CN114000021A - Magnesium alloy for carbon dioxide absorption-release and method for absorbing-releasing carbon dioxide by magnesium alloy - Google Patents
Magnesium alloy for carbon dioxide absorption-release and method for absorbing-releasing carbon dioxide by magnesium alloy Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 297
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 161
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 148
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 95
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000011777 magnesium Substances 0.000 claims abstract description 55
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 52
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 50
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 50
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 20
- 229910045601 alloy Inorganic materials 0.000 claims description 92
- 239000000956 alloy Substances 0.000 claims description 92
- 239000011701 zinc Substances 0.000 claims description 75
- 239000007788 liquid Substances 0.000 claims description 53
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 37
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 21
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 19
- 238000003723 Smelting Methods 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 238000005275 alloying Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000005266 casting Methods 0.000 abstract description 26
- 239000000155 melt Substances 0.000 abstract description 17
- 238000002844 melting Methods 0.000 abstract description 9
- 230000008018 melting Effects 0.000 abstract description 9
- 230000009467 reduction Effects 0.000 abstract description 7
- 239000000654 additive Substances 0.000 abstract description 5
- 230000000996 additive effect Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 38
- RIAXXCZORHQTQD-UHFFFAOYSA-N lanthanum magnesium Chemical compound [Mg].[La] RIAXXCZORHQTQD-UHFFFAOYSA-N 0.000 description 21
- 238000007711 solidification Methods 0.000 description 17
- 230000008023 solidification Effects 0.000 description 17
- 238000001514 detection method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 239000012535 impurity Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000003466 welding Methods 0.000 description 4
- 239000005431 greenhouse gas Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000013079 quasicrystal Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 241000282412 Homo Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- -1 zeolite imidazole ester Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
-
- 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
- B01D53/14—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 absorption
- B01D53/1456—Removing acid components
- B01D53/1475—Removing carbon dioxide
-
- 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
- B01D53/14—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 absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention provides a magnesium alloy for carbon dioxide absorption-release, comprising: 5-18 wt% of Zn, 5-18 wt% of Al and 3-15 wt% of La, wherein the content of Zn is not less than that of Al, the content of Al is not less than that of La, and the balance is magnesium. The application also provides a method for absorbing and releasing carbon dioxide by using the magnesium alloy. The magnesium alloy provided by the invention contains La, Zn and Al, the melt after melting can absorb a large amount of carbon dioxide gas, and in the cooling process of the melt, along with the reduction of temperature, the gas is rapidly separated out from the melt to release high-purity carbon dioxide gas, thereby achieving the effect of absorbing and releasing carbon dioxide; the magnesium alloy can realize the absorption and release of the carbon dioxide without any additive or any special casting process and condition, and can be recycled, and the absorption efficiency of the carbon dioxide is not obviously reduced along with the increase of the cycle number.
Description
Technical Field
The invention relates to the technical field of magnesium alloys, in particular to a magnesium alloy for absorbing and releasing carbon dioxide and a method for absorbing and releasing carbon dioxide by using the magnesium alloy.
Background
The emission sources of greenhouse gases are generated by the development of the world heavy industry, once the greenhouse gases exceed the atmospheric standard, the greenhouse effect can be caused, the global temperature rises, and the survival of human beings is threatened. Therefore, controlling and reducing the emission of greenhouse gases, especially carbon dioxide, has become a major problem facing humans in common. In 2021, at 28 months 5, united states energy ministry commonly issues joint statement about energy technology and policy resolution, indicating that the two countries in the united states have common goals and decisions in dealing with climate change and trying to achieve setting of paris agreement. In 2021, China also started projects of carbon peak reaching and carbon neutralization, started the carbon emission right trading market, and brought the carbon peak reaching and carbon neutralization into central environmental protection supervision for the first time. Therefore, reduction of carbon dioxide has become very urgent.
Scientists in various countries have studied new materials capable of absorbing carbon dioxide, and have developed various new materials capable of absorbing carbon dioxide, including carbon dioxide absorbing-releasing materials (such as zeolite imidazole ester framework materials), special cement materials (such as Novacem cement using magnesium silicate as a basic raw material), ceramic materials (such as lithium silicate), and high molecular materials (such as carbon dioxide degradable plastic PPC, new thin film materials). Many of these materials rely on physical adsorption and chemical reactions to consume carbon dioxide, which is poorly recycled, and carbon dioxide gas, which is relatively pure, is required to produce products from carbon dioxide. Therefore, how to effectively absorb and release carbon dioxide, and the recyclable material can not only effectively reduce the emission of carbon dioxide, but also purify the carbon dioxide to realize further utilization of the carbon dioxide.
Magnesium resources and rare earth resources in China are very rich, and magnesium alloy are also metal materials with lower melting points in engineering metal materials. Many metal melts have some solubility for a particular gas, and most of the gas is expelled during solidification. Therefore, it is theoretically possible to develop a carbon dioxide absorbing/releasing material by relying on such characteristics of a metal material, and it is of great significance to develop an ideal recyclable carbon dioxide absorbing material. At present, no carbon dioxide absorbing material is a metal matrix, and no carbon dioxide purifying method is realized by means of solidification and gassing of a metal melt, so that the recyclable carbon dioxide absorbing/releasing magnesium alloy can realize good carbon dioxide absorption, reduce carbon dioxide emission, obtain high-purity carbon dioxide and realize recovery and value-added utilization of the carbon dioxide.
Disclosure of Invention
The invention aims to provide a magnesium alloy for absorbing and releasing carbon dioxide, which has strong capability of absorbing carbon dioxide, high purity of released carbon dioxide and cyclic utilization.
In view of the above, the present application provides a magnesium alloy for carbon dioxide absorption-release, including:
Zn 5~18wt%;
Al 5~18wt%;
La 3~15wt%;
the balance of Mg;
the Zn content is more than or equal to the Al content, and the Al content is more than or equal to the La content.
Preferably, the Zn content is 6 to 15 wt%.
Preferably, the Al content is 6-14 wt%.
Preferably, the La content is 4 to 13 wt%.
Preferably, the total amount of Fe, Cu and Ni in the magnesium alloy is less than 0.03 wt%.
The application also provides a method for absorbing and releasing carbon dioxide by the magnesium alloy, which comprises the following steps:
mixing a magnesium source, a zinc source, an aluminum source and a lanthanum source according to a ratio, and smelting to obtain an alloy liquid; introducing carbon dioxide in the smelting process;
and (3) placing the alloy liquid in a closed cooling device with a gas overflow outlet for cooling, and collecting to obtain carbon dioxide gas.
Preferably, the smelting temperature is 650-800 ℃.
Preferably, the mixed raw materials also comprise other alloy element sources; the preparation of the alloy liquid comprises the following steps:
smelting a magnesium source and a lanthanum source to obtain a first mixed molten metal;
mixing the first mixed molten metal with other alloy element sources to obtain a second mixed molten metal;
and mixing the second mixed molten metal with a zinc source and an aluminum source to obtain alloy liquid.
The carbon dioxide absorbing-releasing magnesium alloy provided by the invention contains La, Zn and Al, a melt formed by the La, Zn and Al after melting can absorb a large amount of carbon dioxide gas, and the carbon dioxide gas is gradually precipitated along with the reduction of temperature in the solidification process, so that the carbon dioxide absorbing-releasing magnesium alloy provided by the invention can realize the absorption and release of the carbon dioxide without any additive or any special casting process and condition, therefore, the carbon dioxide absorbing-releasing magnesium alloy provided by the invention is a brand new carbon dioxide absorbing/releasing material, and the volume of the carbon dioxide gas absorbed by the unit volume of the carbon dioxide absorbing-releasing magnesium alloy is closely related to the components of the alloy.
The experimental results show that: the carbon dioxide absorption amount of the carbon dioxide absorption-release magnesium alloy provided by the invention is about 6-14 times of the volume of the magnesium alloy, and the recycling frequency is more than 30 times.
Drawings
FIG. 1 is a scanning electron micrograph of a carbon dioxide absorbing-releasing magnesium alloy obtained in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of a carbon dioxide absorbing-releasing magnesium alloy obtained in example 3 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In view of the seriousness of carbon dioxide absorption-release in the prior art, the application provides a magnesium alloy for carbon dioxide absorption-release, which contains La, Zn and Al, a melt formed by the La, Zn and Al can absorb a large amount of gas, and the gas is gradually precipitated along with the reduction of temperature in the solidification process to form bubbles, so that the carbon dioxide absorption-release magnesium alloy provided by the invention can realize carbon dioxide absorption-release without any additive or any special casting process and condition, and the magnesium alloy provided by the invention is an alloy for carbon dioxide absorption-release; the content, size and distribution of the air holes are closely related to the components and the solidification rate of the alloy, so that the adjustment of the air holes of the alloy is very easy to realize. Specifically, the present invention provides a magnesium alloy for carbon dioxide absorption-release, comprising:
Zn 5~18wt%;
Al 5~18wt%;
La 3~15wt%;
the balance of Mg;
the Zn content is more than or equal to the Al content, and the Al content is more than or equal to the La content.
The magnesium alloy for carbon dioxide absorption-release provided by the invention comprises 5-18 wt% of Zn; specifically, the Zn content is 6-15 wt%, and more specifically, the Zn content is 8-12%. The content of Zn in the magnesium alloy for carbon dioxide absorption-release provided by the invention enables the magnesium alloy for carbon dioxide absorption-release to have very good flow property, and further enables the magnesium alloy for carbon dioxide absorption-release provided by the invention to be capable of producing large-size castings with complex structures.
The magnesium alloy for carbon dioxide absorption-release provided by the invention comprises 5-18 wt% of Al. Specifically, the content of Al is 6-14%; more specifically, the content of Al is 8-12 wt%. In the invention, the Al can act together with the Zn in the technical scheme to further improve the fluidity of the alloy liquid and inhibit the hot cracking behavior in the alloy casting process, so that the magnesium alloy with carbon dioxide absorption-release provided by the invention has better casting quality.
The magnesium alloy for carbon dioxide absorption-release provided by the invention comprises 3-15 wt% of La. Specifically, the La content is 4-13 wt%, more specifically, 5-9 wt%. In the invention, the La can be combined with Al and Zn in the technical scheme to form a ternary phase, wherein the ternary phase also comprises a ternary quasicrystal phase; the ternary quasicrystal phase has a regulating effect on the absorption and release of gas in the solidification process, so that the content and the size of the pores of the carbon dioxide absorption-release magnesium alloy provided by the invention can be regulated.
In the invention, the Zn content is more than or equal to the Al content, and the Al content is more than or equal to the La content; without the above content relationship, the amount of solidification-released gas is small, even no gas is released. The magnesium alloy for carbon dioxide absorption-release also comprises impurity elements, the total amount of Fe, Ni, Cu, Be and the like is less than 0.05 wt%, and the balance is magnesium.
The invention also provides a method for absorbing and releasing carbon dioxide by using the magnesium alloy, which comprises the following steps:
mixing a magnesium source, a zinc source, an aluminum source and a lanthanum source according to a ratio, and smelting to obtain an alloy liquid; introducing carbon dioxide in the smelting process;
and (3) placing the alloy liquid in a closed cooling device with a gas overflow outlet for cooling, and collecting to obtain carbon dioxide gas.
In the invention, a magnesium source, a zinc source, an aluminum source and a lanthanum source (or other alloy element sources) are smelted to obtain alloy liquid. In the present invention, the temperature of the melting is preferably 690 to 740 ℃, and most preferably 720 ℃. The smelting method is not particularly limited in the invention, and the technical scheme of metal smelting known to those skilled in the art can be adopted. The smelting is preferably carried out under the condition of carbon dioxide ambient atmosphere, and the ambient atmosphere is preferably N2And CO2. In the present invention, said N2And CO2Is preferably 2: 1. In the present invention, the melting is preferably carried out under stirring.
In the invention, a magnesium source and a lanthanum source are preferably smelted to obtain a first mixed molten metal; and mixing the first mixed metal liquid with a zinc source and an aluminum source (and other alloy element sources) to obtain an alloy liquid. The method for smelting the magnesium source, the zinc source, the aluminum source and the lanthanum source is not particularly limited, and the technical scheme of metal smelting known to those skilled in the art can be adopted. The magnesium source and lanthanum source are preferably preheated in the present invention prior to melting the sources. In the present invention, the temperature for preheating the magnesium source and the lanthanum source is preferably 120 to 400 ℃, more preferably 200 to 360 ℃, and most preferably 300 ℃.
After obtaining the first mixed molten metal, the present invention preferably mixes the first mixed molten metal with other alloying element sources to obtain a second mixed molten metal; in the present invention, the mixing temperature of the first mixed molten metal and the other alloying element source is preferably 720 ℃ to 750 ℃, more preferably 725 ℃ to 740 ℃, and most preferably 730 ℃. In the present invention, the mixing time of the first mixed molten metal and the other alloying element source is preferably 5 minutes to 10 minutes, and more preferably 6 minutes to 8 minutes; there is no second mixed metal liquid if no other alloying element source is added.
After the first or second mixed molten metal is obtained, the invention preferably mixes the first or second mixed molten metal with a zinc source and an aluminum source to obtain an alloy liquid; in the present invention, the mixing time of the first or second mixed metal solution with the zinc source and the aluminum source is preferably 10 minutes to 20 minutes, and more preferably 6 minutes to 12 minutes.
In the present invention, the zinc source is preferably pure zinc. In the present invention, the aluminum source is preferably pure aluminum. In the present invention, the magnesium source is preferably pure magnesium. The sources of the zinc source, the aluminum source and the magnesium source are not particularly limited in the present invention and are commercially available. In the present invention, the lanthanum source is preferably a magnesium-lanthanum master alloy. In the invention, the mass fraction of lanthanum in the magnesium-lanthanum intermediate alloy is preferably 15-40%, and more preferably 20-30%. In the present invention, the other alloying element source is preferably a magnesium-other alloying element master alloy. In the invention, the mass fraction of the magnesium-other alloy element intermediate alloy is not particularly limited, and the alloy preparation conditions can be met. The source of the lanthanum source and the source of other alloying elements are not particularly limited in the present invention, and any sources of the above kind known to those skilled in the art may be used, and may be commercially available. In embodiments of the invention, the lanthanum source and the other alloying element sources are commercially available.
After obtaining the alloy liquid, argon gas may be introduced into the alloy liquid to refine the alloy liquid. In the present invention, it is preferable that the alloy liquid is left to stand without refining. In the invention, the standing time is preferably 1-8 minutes, and the melt temperature during standing is preferably 630-730 ℃.
Before the magnesium source, the zinc source, the aluminum source, the lanthanum source and the other alloying element sources are smelted, the magnesium source, the zinc source, the aluminum source, the lanthanum source and the other alloying element sources are preferably preheated in the invention. In the present invention, the temperature for preheating the magnesium source, the zinc source, the aluminum source, the lanthanum source, and the other alloying element source is preferably 120 to 400 ℃, more preferably 200 to 360 ℃, and most preferably 300 ℃.
After obtaining the alloy liquid, the alloy liquid is cast, and in the invention, the casting temperature is preferably 630-730 ℃, more preferably 650-700 ℃, and most preferably 660-680 ℃. In the present invention, the casting rate is not particularly limited, and a magnesium alloy casting method known to those skilled in the art may be used. The invention has special limitation on the casting mould, and the casting mould is completely sealed after casting and is provided with a gas overflow collecting port; during casting, as the melt cools, carbon dioxide is gradually released from the melt, providing a high purity gas that can be recycled.
In the invention, the carbon dioxide absorption-release magnesium alloy comprises 5-18 wt% of Zn, 5-18 wt% of Al and 3-15 wt% of La, wherein the content of Zn is not lower than that of Al, the content of Al is not lower than that of La, the total amount of impurity elements Fe, Ni, Cu, Be and the like is less than 0.05 wt%, and the balance is magnesium. The invention can control the dosage of the magnesium source, the zinc source, the aluminum source and the lanthanum source (and other alloy element sources) in the technical scheme to obtain the carbon dioxide absorption-release magnesium alloy with the components.
The experimental result shows that the carbon dioxide absorbing-releasing magnesium alloy provided by the invention absorbs carbon dioxide in a molten state by about 6-14 times of the volume of the magnesium alloy melt, the purity is more than 99.9%, and the cycle time is more than 30 times.
The invention provides a carbon dioxide absorbing-releasing magnesium alloy, comprising: 5-18 wt% of Zn, 5-18 wt% of Al and 3-15 wt% of La, wherein the content of Zn is not lower than that of Al, the content of Al is not lower than that of La, and the balance is magnesium. The carbon dioxide absorbing-releasing magnesium alloy provided by the invention contains La, Zn and Al, a melt formed by the La, Zn and Al after melting can absorb a large amount of carbon dioxide gas, and the carbon dioxide gas is rapidly separated out from the melt along with the reduction of temperature in the solidification process, so that the carbon dioxide absorbing-releasing magnesium alloy provided by the invention can realize the effective absorption and release of the carbon dioxide without any additive or any special process and condition. In addition, the carbon dioxide absorbing-releasing magnesium alloy provided by the invention contains Zn and Al, and also contains La, and the solid solubility of carbon dioxide in the melt can be greatly changed by the melt formed by the Zn, the Al and the La, so that the absorption of carbon dioxide gas is realized; with the reduction of the temperature, the solubility of the carbon dioxide in the melt is rapidly reduced, so that carbon dioxide gas is released; therefore, the carbon dioxide absorbing-releasing magnesium alloy provided by the invention can effectively absorb carbon dioxide in a molten state, and release carbon dioxide in a cooling process, provides high-purity gas, and can be recycled.
For further understanding of the present invention, the following examples are given to illustrate the magnesium alloy of the present invention, and the scope of the present invention is not limited by the following examples.
The raw materials used in the following examples of the present invention are all commercial products, the mass fraction of lanthanum in the magnesium lanthanum master alloy used is 28%, and the aluminum and zinc used are pure aluminum and pure zinc.
Example 1
7800g of pure magnesium, 1600g of pure zinc, 1600g of pure aluminum and 4000g of magnesium-lanthanum intermediate alloy are preheated to 300 ℃; firstly, putting preheated pure magnesium and magnesium lanthanum intermediate alloy into a crucible preheated to 300 ℃, and introducing N into the crucible2And CO2Is 2:1 of the gas mixture of the first and second gases,adding the pure zinc and the pure aluminum preheated to 300 ℃ into the crucible at 730 ℃ under the stirring condition, and mixing for 8 minutes to obtain alloy liquid; cooling the alloy liquid to 670 ℃, and standing for 1 minute;
and directly casting the alloy liquid after standing into a specific mould, and collecting gas generated in the solidification process through an exhaust port.
The component detection of the carbon dioxide absorption-release magnesium alloy obtained in the embodiment 1 of the invention is carried out by adopting a spectrum analyzer, and the detection result is as follows: the carbon dioxide absorption-release magnesium alloy obtained in embodiment 1 of the present invention includes: 9.94 wt% of Zn, 9.83 wt% of Al, 7.47 wt% of La, the total amount of impurity elements Fe, Cu and Ni is less than 0.03 wt%, and the balance is magnesium. As shown in fig. 1, it can be seen that the magnesium alloy for absorbing and releasing carbon dioxide obtained in example 1 of the present invention has a uniform structure and includes two forms of the second phase, when the magnesium alloy for absorbing and releasing carbon dioxide obtained in example 1 of the present invention is analyzed by scanning electron micrographs.
The experimental results are as follows: the amount of carbon dioxide absorbed was about 12 times the volume of the magnesium alloy melt, and the purity was measured according to HG/T2537-1993 carbon dioxide for welding, resulting in a purity of greater than 99.9%.
Example 2
11800g of pure magnesium, 800g of pure zinc, 800g of pure aluminum and 1600g of magnesium-lanthanum intermediate alloy are preheated to 300 ℃; firstly, putting preheated pure magnesium and magnesium lanthanum intermediate alloy into a crucible preheated to 300 ℃, and introducing N into the crucible2And CO2Is 2:1, adding the pure zinc and the pure aluminum preheated to 300 ℃ into the crucible at 730 ℃ under the stirring condition, and mixing for 8 minutes to obtain alloy liquid; cooling the alloy liquid to 680 ℃, and standing for 6 minutes;
and directly casting the alloy liquid after standing into a specific mould, and collecting gas generated in the solidification process through an exhaust port.
The component detection of the carbon dioxide absorption-release magnesium alloy obtained in the embodiment 2 of the invention is carried out by adopting a spectrum analyzer, and the detection result is as follows: the carbon dioxide absorption-release magnesium alloy obtained in embodiment 2 of the present invention includes: 5.02 wt% of Zn, 4.93 wt% of Al, 2.97 wt% of La, less than 0.05 wt% of the total amount of impurity elements Fe, Cu and Ni, and the balance of magnesium.
The experimental results are as follows: the amount of carbon dioxide absorbed was about 6 times the volume of the magnesium alloy melt, and the purity was measured according to HG/T2537-1993 carbon dioxide for welding, resulting in a purity of more than 99.9% for carbon dioxide.
Example 3
Preheating 2240g of pure magnesium, 2880g of pure zinc, 2880g of pure aluminum and 8000g of magnesium-lanthanum intermediate alloy to 300 ℃; firstly, putting preheated pure magnesium and magnesium lanthanum intermediate alloy into a crucible preheated to 300 ℃, and introducing N into the crucible2And CO2Is 2:1, adding the pure zinc and the pure aluminum preheated to 300 ℃ into the crucible at 730 ℃ under the stirring condition, and mixing for 8 minutes to obtain alloy liquid; cooling the alloy liquid to 690 ℃, and standing for 3 minutes;
and directly casting the alloy liquid after standing into a specific mould, and collecting gas generated in the solidification process through an exhaust port.
The component detection of the carbon dioxide absorption-release magnesium alloy obtained in the embodiment 3 of the invention is carried out by adopting a spectrum analyzer, and the detection result is as follows: the carbon dioxide absorption-release magnesium alloy obtained in embodiment 3 of the present invention includes: 17.84 wt% Zn, 17.65 wt% Al, 14.21 wt% La, the total amount of impurity elements Fe, Cu and Ni being less than 0.03 wt%, the balance being magnesium. The carbon dioxide absorbing-releasing magnesium alloy obtained in example 3 of the present invention was photographed by a scanning electron microscope, as shown in fig. 2.
As a result of the experiment, the absorption amount of carbon dioxide was about 14 times the volume of the magnesium alloy melt, and the purity thereof was measured according to the standard of HG/T2537-1993 carbon dioxide for welding, resulting in that the purity of carbon dioxide was more than 99.9%.
Example 4
8200g of pure magnesium, 1600g of pure zinc, 1600g of pure aluminum and 4600g of magnesium lanthanum intermediate alloy are preheated to 300 ℃; firstly, preheated pure magnesium and magnesium lanthanum are addedPlacing the master alloy into a crucible preheated to 300 ℃, and introducing N into the crucible2And CO2Is 2:1, adding the pure zinc and the pure aluminum preheated to 300 ℃ into the crucible at 730 ℃ under the stirring condition, and mixing for 8 minutes to obtain alloy liquid; cooling the alloy liquid to 680 ℃, and standing for 8 minutes;
and directly casting the alloy liquid after standing into a specific mould, and collecting gas generated in the solidification process through an exhaust port.
The component detection of the magnesium alloy absorbed and released by carbon dioxide obtained in the embodiment 4 of the invention is carried out by a spectrum analyzer, and the detection result is as follows: the carbon dioxide absorption-release magnesium alloy obtained in embodiment 4 of the present invention includes: 10.09 wt% of Zn, 9.78 wt% of Al, 7.97 wt% of La, less than 0.03 wt% of the total amount of impurity elements Fe, Cu and Ni, and the balance of magnesium. The experimental results are as follows: the carbon dioxide absorption amount is about 7 times of the volume of the magnesium alloy melt.
Example 5
8800g of pure magnesium, 1600g of pure zinc, 1600g of pure aluminum and 4000g of magnesium-lanthanum intermediate alloy are preheated to 300 ℃; firstly, putting preheated pure magnesium and magnesium lanthanum intermediate alloy into a crucible preheated to 300 ℃, and introducing N into the crucible2And CO2Is 2:1, adding the pure zinc and the pure aluminum preheated to 300 ℃ into the crucible at 730 ℃ under the stirring condition, and mixing for 8 minutes to obtain alloy liquid; cooling the alloy liquid to 680 ℃, and standing for 5 minutes; and directly casting the alloy liquid after standing into a specific mould, and collecting gas generated in the solidification process through an exhaust port to obtain an alloy ingot.
And (3) detecting the components of the obtained carbon dioxide absorption-release magnesium alloy by using a spectrum analyzer, wherein the detection result is as follows: the carbon dioxide absorption-release magnesium alloy obtained in embodiment 5 of the present invention includes: 9.94 wt% of Zn, 9.68 wt% of Al, 7.25 wt% of La, less than 0.03 wt% of the total amount of impurity elements Fe, Cu and Ni, and the balance of magnesium.
Then preheating the alloy ingot to 300 ℃, and putting the alloy ingot into the furnace againHeating to 300 deg.C in crucible, introducing N into the crucible2And CO2Is 2:1 to obtain alloy liquid, stirring for 6 minutes at 730 ℃, then cooling to 680 ℃, standing for 5 minutes, and then casting to obtain an alloy ingot. The melting step of the alloy ingot is repeated for 30 times. The carbon dioxide emissions and purity were measured for each casting.
The experimental results are as follows: the amount of carbon dioxide absorbed was about 13 times the volume of the magnesium alloy melt, and the purity was measured according to HG/T2537-1993 carbon dioxide for welding, resulting in a purity of more than 99.9% for carbon dioxide. After 30 absorption-release cycles, the carbon dioxide absorption amount is not less than 12.5 times of the volume of the magnesium alloy melt.
Comparative example 1
11800g of pure magnesium, 1600g of pure zinc, 1600g of pure aluminum: firstly, putting preheated pure magnesium into a crucible preheated to 300 ℃, and introducing N into the crucible2And CO2Is 2:1, adding the pure zinc and the pure aluminum preheated to 300 ℃ into the crucible at 730 ℃ under the stirring condition, and mixing for 8 minutes to obtain alloy liquid; cooling the alloy liquid to 670 ℃, and standing for 5 minutes;
and directly casting the alloy liquid after standing into a specific mould, and collecting gas generated in the solidification process through an exhaust port.
The composition detection of the carbon dioxide absorption-release magnesium alloy obtained in the comparative example 1 of the invention is carried out by a spectrum analyzer, and the detection result is as follows: the carbon dioxide absorbing-releasing magnesium alloy obtained in comparative example 1 of the present invention includes: 10.03 wt% of Zn, 9.56 wt% of Al, less than 0.03 wt% of the total amount of impurity elements Fe, Cu and Ni, and the balance of magnesium. The experimental result shows that the carbon dioxide absorption amount is less than 0.1 time of the volume of the magnesium alloy melt.
Comparative example 2
9400g of pure magnesium, 1600g of pure zinc and 4000g of magnesium-lanthanum intermediate alloy are preheated to 300 ℃; firstly, putting preheated pure magnesium and magnesium lanthanum intermediate alloy into a crucible preheated to 300 ℃, and introducing N into the crucible2And CO2Is 2:1, adding the pure zinc preheated to 300 ℃ into the crucible at 730 ℃ under the stirring condition, and mixing for 8 minutes to obtain alloy liquid; cooling the alloy liquid to 680 ℃, and standing for 5 minutes;
and directly casting the alloy liquid after standing into a specific mould, and collecting gas generated in the solidification process through an exhaust port.
And (3) detecting the components of the magnesium alloy absorbed and released by carbon dioxide obtained in the comparative example 2 by using a spectrum analyzer, wherein the detection result is as follows: the carbon dioxide absorbing-releasing magnesium alloy obtained in comparative example 2 of the present invention includes: 9.98 wt% of Zn, 7.38 wt% of La, less than 0.03 wt% of the total amount of impurity elements Fe, Cu and Ni, and the balance of magnesium. The experimental result shows that the carbon dioxide absorption amount is less than 0.1 time of the volume of the magnesium alloy melt.
Comparative example 3
9400g of pure magnesium, 1600g of pure aluminum and 4000g of magnesium-lanthanum intermediate alloy are preheated to 300 ℃; firstly, putting preheated pure magnesium and magnesium lanthanum intermediate alloy into a crucible preheated to 300 ℃, and introducing N into the crucible2And CO2Is 2:1, adding the pure aluminum preheated to 300 ℃ into the crucible at 730 ℃ under the stirring condition, and mixing for 8 minutes to obtain alloy liquid; cooling the alloy liquid to 680 ℃, and standing for 5 minutes;
and directly casting the alloy liquid after standing into a specific mould, and collecting gas generated in the solidification process through an exhaust port.
The composition detection of the carbon dioxide absorption-release magnesium alloy obtained in the comparative example 3 of the invention is carried out by adopting a spectrum analyzer, and the detection result is as follows: the carbon dioxide absorbing-releasing magnesium alloy obtained in comparative example 3 of the present invention includes: 9.84 wt% of Al, 7.31 wt% of La, the total amount of impurity elements Fe, Cu and Ni is less than 0.03 wt%, and the balance is magnesium. The experimental result shows that the carbon dioxide absorption amount is less than 0.1 time of the volume of the magnesium alloy melt.
Comparative example 4
9400g of pure magnesium, 1600g of pure zinc, 800g of pure aluminum and 3200g of magnesium-lanthanum intermediate alloy are preheated to 300 DEG C(ii) a Firstly, putting preheated pure magnesium and magnesium lanthanum intermediate alloy into a crucible preheated to 300 ℃, and introducing N into the crucible2And CO2Is 2:1, adding the pure aluminum and the pure zinc preheated to 300 ℃ into the crucible at 730 ℃ under the stirring condition, and mixing for 8 minutes to obtain alloy liquid; cooling the alloy liquid to 680 ℃, and standing for 5 minutes;
and directly casting the alloy liquid after standing into a specific mould, and collecting gas generated in the solidification process through an exhaust port.
And (3) detecting the components of the magnesium alloy absorbed and released by carbon dioxide obtained in the comparative example 4 by using a spectrum analyzer, wherein the detection result is as follows: the carbon dioxide absorbing-releasing magnesium alloy obtained in comparative example 4 of the present invention includes: 9.93 wt% Zn, 4.86 wt% Al, 5.85 wt% La, less than 0.03 wt% of the total amount of impurity elements Fe, Cu and Ni, the balance being magnesium. The experimental result shows that the carbon dioxide absorption amount is less than 0.5 time of the volume of the magnesium alloy melt.
Comparative example 5
9400g of pure magnesium, 1600g of pure aluminum, 800g of pure zinc and 3200g of magnesium-lanthanum intermediate alloy are preheated to 300 ℃; firstly, putting preheated pure magnesium and magnesium lanthanum intermediate alloy into a crucible preheated to 300 ℃, and introducing N into the crucible2And CO2Is 2:1, adding the pure aluminum and the pure zinc preheated to 300 ℃ into the crucible at 730 ℃ under the stirring condition, and mixing for 8 minutes to obtain alloy liquid; cooling the alloy liquid to 680 ℃, and standing for 5 minutes;
and directly casting the alloy liquid after standing into a specific mould, and collecting gas generated in the solidification process through an exhaust port.
And (3) detecting the components of the magnesium alloy obtained in the comparative example 5 by using a spectrum analyzer, wherein the detection result is as follows: the carbon dioxide absorbing-releasing magnesium alloy obtained in comparative example 3 of the present invention includes: 4.91 wt% of Zn, 9.76 wt% of Al, 5.91 wt% of La, less than 0.03 wt% of the total amount of impurity elements Fe, Cu and Ni, and the balance of magnesium. The experimental result shows that the carbon dioxide absorption amount is less than 0.5 time of the volume of the magnesium alloy melt.
The carbon dioxide absorbing/releasing magnesium alloy provided by the invention contains La, Zn and Al, a melt formed by the La, Zn and Al after melting can absorb a large amount of carbon dioxide gas, and the carbon dioxide gas is rapidly separated out from the melt along with the reduction of temperature in the cooling process of the melt, so that the carbon dioxide absorbing/releasing magnesium alloy provided by the invention can realize the effective absorption and release of the carbon dioxide without any additive or any special casting process and condition, therefore, the carbon dioxide absorbing/releasing magnesium alloy provided by the invention can absorb the carbon dioxide and can also be separated to prepare the high-purity carbon dioxide gas. In addition, the carbon dioxide absorbing-releasing magnesium alloy provided by the invention can be recycled, and the absorption efficiency of carbon dioxide is not obviously reduced after 30 times of circulation.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A magnesium alloy for carbon dioxide absorption-release, comprising:
Zn 5~18wt%;
Al 5~18wt%;
La 3~15wt%;
the balance of Mg;
the Zn content is more than or equal to the Al content, and the Al content is more than or equal to the La content.
2. The magnesium alloy according to claim 1, wherein the Zn content is 6 to 15 wt%.
3. The magnesium alloy according to claim 1, wherein the content of Al is 6 to 14 wt%.
4. The magnesium alloy according to claim 1, wherein the La content is 4 to 13 wt%.
5. The magnesium alloy of claim 1, wherein the total amount of Fe, Cu and Ni in the magnesium alloy is less than 0.03 wt%.
6. The method for absorbing-releasing carbon dioxide of a magnesium alloy as set forth in claim 1, comprising the steps of:
mixing a magnesium source, a zinc source, an aluminum source and a lanthanum source according to a ratio, and smelting to obtain an alloy liquid; introducing carbon dioxide in the smelting process;
and (3) placing the alloy liquid in a closed cooling device with a gas overflow outlet for cooling, and collecting to obtain carbon dioxide gas.
7. The method of claim 6, wherein the temperature of the smelting is 650-800 ℃.
8. The method of claim 6, wherein the mixed feedstock further comprises a source of other alloying elements; the preparation of the alloy liquid comprises the following steps:
smelting a magnesium source and a lanthanum source to obtain a first mixed molten metal;
mixing the first mixed molten metal with other alloy element sources to obtain a second mixed molten metal;
and mixing the second mixed molten metal with a zinc source and an aluminum source to obtain alloy liquid.
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CN112680643A (en) * | 2020-12-17 | 2021-04-20 | 中国科学院长春应用化学研究所 | Rare earth Y-containing self-foaming porous magnesium alloy and preparation method thereof |
CN112680645A (en) * | 2020-12-17 | 2021-04-20 | 中国科学院长春应用化学研究所 | Rare earth Sm-containing self-foaming porous magnesium alloy and preparation method thereof |
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CN112680643A (en) * | 2020-12-17 | 2021-04-20 | 中国科学院长春应用化学研究所 | Rare earth Y-containing self-foaming porous magnesium alloy and preparation method thereof |
CN112680645A (en) * | 2020-12-17 | 2021-04-20 | 中国科学院长春应用化学研究所 | Rare earth Sm-containing self-foaming porous magnesium alloy and preparation method thereof |
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