined solid in the first stage in a nitrogen gas environment to 100 ℃;
then cooling to room temperature in the second stage in air;
and finally, grinding the cooled solid into powder with the particle size not exceeding 0.3mm to obtain the calcium-based adsorbent product.
Comparative example 4,
Calcining limestone in air at 950 ℃ for 0.5 hour to obtain quicklime;
adding 50 g of quicklime into 50 g (2% of potassium chloride solution), fully mixing and stirring to obtain a pasty mixture, and airing to obtain a salt-doped lime solid;
calcining the salt-doped lime solid in air at 900 ℃ for 1 hour;
cooling to room temperature;
and finally, grinding the cooled solid into powder with the particle size not exceeding 0.3mm to obtain the calcium-based adsorbent product.
Comparative example 5,
Calcining limestone in the air at 850 ℃ for 2 hours to obtain quicklime;
adding 50 g of quicklime into 50 g (2% of potassium carbonate solution), fully mixing and stirring to obtain a pasty mixture, and airing to obtain a salt-doped lime solid;
calcining the salt-doped lime solid in air at 850 ℃ for 2 hours;
cooling to room temperature;
and finally, grinding the cooled solid into powder with the particle size not exceeding 0.3mm to obtain the calcium-based adsorbent product.
Comparative example 6,
Calcining limestone in air at 950 ℃ for 1 hour to obtain quicklime;
adding 50 g of quicklime into 100 g (1% of potassium chloride solution), fully mixing and stirring to obtain a pasty mixture, and airing to obtain a salt-doped lime solid;
calcining the salt-doped lime solid in air at 950 ℃ for 0.5 hour;
cooling to room temperature;
and finally, grinding the cooled solid into powder with the particle size not exceeding 0.3mm to obtain the calcium-based adsorbent product.
Test example 7,
The calcium-based adsorbent products obtained in examples 1 to 3 and comparative examples 4 to 6 were fed with CO-enriched adsorbent respectively 2 For 15min to enable the calcium-based adsorbent to fully adsorb CO 2 Taking out the calcium-based adsorbent to detect the adsorption capacity, detecting each sample three times, and taking an average value; the test data results are shown in table 1:
TABLE 1 CO after multiple cycle stabilization 2 Adsorption amount (g-CO) 2 G-adsorbent
Example 1 Example 2 Example 3 Comparative example 4 Comparative example 5 Comparative example 6
1 0.35 0.33 0.34 0.27 0.23 0.26
2 0.35 0.32 0.33 0.26 0.23 0.27
3 0.34 0.32 0.33 0.26 0.24 0.27
Average value of 0.35 0.32 0.33 0.26 0.23 0.27
As is clear from the data in Table 1, CO using the calcium-based adsorbents obtained in examples 1 to 3 of the present application 2 The adsorption quantity is 0.32-0.35 g-CO 2 G-adsorbent; CO of the calcium-based adsorbents obtained in comparative examples 4 to 6 2 The adsorption quantity is 0.23-0.27 g-CO 2 G-adsorbent;
the calcium-based adsorbents obtained in examples 1 to 3 of the present invention were shown to be CO relative to the calcium-based adsorbents obtained in comparative examples 4 to 6 2 The adsorption amount of CO is significantly higher than that of the calcium-based adsorbents obtained in comparative examples 4 to 6 2 Adsorption amount; CO of the calcium-based adsorbents obtained in examples 1 to 3 of the present invention 2 The adsorption performance is improved by 30% compared with the comparative example;
other technical schemes of the invention have similar beneficial effects as described above.
Finally, it is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.

Claims (9)

1. A method for reducing complex molten salts in an adsorbent by adding a basic ion blocking agent, comprising calcining quicklime and an alkali metal salt in the presence of a basic ion blocking agent, and then performing step cooling to obtain a calcium-based adsorbent, comprising the steps of:
step 1, calcining limestone in air at 700-1100 ℃ for 0.5-2 hours to obtain quicklime;
step 2, adding the quicklime obtained in the step 1 into an alkali metal salt solution, then adding an alkaline ion blocker, mixing and stirring to form paste, and airing to obtain a salt-doped lime solid;
step 3, calcining the salt-doped lime solid obtained in the step 2 at 850-1000 ℃ for 0.5-2 hours;
step 4, calcining the solid obtained in the step 3 until the solid does not contain CO 2 In the first stage of cooling to 100-400 deg.c;
step 5, placing the solid cooled in the step 4 in air to continue the second stage of cooling, and cooling to room temperature to obtain the calcium-based adsorbent;
the alkaline ion blocking agent is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide and magnesium hydroxide, and the addition amount of the alkaline ion blocking agent is 0.1-0.3%.
2. The method of claim 1, wherein the method comprises the steps of,
the step cooling comprises two stages of cooling, wherein the first stage of cooling is in the absence of CO 2 Cooling to 100-400 ℃ in the gas environment; the second stage of cooling is cooling to room temperature in air.
3. The method of claim 2, wherein the step of,
the said composition does not contain CO 2 The gas environment is one or more of water vapor gas environment, nitrogen gas environment, argon gas environment and oxygen gas environment.
4. The method of claim 1, wherein the method comprises the steps of,
the alkali metal salt includes alkali metal sodium salt and alkali metal potassium salt;
the temperature of the calcination is not less than 850 ℃;
the calcination time is 0.5-2 hours.
5. The method of claim 4, wherein the step of,
the alkali metal sodium salt is NaCl, naBr, na 2 CO 3 、NaHCO 3 One or more of (a) and (b); the alkali metal potassium salt is KCl, KBr, KHCO 3 、K 2 CO 3 One or more of the following;
the calcining temperature is 850-1000 ℃.
6. The method according to claim 1, wherein said step 2,
the percentage content of the alkali metal salt solution is 1% -3%;
the weight ratio of the quicklime to the alkali metal salt compound in the alkali metal salt solution is 100:1-30:1.
7. The method according to claim 1, wherein said step 2,
the weight ratio of the quicklime to the alkaline ion blocker is 1000:1-300:1.
8. The method according to claim 1, wherein said step 5,
the obtained calcium-based adsorbent is further subjected to grinding treatment, and the particle size of the ground calcium-based adsorbent is not more than 0.3mm.
9. The calcium-based adsorbent prepared by the method of any one of claims 1 to 8, wherein the calcium-based adsorbent comprises a macroporous structure having a diameter of 100-200 nm.
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