CN115010160A - Method for preparing calcium carbonate by using desulfurized ash of glass plant to solidify carbon dioxide - Google Patents
Method for preparing calcium carbonate by using desulfurized ash of glass plant to solidify carbon dioxide Download PDFInfo
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- CN115010160A CN115010160A CN202210641915.5A CN202210641915A CN115010160A CN 115010160 A CN115010160 A CN 115010160A CN 202210641915 A CN202210641915 A CN 202210641915A CN 115010160 A CN115010160 A CN 115010160A
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- carbon dioxide
- calcium carbonate
- fly ash
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
- C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
- Y02P40/18—Carbon capture and storage [CCS]
Abstract
The invention discloses a method for preparing calcium carbonate by using glass factory desulfurized fly ash to solidify carbon dioxide, which solves the technical problems of manpower and material resource waste and higher cost caused by a conventional disposal method in the prior art. The preparation method comprises the following steps of S1, mixing the desulfurized fly ash and distilled water uniformly to form slurry; s2 adding urea and KMnO into the slurry formed in S1 4 Stirring with distilled water; s3, introducing carbon dioxide gas into the uniform material formed in the step S2, solidifying the carbon dioxide, adding water for multiple washing and filtering after the material is in a suspension state; and S4, drying the solid filter residue at 90-110 ℃ to obtain calcium carbonate. The invention successfully captures and solidifies the carbon dioxide and prepares the calcium carbonate, can be used for capturing the carbon dioxide in cement enterprises, can use the solidified product as a raw material required by cement production, has important significance for cost reduction and efficiency improvement in building material industry and achievement of double-carbon target first, and has certain practical significancePopularization and application value.
Description
Technical Field
The invention belongs to the field of building materials, and particularly relates to a method for preparing calcium carbonate by solidifying carbon dioxide by using desulfurization ash in a glass plant.
Background
Climate change is one of the major challenges facing the world today, and since the first industrial revolution, the discovery and utilization of fossil energy greatly improves the production efficiency, promotes the prosperity and development of human society, but at the same time brings about serious problems of environmental and climate change and the like. Global warming caused by the emission of greenhouse gases mainly comprising carbon dioxide is a global problem, and seriously threatens the survival and sustainable development of human beings. According to the '30.60' double-carbon target proposed by China, China needs to achieve 'carbon peak reaching' before 2030 years, namely, carbon emission does not increase after reaching the peak value, and 'carbon neutralization' is achieved before 2060 years, namely, the 'emitted carbon' is equal to the 'absorbed carbon'. The reduction of fossil energy, the reasonable utilization of industrial solid wastes for capturing and utilizing carbon dioxide are important ways for the building material industry to strive to realize the double-carbon target. Calcium carbonate has a wide industrial application range, and is widely used in the fields of paper making, coatings, metallurgy, rubber, glass, adhesives, medicines, foods and the like.
The carbon capture and purification technology is complex, and the actual breakthrough can not be achieved in the field of production and research for many years, a certain cement enterprise in China captures carbon dioxide by a chemical absorption method, waste gas generated in cement production sequentially enters a desulfurization water washing tower, an absorption tower, an analytic tower and a fine sulfur bed to complete various processes of impurity removal, purification and the like, and finally, the waste gas is stored in a tank in a liquid state. However, the method has high comprehensive cost, is difficult to popularize on a large scale, and does not meet the development trend of the cement industry under the double-carbon target requirement.
The applicant has found that the prior art has at least the following technical problems:
1. in the prior art; the traditional calcium carbonate production process usually only adopts a single crushing method or a carbonization method, and also needs a high-temperature calcination method, so that the manpower, material resources and resources are consumed, the produced calcium carbonate has high viscosity and low purity, and the use value of the calcium carbonate is greatly reduced.
2. In the prior art; the carbon capture and purification technology is complex, and the actual breakthrough can not be achieved in the field of production and research for many years, a certain cement enterprise in China captures carbon dioxide by a chemical absorption method, waste gas generated in cement production sequentially enters a desulfurization water washing tower, an absorption tower, an analytic tower and a fine sulfur bed to complete various processes of impurity removal, purification and the like, and finally, the waste gas is stored in a tank in a liquid state. The comprehensive cost is high, the large-scale popularization is difficult, and the development trend of the cement industry under the double-carbon target requirement is not met.
3. In the prior art; national patent CN 103663529A discloses a method for preparing nano calcium carbonate slurry by using waste gypsum as a calcium source, water is added into the waste gypsum to prepare gypsum slurry, ammonia water and the gypsum slurry are stirred and mixed, carbon dioxide is introduced, the mixture is stirred until calcium sulfate in the waste gypsum is completely converted into nano calcium carbonate, the nano calcium carbonate slurry is obtained after filtration and filter cakes are dispersed in the water. The method has the advantages that the ardealite contains more impurities, the purity of a solidified product is influenced to a certain degree, ammonia water is directly introduced into waste gypsum slurry, ammonia water leakage and ammonia escape are easily caused, safety risks and environmental protection risks are realized, the method does not accord with the enterprise development trend under the double-carbon target, and waste of manpower and material resources is easily caused. The reasons for the defects are that ammonia water is volatile and has certain corrosivity, certain potential safety hazards exist in direct industrial application, a certain amount of impurities exist in phosphogypsum, the yield of calcium carbonate is unstable, certain dangerousness and environmental protection risks exist, and large-scale industrial application is not facilitated.
At present, no relevant research and report exists for preparing calcium carbonate by directly utilizing desulfurized fly ash of a glass plant to solidify carbon dioxide. In conclusion, how to design a simple and practical method which has low cost and directly utilizes industrial solid wastes to solidify carbon dioxide has important significance for cost reduction and efficiency improvement in the building material industry and the achievement of the double-carbon target in the first place.
In order to overcome the defects of the prior art, the method for preparing calcium carbonate by solidifying carbon dioxide by utilizing the desulfurized ash of the glass plant is provided for overcoming the manpower and material resource waste and higher cost caused by the conventional disposal method by respectively researching, analyzing and comparing the characteristics of calcareous raw materials and combining the characteristics of calcium sulfite in the desulfurized ash of the glass plant. The calcium sulfite in the desulfurized ash is catalyzed and oxidized by adding urea and potassium permanganate which are convenient to operate and high in safety, so that carbon dioxide is solidified, and the environmental protection risk and the safety risk of enterprises are reduced. The method can realize the high-efficiency solidification of the carbon dioxide, improve the production efficiency of the building material industry, and reduce the environmental protection and economic pressure of enterprises, and the scheme is economical and practical and has low cost.
Disclosure of Invention
The invention aims to provide a method for preparing calcium carbonate by using glass factory desulfurized ash to solidify carbon dioxide, which aims to solve the technical problems of manpower and material waste and high cost caused by the conventional disposal method in the prior art.
In order to achieve the purpose, the invention provides a method for preparing calcium carbonate by using desulfurized ash to solidify carbon dioxide, and the invention provides the following technical scheme for achieving the purpose:
the preparation method of calcium carbonate by using the desulfurized fly ash of a glass plant to solidify carbon dioxide needs to use the following raw materials:
desulfurization ash: 10% -20%;
distilled water: 77.5 to 89 percent;
urea: 0.75 to 1.5 percent;
KMnO 4 ：0.25％～1％。
a method for preparing calcium carbonate by solidifying carbon dioxide by using desulfurization ash in a glass plant comprises the following steps:
s1, pretreating the desulfurized fly ash, and uniformly mixing the desulfurized fly ash with distilled water to form slurry;
s2, adding a certain amount of urea and KMnO into the slurry formed in the step S1 4 And distilled water, and the materials are stirred and mixed evenly by magnetic force;
s3, introducing carbon dioxide gas into the uniform material formed in the step S2 at a constant speed, solidifying the carbon dioxide, adding water into the material in a suspension state, washing and filtering the mixture for multiple times to obtain solid filter residues, and obtaining filtrate for later use;
and S4, drying the solid filter residue to obtain the calcium carbonate.
Further, the desulfurized fly ash is obtained from industrial waste residues discharged after desulfurization in a glass plant.
Furthermore, the used desulfurized ash accounts for 10-20%, the distilled water accounts for 77.5-89%, the usage amount of urea is 0.75-1.50%, and the usage amount of potassium permanganate is 0.25-1.00%.
Further, in the step S2, the stirring speed of the magnetic stirrer is 450rpm to 550rpm, and the time is 20 min.
Furthermore, the ambient temperature in the preparation process is 20-30 ℃.
Further, in the step S3, the introduction amount of carbon dioxide is 200mL/min, and the time is 2.5 hours.
Further, the filtrate obtained in step S3 is left to stand to remove the supernatant, and then evaporated to crystallize to obtain an ammonium compound.
Further, in the step S4, the drying temperature of the solid filter residue is 90 to 110 ℃.
Based on the technical scheme, the embodiment of the invention can at least produce the following technical effects:
(1) the desulfurization ash is industrial waste residue discharged after desulfurization of a certain glass plant in the southwest region, and the desulfurization ash which is cheap and difficult to treat in the southwest region is used for curing carbon dioxide, so that the resource utilization of wastes is realized, the important significance is provided for cost reduction and efficiency improvement in the building material industry and the achievement of the double-carbon goal in advance, and good social and economic benefits can be brought.
(2) The invention is realized by the incorporation of urea and KMnO 4 The method oxidizes the calcium sulfite in the desulfurized fly ash and traps and solidifies the carbon dioxide, has the advantages of simple process flow, strong operability, energy conservation and emission reduction, low cost, economy and practicality, high safety and certain popularization value.
(3) The method utilizes the cheap desulfurized fly ash which is low in cost and causes headaches of glass enterprises in southwest to capture carbon dioxide, can be popularized and utilized to the cement industry to develop carbon emission reduction, has positive promotion effect and very wide application prospect on solving the problem of environmental protection in the building material industry, reducing the environmental protection risk and safety risk of the enterprises, leading to the realization of double-carbon targets and the like.
In conclusion, the technical scheme of the invention has good social value, ecological environmental value and economic value, and the produced calcium carbonate has wide industrial application, is widely used in various fields such as paper making, coating, metallurgy, rubber, glass, adhesive, medicine, food and the like, and is easy to popularize and apply.
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart of an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The technical solution of the present invention will be described in further detail with reference to specific embodiments.
Example 1:
preparing calcium carbonate by using desulfurized fly ash of a glass plant to solidify carbon dioxide:
1.1 raw materials: the raw material composition is shown in the following table 1:
table 1 example 1 material ratio (%)
| Examples | Desulfurized fly ash | Distilled water | Urea | KMnO 4 |
| Example 1 | 10.00 | 89.00 | 0.75 | 0.25 |
1.2 the preparation method comprises the following steps:
it comprises the following steps:
s1, pretreating the desulfurized fly ash, and uniformly mixing 10.00 percent of desulfurized fly ash and 89.00 percent of distilled water to form slurry;
s2, adding 0.75 percent of urea and KMnO into the slurry formed in the step S1 4 0.25 percent, and uniformly mixing the materials by magnetic stirring;
s3, introducing carbon dioxide gas into the uniform material formed in the step S2 at a constant speed, adding distilled water to wash and filter for multiple times after the material is in a suspension state;
and S4, drying the solid filter residue at 90 ℃ to obtain calcium carbonate, standing the filtrate to remove supernatant, and then evaporating and crystallizing to obtain an ammonium compound.
And the mass fraction of the finally obtained calcium carbonate is 91.78%.
In this example, the method for preparing calcium carbonate by using desulfurized fly ash from a glass plant to solidify carbon dioxide is applied to the preparation of calcium carbonate products.
Example 2:
preparing calcium carbonate by using desulfurized fly ash of a glass plant to solidify carbon dioxide:
2.1, raw materials: the raw material composition is shown in the following table 2:
table 2 example 2 material ratio (%)
| Examples | Desulfurized fly ash | Distilled water | Urea | KMnO 4 |
| Example 2 | 13.00 | 85.50 | 1.00 | 0.50 |
2.2 the preparation method comprises the following steps:
the method comprises the following steps:
s1, pretreating the desulfurized fly ash, and uniformly mixing 13.00 percent of desulfurized fly ash and 85.50 percent of distilled water to form slurry;
s2 adding 1.00% of urea and KMnO into the slurry formed in the step S1 4 0.50 percent, and the materials are stirred and mixed evenly by magnetic force;
s3, introducing carbon dioxide gas into the uniform material formed in the step S2 at a constant speed, solidifying the carbon dioxide, adding distilled water to wash and filter the material for multiple times when the material is in a suspension state;
s4, drying the solid filter residue at 95 ℃ to obtain calcium carbonate, standing the filtrate to remove supernatant, and then evaporating and crystallizing to obtain an ammonium compound.
The mass fraction of the finally obtained calcium carbonate is 90.84%.
In this example, the method for preparing calcium carbonate by using desulfurized fly ash from a glass plant to solidify carbon dioxide is applied to the preparation of calcium carbonate products.
Example 3:
preparing calcium carbonate by using desulfurized fly ash of a glass plant to solidify carbon dioxide:
3.1 raw materials: the raw material composition is shown in the following table 3:
table 3 example 3 material ratio (%)
| Examples | Desulfurized fly ash | Distilled water | Urea | KMnO 4 |
| Example 3 | 16.00 | 82.00 | 1.25 | 0.75 |
3.2 the preparation method comprises the following steps:
it comprises the following steps:
s1, pretreating the desulfurized fly ash, and uniformly mixing 16.00 percent of desulfurized fly ash and 82.00 percent of distilled water to form slurry;
s2 adding 1.25% of urea and KM into the slurry formed in the step S1nO 4 0.75 percent of distilled water, and the materials are stirred and mixed evenly by magnetic force;
s3, introducing carbon dioxide gas into the uniform material formed in the step S2 at a constant speed, solidifying the carbon dioxide, adding distilled water to wash and filter the material for multiple times when the material is in a suspension state;
and S4, drying the solid filter residue at 105 ℃ to obtain calcium carbonate, standing the filtrate to remove supernatant, and then evaporating and crystallizing to obtain an ammonium compound.
And the mass fraction of the finally obtained calcium carbonate is 89.98%.
In this example, the method for preparing calcium carbonate by using desulfurized fly ash from a glass plant to solidify carbon dioxide is applied to the preparation of calcium carbonate products.
Example 4:
preparing calcium carbonate by using desulfurized fly ash of a glass plant to solidify carbon dioxide:
4.1 raw materials: the raw material composition is shown in the following table 4:
table 4 example 4 material ratio (%)
| Examples | Desulfurized fly ash | Distilled water | Urea | KMnO 4 |
| Example 4 | 20.00 | 77.50 | 1.50 | 1.00 |
4.2 the preparation method comprises the following steps:
it comprises the following steps:
s1, pretreating the desulfurized fly ash, and uniformly mixing 20.00 percent of desulfurized fly ash and 77.50 percent of distilled water to form slurry;
s2, adding 1.50 percent of urea and KMnO into the slurry formed in the step S1 4 1.00 percent of distilled water, and uniformly mixing the materials by magnetic stirring;
s3, introducing carbon dioxide gas into the uniform material formed in the step S2 at a constant speed, solidifying the carbon dioxide, adding distilled water to wash and filter the material for multiple times when the material is in a suspension state;
s4, drying the solid filter residue at 110 ℃ to obtain calcium carbonate, standing the filtrate to remove supernatant, and then evaporating and crystallizing to obtain an ammonium compound.
The mass fraction of the finally obtained calcium carbonate is 89.58%.
In this example, the method for preparing calcium carbonate by using the desulfurized fly ash of a glass plant to solidify carbon dioxide is applied to the preparation of calcium carbonate products.
The results of the calcium carbonate mineral analysis test of the product obtained are shown in table 5:
TABLE 5 dried product calcium carbonate mineral composition (%)
| Mineral name | Calcite | Dolomite | Siderite ore | Quartz | Illite stone | Cristobalite | White mica | Chlorite (chlorite) | Microcline feldspar |
| Example 1 | 91.78 | 5.13 | 0.58 | 0.93 | 0.24 | 0.99 | 0.08 | 0.06 | 0.21 |
| Example 2 | 90.84 | 5.98 | 0.65 | 0.97 | 0.34 | 0.86 | 0.12 | 0.09 | 0.15 |
| Example 3 | 89.98 | 6.58 | 0.87 | 0.89 | 0.28 | 0.91 | 0.11 | 0.12 | 0.26 |
| Example 4 | 89.58 | 6.96 | 0.94 | 0.83 | 0.33 | 0.76 | 0.17 | 0.14 | 0.29 |
From the data of the dried product mineral, the main component is calcite type calcium carbonate, which shows that the carbon dioxide is successfully captured and solidified to prepare the calcium carbonate.
The invention has the beneficial effects that the cheap and difficult-to-treat desulfurized ash in southwest area is utilized to carry out solidification treatment on carbon dioxide, so that the resource utilization of wastes is realized, and good social and economic benefits can be brought. By incorporating urea and KMnO 4 The method for oxidizing the calcium sulfite in the desulfurized fly ash and capturing and solidifying the carbon dioxide has the advantages of concise process flow, strong operability, energy conservation, emission reduction, low cost, high safety and certain popularization value. The method also utilizes the cheap desulfurized fly ash which is very painful for glass enterprises in southwest to capture carbon dioxide, can be popularized and utilized to the cement industry to develop carbon emission reduction, solves the problem of environmental protection in the building material industry, and first realizes the double-carbonTargets, etc., and has positive promoting effect and wide application prospect.
The foregoing is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalents of the above embodiments according to the technical spirit of the present invention are included in the scope of the present invention.
Claims (8)
1. A method for preparing calcium carbonate by using desulfurized fly ash of a glass plant to solidify carbon dioxide is characterized by comprising the following steps:
the method comprises the following steps:
s1: firstly, pretreating desulfurized fly ash, and uniformly mixing the desulfurized fly ash with distilled water to form slurry;
s2: adding urea, potassium permanganate and distilled water into the slurry formed in the step S1, and uniformly mixing by magnetic stirring;
s3: introducing carbon dioxide gas into the uniform material formed in the step S2 at a constant speed, adding distilled water after the material is in a suspension state, washing and filtering for multiple times to obtain solid filter residues, and obtaining filtrate for later use;
s4: and drying the solid filter residue to obtain the calcium carbonate.
2. The method for preparing calcium carbonate by using the glass plant desulfurized fly ash to solidify carbon dioxide according to claim 1, wherein: the desulfurized ash is obtained from industrial waste residues discharged after desulfurization in a glass plant.
3. The method for preparing calcium carbonate by using the glass factory desulfurized fly ash to solidify carbon dioxide according to claim 1, wherein: the desulfurization ash accounts for 10-20%, the distilled water accounts for 77.5-89%, the usage amount of urea is 0.75-1.50%, and the usage amount of potassium permanganate is 0.25-1.00%.
4. The method for preparing calcium carbonate by using the glass factory desulfurized fly ash to solidify carbon dioxide according to claim 1, wherein: in the step S2, the stirring speed of the magnetic stirrer is 450 rpm-550 rpm, and the time is 20 min.
5. The method for preparing calcium carbonate by using the glass factory desulfurized fly ash to solidify carbon dioxide according to claim 1, wherein: the environmental temperature of the preparation process is 20-30 ℃.
6. The method for preparing calcium carbonate by using the glass factory desulfurized fly ash to solidify carbon dioxide according to claim 1, wherein: in the step S3, the introduction amount of the carbon dioxide is 200mL/min, and the time is 2.5 h.
7. The method for preparing calcium carbonate by using the glass factory desulfurized fly ash to solidify carbon dioxide according to claim 1, wherein: and (4) standing the filtrate obtained in the step S3 to remove the supernatant, and then evaporating and crystallizing to obtain an ammonium compound.
8. The method for preparing calcium carbonate by using the glass factory desulfurized fly ash to solidify carbon dioxide according to claim 1, wherein: in the step S4, the drying temperature of the solid filter residue is 90-110 ℃.
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| CN101734875A (en) * | 2009-12-28 | 2010-06-16 | 华北电力大学（保定） | Method for catalytic oxidation of calcium sulfite in desulphurization ash by dry method and semi-dry method |
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