CN114426419B

CN114426419B - Method for storing carbon dioxide in inorganic solid waste ceramsite mineralized concrete

Info

Publication number: CN114426419B
Application number: CN202210338660.5A
Authority: CN
Inventors: 苏斌; 苏文锦; 苏文雯
Original assignee: Beijing Jinxiu New Technology Development Co ltd
Current assignee: Beijing Jinxiu New Technology Development Co ltd
Priority date: 2022-04-01
Filing date: 2022-04-01
Publication date: 2022-07-12
Anticipated expiration: 2042-04-01
Also published as: CN114426419A

Abstract

The invention relates to a method for storing carbon dioxide by mineralizing concrete with inorganic solid waste ceramsite, which comprises the following steps of preparing inorganic solid waste ceramsite filter balls; preparing an aminated ceramsite filter ball; fully absorbing carbon dioxide by the aminated ceramsite filter ball to obtain an adsorption saturated carbon dioxide filter ball; and mixing and stirring the saturated carbon dioxide adsorption filter balls and the cement mortar concrete uniformly to prepare the mineralized lightweight concrete test piece. The invention introduces high-concentration CO such as factory chimney gas and the like after treating inorganic solid waste ceramsite filter balls with amino acid salt solution and/or amino ionic liquid₂Adsorption of saturated CO in the environment₂Then directly adding the additive into concrete, and using the additive as additive to make CO escaped from cement mixing water, hydration heat or steam curing process₂The rapid mineralization and maintenance of the cementing material is converted into the main component of the concrete, namely calcium carbonate and CO₂And (4) transforming and sealing.

Description

Method for storing carbon dioxide in inorganic solid waste ceramsite mineralized concrete

Technical Field

The invention relates to a method for sealing carbon dioxide in inorganic solid waste ceramsite mineralized concrete, belonging to the field of carbon dioxide absorption sealing methods.

Background

Negative carbon is a global solution for really coping with climate change, and not only all CO generated in production and life needs to be eliminated₂Additional consumption of large amounts of already existing CO₂The carbon dioxide needs to be converted and sealed to avoid leakage and secondary escape of the carbon dioxide. The key point for realizing the carbon-negative industry and the carbon-negative economy lies in system technical innovation. And establishing a negative carbon scale, industrialization and commercialization industrial economy body consisting of the parts of carbon absorption, carbon emission reduction and carbon utilization 3. At present, the carbon removal technology in the global scope can hardly meet the requirement of net carbon (negative carbon) through the analysis of the whole life cycle, the cost for treating carbon dioxide is more than or equal to 600$/t, the direct income for investing and removing carbon dioxide is negative, and the commercial popularization for removing carbon dioxide in a large scale is limited.

Currently, the CCS technology is mainly adopted in the world and can be divided into three steps of trapping, transporting and sealing, but the technologies have obvious disadvantages. The trapping material is mostly organic amine material, so the cost is high, the trapping equipment is complex, and high temperature and high pressure are required; organic amine chemical absorption method at low temperature (40-50 deg.C)) The carbon dioxide in the flue gas is absorbed, and then the carbon dioxide is released from the chemical solvent when the solution is heated (100-120 ℃), so that the high-concentration carbon dioxide is obtained. The method has the advantages of high absorption speed, high absorption capacity, high purity of recovered carbon dioxide and the like; nevertheless, the chemical absorption method based on representative MEA still has obvious limitation in large-scale commercial popularization and application, wherein one of the main reasons is that the operation energy consumption is too high, which causes the net efficiency of power generation of a power plant to be reduced by about 10%, and the regeneration energy consumption of the absorbent accounts for about 70% of the energy consumption of the whole system. In addition, the MEA absorbent also has a problem of excessive loss during operation due to oxidation and degradation. The mixed amine absorbent combines the advantages of a plurality of single absorbents, has higher absorption capacity and absorption rate and lower regeneration energy consumption, and absorbs CO in the flue gas by using the mixed organic amine absorbent₂The higher the total amine concentration and the higher the temperature, the faster the rate of amine degradation; CO2₂The load of (2) is large, and the degradation of amine can be inhibited; the amine is not degraded only in the absence of oxygen, but its large-scale industrialization is limited by the high raw material cost.

High desorption cost, complex desorption equipment and process, high temperature and high pressure requirement, and high energy consumption for desorption; the chemical absorption method is the most widely used CO at present₂A trapping technology capable of well treating low-concentration CO₂Gas, chemical absorption method utilizes alkaline absorbent and acidic gas CO in flue gas₂The reaction is carried out to generate unstable salts (such as carbonate, carbamate and the like), and the generated salts can be reversely decomposed under certain conditions to realize CO₂Separation and recovery of the absorbent, existing CO₂The absorption pregnant solution mainly adopts a thermal desorption mode to realize the regeneration of the absorbent, the desorption energy consumption is overlarge, and the cost is further increased due to the corrosion of corresponding equipment, so that the industrial scale industrialization of the absorption pregnant solution is limited.

On the other hand, the captured carbon dioxide must be transported to a suitable location for sequestration, and may be transported using automobiles, trains, ships, and pipelines. In contrast, pipeline is the most economical means of transportation. However, the density of carbon dioxide at normal temperature and normal pressure is 1.977kg/m, the transportation cost is very high, and particularly, the transportation energy consumption and the pipeline laying cost are unacceptable for inland cities, such as vehicles and pipeline transportation modes. A large amount of secondary energy consumption and regenerated emissions and pollutants exist in the whole capturing, desorbing and transporting processes, and the risk of secondary environmental pollution caused by carbon dioxide leakage is caused due to the influence of various factors.

The high-cost carbon dioxide obtained in the capturing, desorbing and transporting stages is stored in Geological Storage (Geological Storage) and Ocean Storage (Ocean Storage), and the carbon dioxide is not recycled. The overall capacity to remove carbon dioxide is small and does not meet the large scale removal requirements. The removal cost of carbon dioxide is too high, and the investment cost is too high to meet the commercial operation. Although the carbon dioxide capture of CCS technology commercialization has been in operation for some time, carbon dioxide sequestration technology is still experimenting on a large scale in various countries. Implementation of CO₂The most important thing of geological storage engineering is to ensure the effectiveness, safety and durability of geological storage. The current method and potential drawbacks are as follows:

ocean disposal, which means transporting carbon dioxide to the site where the ocean is sealed by pipeline or ship, injecting carbon dioxide into the water column or sea bottom of the ocean. The dissolved and dissipated carbon dioxide will then become part of the global carbon cycle. There are a number of problems with this approach. One is that ocean disposal is expensive. Secondly, carbon dioxide entering the ocean can cause harm to the ocean ecosystem. If too much carbon dioxide is dissolved in the seawater, the pH of the seawater will drop, which may have a significant effect on the growth of marine organisms. Thirdly, the disposal of the ocean is not always once for all, and the carbon dioxide stored in the ocean slowly escapes from the water surface and returns to the atmosphere. Thus, the marine disposal of carbon dioxide can only temporarily mitigate the build up of carbon dioxide in the atmosphere. The underground deep saline water layer is regarded as an optimal site for long-term carbon dioxide storage due to the characteristics of wide distribution, large storage capacity and the like. However, carbon dioxide presents a risk of leakage during sequestration due to changes in the reservoir stress field and the presence of geological structures, formations such as natural fractures, faults, etc.

And (4) geological sealing, wherein the geological sealing is to inject carbon dioxide into a proper stratum under pressure, and the pore space of the stratum is used for storing the carbon dioxide. A water permeable layer must be placed above the formation as a cap layer to sequester the injected carbon dioxide from leaks. In the oil recovery drilling industry, it is common practice to inject carbon dioxide into the formation with a drill to recover more oil. Sedimentary basins suitable for carbon dioxide sequestration may exist globally, including coastal areas. If carbon dioxide leaks into the atmosphere from a sequestration site, significant climate change may be induced. If leaked deep into the formation, disasters may be caused to humans, ecosystems and ground water. In addition, scientists testing the effectiveness of geological sequestration of carbon dioxide find that carbon dioxide injected deep into the formation can also damage minerals in the reservoir zone.

Ore carbonization, which refers to the solidification of carbon dioxide using basic and alkaline earth oxides, such as magnesium oxide and calcium oxide, is now present in naturally occurring silicate rocks such as olivine and the like. These substances chemically react with carbon dioxide to produce compounds such as magnesium carbonate and calcium carbonate (i.e., limestone). Carbon dioxide is not released to the atmosphere after carbonization and the associated risks are therefore small. The naturally occurring process of ore carbonization is very slow and often takes hundreds of years or even thousands of years to observe significant changes. The carbon dioxide concrete curing technology is characterized in that the carbon dioxide can be utilized to carry out chemical reaction with clinker components of cement to cause concrete hardening and strength development, and the main reaction product calcium carbonate has good stability and can convert and store carbon dioxide better, so that the carbon dioxide mineralized and cured concrete has good dimensional stability; meanwhile, compared with the steam curing concrete, the carbon dioxide mineralization curing concrete can reduce energy consumption and improve the performance of the concrete. And (3) immediately carrying out carbon dioxide mineralization curing on the molded mortar test piece, wherein the obtained strength can reach the compressive strength of the test piece after standard curing for 1d within a few minutes.By CO₂The mechanical property of the recycled concrete can be improved by the mineralization maintenance mode. The waste utilization rate can be improved by carrying out carbonization curing on the concrete doped with the recycled aggregate, and the fire resistance and the strength of the concrete are enhanced. Before carbonization and maintenance, the drying pretreatment of the concrete containing the recycled aggregate can obviously increase CO₂The mineralization curing degree is higher than that of 6h autoclaved curing, and the strength can be higher after 2h carbonization curing. CO for recycled concrete₂Mineralizing and curing can be regarded as a carbon fixation process, CO₂The mineralization curing can improve the early strength of the concrete and reduce the drying shrinkage of the concrete.

Factors influencing the carbon dioxide mineralization curing of concrete include the concentration of carbon dioxide, the pressure of carbon dioxide gas, the curing time, the water-gel ratio of a test piece, the components of cementing materials in concrete and the like. In the presence of CO₂In the process of mineralization and maintenance, CO₂The water can only enter the interior of a test piece through diffusion, the diffusion is greatly influenced by the water content and the porosity of the interior of the cement-based material, and the fixation effect of the water on the converted and sealed carbon dioxide is limited. Prof of Standby et al found that the moisture content of concrete has an obvious influence on the conversion and storage of carbon dioxide and the curing degree, and that the curing degree and the early strength can reach 36% and 14.9MPa respectively when the residual water-to-gel ratio is 0.16 after drying and pre-curing. The factors influencing the process of curing concrete by mineralizing with carbon dioxide are many, and one of the most critical factors is the water content of concrete in the reaction process. If the freshly mixed ordinary concrete mixture is contacted with carbon dioxide immediately after the forming, the carbonization reaction degree is very low, and the permeation speed of carbon dioxide gas in saturated micropores (D =1O-9 m)²/s) is less than 10000 times lower than in unsaturated micropores. In order to improve the reaction degree, researchers use concrete with a very low water-cement ratio to perform carbon dioxide mineralization curing, or use supercritical carbon dioxide, but the carbon dioxide mineralization curing degree is still low, and the mechanical property can not reach the expected target. Using autoclaved lightweight concrete and CO₂The reaction was carried out and CO was found to be at a pressure of 0.4MPa₂The test piece cured for 1h at a concentration of 100% can be completely carbonized, but when the gas concentration is only 3%, at least 200h is required to achieve the sameThe degree of carbonization of (a). CO2₂Influence factors of mineralized curing concrete blocks, and the fact that the water content in the test piece reaches 1.4-1.8 through pre-curing is found that better CO can be obtained₂Mineralizing and curing effect, CO₂The gas concentration, pressure and environmental humidity in the mineralization curing process are all important influencing factors. In addition, in the process of curing concrete by carbon dioxide mineralization, in order to increase CO₂The diffusion effect of (2) enters the inside of a test piece, pressure maintenance needs to be increased in a closed mode, and large-area cracking of a product is often caused due to improper pressure control.

Disclosure of Invention

The invention aims to solve the technical problem of providing a method for storing carbon dioxide by mineralizing concrete with inorganic solid waste ceramsite, and overcoming the defects that in the prior art, carbon dioxide is high in adsorption, analysis and storage cost, and the existing concrete curing by using carbon dioxide has more influence factors, is difficult to control, and is easy to cause large-area cracking and other unqualified concrete blocks.

The technical scheme for solving the technical problems is as follows: a method for storing carbon dioxide in inorganic solid waste ceramsite mineralized concrete comprises the following steps of (1) preparing inorganic solid waste ceramsite filter balls;

preparing an aminated ceramsite filter ball, and impregnating the inorganic solid waste ceramsite filter ball obtained in the step (1) with an amino acid salt solution and/or an amino ionic liquid;

fully absorbing carbon dioxide by using the aminated ceramsite filter ball to obtain an adsorption saturated carbon dioxide filter ball;

and (4) mixing and uniformly stirring the adsorption saturated carbon dioxide filter ball prepared in the step (3) and the cement mortar concrete to prepare the mineralized lightweight concrete test piece. Preferably, the cement mortar concrete comprises cement, construction waste reclaimed sand, common sand water, anti-cracking fiber and a water reducing agent, wherein the mass volume ratio of the cement to the adsorption saturated carbon dioxide filter ball is 300-800kg/m³。

The conventional main physical adsorption or Van der Waals force acts among all molecules, but is weak, so that carbon dioxide is easily desorbed under the condition of certain temperature, pressure or water pressure.

The invention has the beneficial effects that: the invention introduces high-concentration CO such as factory chimney gas and the like after treating inorganic solid waste ceramsite filter balls with amino acid salt solution and/or amino ionic liquid₂After absorbing saturated carbon dioxide in the environment, directly adding the carbon dioxide serving as an additive into concrete, and discharging CO in the cement mixing water, hydration heat or steam curing process₂The rapid mineralization maintenance cementing material is converted into the main component calcium carbonate of the concrete, and is relatively firm to the conversion and the sealing of the carbon dioxide.

The inorganic solid waste ceramsite filtering ball can be inorganic solid waste materials such as fly ash, slag micro powder, water granulated slag, blast furnace slag, mineral mud, red mud and the like, and the fly ash can be prepared into a non-fired fly ash ceramsite filtering ball.

The invention utilizes the solid waste produced in the factory as much as possible, and reduces the transportation and raw material cost. For example: fly ash is close to CO₂The emission source, such as a thermal power plant, really realizes the aim of treating the pollution at any place, and the problem of high-value utilization of the fly ash is well solved.

By utilizing the method disclosed by the invention, through full life cycle analysis and energy and mass balance analysis, a negative carbon index 893.79kg can be generated by capturing 1000 tons of carbon dioxide, and the balance of mass, carbon and energy is achieved. The positive income can be 1300-1600 yuan per ton of carbon dioxide, and the method is completely suitable for large-scale, industrialized and commercialized market promotion. About 70 million parts of concrete is consumed in China one year, 2 billion cubic meters of steam-cured aerated concrete is used, 500kg of the capture agent is added in each cubic meter, 5 million tons of sealed carbon dioxide can be captured and stored in the market capacity one year, and 45 million tons of solid waste can be processed.

On the basis of the technical scheme, the invention can be further improved as follows.

The invention relates to a method for sealing and storing carbon dioxide by using inorganic solid waste ceramsite mineralized concrete, which is characterized in that the inorganic solid waste ceramsite filter ball is a fly ash ceramsite filter ball.

The invention relates to a method for storing carbon dioxide in inorganic solid waste ceramsite mineralized concrete, which comprises the following raw materials in parts by weight: 1500 parts of fly ash, 450 parts of slag cement 350-.

Furthermore, the fly ash ceramsite filter ball comprises the following raw materials in parts by weight: 1500 parts of fly ash, 400 parts of slag cement, 400 parts of clay, 500 parts of quicklime, 100 parts of mineral soil, 60 parts of desulfurized gypsum, 180 parts of foaming agent, 100 parts of cationic interface modification modifier and 421 parts of water.

The invention relates to a method for sealing and storing carbon dioxide in inorganic solid waste ceramsite mineralized concrete, which comprises the following steps:

1) dividing the cationic interface modification modifier and water into two parts,

2) grinding the fly ash, slag cement, clay, quicklime, mineral soil and desulfurized gypsum, respectively adding a first part of water and a first part of cationic interface modification modifier during grinding, grinding fine powder and sieving to obtain superfine powder;

3) and adding a second part of water and a second part of cation interface modification modifier into the ultrafine powder, uniformly mixing, adding a foaming agent to prepare a filter ball raw material, aging the filter ball raw material, transferring the filter ball raw material into a drying chamber, drying, and naturally cooling to prepare the fly ash ceramsite filter ball.

The grinding can be carried out in a ball milling mode, wherein the first part of water and the first part of cation interface modification modifier are both 50% of the total amount of the water and the cation interface modification modifier, the ground powder is sieved by a 15-micron sieve, the filter ball raw material is aged, namely, the filter ball raw material is placed at room temperature for 2 hours, then the filter ball raw material is moved into a drying chamber, heated and dried at 120 ℃ for 3-4 hours, and then naturally cooled for 0.5 hour, so that the ceramsite filter ball with the particle size of 1-4mm is prepared.

Fly ash, slag cement, clay, quicklime, mineral soil and desulfurized gypsum are ground into superfine powder, and the superfine powder generally comprises micron-sized (1-30um), submicron-sized (0.1-1um) and nano-sized (1-100nm) particles. Since the particle size of the ultrafine powder is small, the specific surface area is correspondingly increased, and the surface energy is also increased. Along with the size of the particle size, the surface atomic number of the particle is multiplied, so that the particle has stronger surface activity and catalytic property, can obviously accelerate the reaction speed when participating in the reaction, and has good chemical reactivity.

During the process of loading ionic liquid or amino acid salt solution, the fly ash ceramsite filter ball containing the cationic surfactant can generate corresponding pore channels due to the loss of part of the cationic surfactant, and after the fly ash ceramsite filter ball is loaded with the ionic liquid or the amino acid salt solution, the fly ash ceramsite filter ball can react with CO₂Compared with the fly ash ceramsite filter ball without the cationic surfactant, the adsorption performance of the fly ash ceramsite filter ball is improved by 2-3 times after the fly ash ceramsite filter ball is loaded with the ionic liquid or the amino acid salt solution; the cationic surfactant micelles of the fly ash ceramsite filter ball adopting the cationic surfactant form a microenvironment, and the molecules of the ionic liquid or the amino acid salt solution can be inserted into the micelles to avoid agglomeration, so that the dispersibility of the ionic liquid or the amino acid salt solution is improved, and the ionic liquid is CO₂Exposing more active sites.

The method for sealing carbon dioxide by using inorganic solid waste ceramsite mineralized concrete further comprises the following steps that the mineral soil is mainly one or more of clay minerals in shale, kaolinite, montmorillonite, illite and illite mixed layers;

the cation interface modification modifier is one or more of dodecyl dimethyl benzyl ammonium chloride, bis-decyl dimethyl ammonium chloride, octyl decyl dimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide.

The cationic surfactant is used for efficiently adsorbing CO₂The organic amine is also a better organic amine dispersion medium. The cation of the cationic surfactant acts with siloxy anion (≡ SiO-) in a silicon-based framework by virtue of electrostatic force, and outside the interface region, counter ions of micelles of the cationic surfactant can form an ion diffusion layer, so that when an amino acid salt or polyamine ionic liquid is loaded on the fly ash ceramsite filter ball, the electrostatic force between the counter ions of the micelles of the cationic surfactant and cations of the ionic liquid, and between the cations of the surfactant and anions of the ionic liquid can cause redistribution of charges on the ionic liquid, and further cause weakening of interaction between anions and cations. The existence of the cationic surfactant weakens the interaction between cations and anions of the ionic liquid and also causes-NH in the ionic liquid₂Increase in upper electron cloud density, thus CO₂Can act with the catalyst more easily, and can remarkably increase the CO adsorption of the catalyst₂And (4) performance.

The invention provides the method for storing carbon dioxide in the inorganic solid waste ceramsite mineralized concrete, and further, the amino acid in the amino acid salt solution in the step (2) is one or more than two of alanine, glycine, sarcosine, L-ornithine, arginine and L-proline;

the cement mortar concrete in the step (4) comprises cement, construction waste reclaimed sand, common sand water, anti-crack fibers and a water reducing agent, wherein the mass volume ratio of the cement to the adsorption saturated carbon dioxide filter ball is 300-800kg/m³。

The method for storing carbon dioxide in inorganic solid waste ceramsite mineralized concrete further comprises the step (2), wherein the amine-based ionic liquid is amine-based plasma dissolved in absolute ethyl alcohol, and the amine-based plasma is 1-aminopropyl-3-methylimidazole glycinate ([ APMim ] [ Gly ]), 1-aminopropyl-3-methylimidazole alaninate ([ APMim ] [ Ala ]), 1-aminopropyl-3-methylimidazole lysinate ([ APMim ] [ Lys ]), tetramethylammonium glycine ([ N1111] [ Gly ]), tetramethylammonium lysine ([ N1111] ] [ Lys ]), 1-aminopropyl-3-methylimidazole hexafluorophosphate ([ NH2p-mim ] [ PF6]), ethylenediamine tetra-fluoroborate ([ EDTAH ] [ BF4]), diethylenetriamine tetrafluoroborate ([ DETDET ] [ BF4]), or ammonium hydroxide, One or more of triethylene tetramine tetrafluoroborate ([ TETAH ] [ BF4]) and tetraethylene pentamine tetrafluoroborate ([ TEPAH ] [ BF4 ]).

The amino acid salt solution is obtained by reacting amino acid waste liquid generated in industrial amino acid production or amino acid solution with organic alkali or inorganic alkali. The amino acid waste liquid is amino acid waste liquid formed by leftovers generated in the industrial production of amino acid. The amino acid waste liquid or amino acid solution and alkali (organic alkali or inorganic alkali) can be mixed according to the molar ratio of amino acid to organic alkali or inorganic alkali of 1: 1 reacting for 60min to prepare amino acid salt solution.

The mass volume concentration of the amino acid salt solution adopted by the invention can be selected to be 50-500 g/L.

The invention provides a method for sealing carbon dioxide in inorganic solid waste ceramsite mineralized concrete, and further, the inorganic base comprises potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and trisodium phosphate; the organic base comprises one or more than two of Monoethanolamine (MEA), Diethanolamine (DEA), Triethanolamine (TEA), 3-methylaminopropylamine, N-Methyldiethanolamine (MDEA), Piperazine (PZ), Tetraethylenepentamine (TEPA), Diethylenetriamine (DETA), triethylenetetramine (TETA) and 2-amino-2-methyl-1-propanolamine (AMP).

The method for sealing and storing carbon dioxide by inorganic solid waste ceramsite mineralized concrete further comprises the steps of dissolving the amino group plasmas into absolute ethyl alcohol, wherein the mass volume concentration of the amino group plasmas is 12-13g/L, and magnetically stirring the amino group plasmas for 8-15min at room temperature under the atmosphere of nitrogen to obtain the amino group ionic liquid.

Adopting an amino acid salt solution and/or an amino ionic liquid to dip the inorganic solid waste ceramsite filter ball prepared in the step (1), wherein the mass ratio of the amino acid salt solution or the amino ionic liquid to the inorganic solid waste ceramsite filter ball is (15-25): 1. and the more preferable ratio is 20:1, stirring is continuously carried out for 2 to 4 hours, the preferable ratio is 3 hours, drying and evaporation are carried out, and the carbon dioxide trapping agent of the amination ceramsite filter ball is obtained.

The amino acid salt solution and the amino ion of the present inventionIn order to overcome the defects of high viscosity and low absorption rate, an amino acid salt solution or an amino ionic liquid is loaded on a fly ash ceramsite filter ball, the amino acid salt solution or the amino ionic liquid is well dispersed on a porous material, and the amino ionic liquid or the amino acid salt solution and CO are added₂The contact area of the amino ionic liquid overcomes the defect of high viscosity of the amino ionic liquid, not only improves the reaction rate, but also reduces the dosage of the ionic liquid. And the amino acid salt solution or the amine ionic liquid is loaded on the fly ash ceramsite filter ball, and the fly ash ceramsite filter ball is macroscopically formed into a solid phase, so that the recovery is convenient, the absorption time is favorably shortened, the mass transfer process is promoted, and the advantages of large-scale industrial application are achieved.

The carbon dioxide mineralized concrete is prepared by using concrete cementing material and alkaline components in concrete aggregate, including unhydrated dicalcium silicate and tricalcium silicate, hydration products of calcium hydroxide and C-S-H gel and the like, to perform carbonation reaction so as to realize CO₂And reduce the overall CO of the cement building industry over the life cycle₂And (4) discharging, namely a technology for mineralizing and curing concrete by using carbon dioxide. The technology mainly comprises the following chemical reactions: carbon dioxide dissolves in water to produce carbonic acid, as shown in the following reaction scheme:

(ii) a The resulting carbonic acid reacts with the partially hydrated product calcium hydroxide to form calcium carbonate according to the following reaction scheme:

(ii) a The calcium silicate hydrate is gradually converted into calcium carbonate, and the final mineralization reaction product is calcium carbonate, which has the following reaction formula:

。

based on the presence of CO₂In the process of mineralization and maintenance, CO₂Can only enter the interior of a test piece through diffusion, the diffusion of the material is greatly influenced by the water content and the porosity in the cement-based material, and the material can be used for CO₂Has a limited fixing effect. The dynamic research on the carbon dioxide mineralization curing concrete shows that the mineralization curing process of the solid concrete block is mainly influenced by CO₂Gas diffusion and product layer diffusion control, and the essence of increasing gas pressure during curing is to increase CO₂Gas diffusion capacity, thereby improving the mineralization and maintenance degree of the test piece. On the other hand, the internal porosity of the concrete before curing is improved by doping mineral admixtures such as fly ash, mineral powder and the like, and CO is added₂Gas channeling to enhance CO₂The diffusion process also enables an increase in the degree of mineralisation maintenance. To sum up, enhance CO₂Diffusion capacity, increase of CO₂The methods such as a diffusion channel and the like all have positive effects on improving the carbon dioxide maintenance effect. For further improving CO content of cement-based materials₂The fixation rate of (c).

The invention adopts the carbon dioxide catching agent of the aminated ceramsite filter ball to catch CO in a factory₂Catching, directly taking the saturated fly ash microporous balls as an additive to be added into concrete, and adding CO escaped from the concrete in the cement hydration heat or steam curing process₂The rapid mineralization and maintenance of the gelled material is converted into the main component calcium carbonate of the concrete. The mineralization desorption is a low-energy-consumption regeneration method without heating, and the raw materials mainly adopt natural ore rich in calcium oxide (CaO) and alkaline solid wastes such as steel slag, coal ash and the like; in particular, the cement (concrete) contains calcium oxide per se, and the main product of the cement in the hydration process is Ca (OH)₂Can be directly used for mineralizing, desorbing and absorbing the carbon dioxide which is saturated by the amination fly ash ceramsite filtering ball; after portland cement (concrete) is mixed with water, four main clinker minerals react with water, and the hydration reaction is as follows:

(1) hydration of tricalcium silicate

The hydration reaction of tricalcium silicate at normal temperature generates calcium silicate hydrate (C-S-H gel) and calcium hydroxide, and the reaction formula is

。

(2) Hydration of dicalcium silicate

The hydration of beta-C2S is similar to C3S, and the reaction formula is

。

(3) Hydration of tricalcium aluminate

The tricalcium aluminate hydrates rapidly and releases a large amount of heat, the composition and the structure of the hydration product are greatly influenced by the concentration and the temperature of liquid-phase CaO, the metastable hydrated calcium aluminate is generated first and is finally converted into the garnet (C)₃AH₆）。

In the presence of gypsum, C₃The final product of hydration A is related to the amount of gypsum added, the initial calcium sulphoaluminate hydrate of the trisulphide type, called ettringite for short, usually expressed by AFt, if the gypsum is at C₃If A is exhausted before complete hydration, ettringite and C will be present₃The A function is converted into the monosulfuric hydrated calcium sulphoaluminate (AFm).

(4) Hydration of iron phase solid solution

The iron phase solid solution in the cement clinker can be C₄AF is representative. Its hydration rate ratio C₃A is slightly slow, has low heat of hydration, and does not cause rapid setting even if hydrated alone. Hydration reaction thereof and products thereof with C₃A is very similar. The mineralization and desorption of the carbon dioxide which is saturated and adsorbed by the aminated fly ash ceramsite filter ball are as follows:

。

CO based on aminated ceramsite filter balls₂The mechanical property of the recycled concrete can be improved by the mineralizing and curing mode of the catcher. The waste utilization rate can be improved by carrying out carbonization curing on the concrete doped with the recycled aggregate, and the fire resistance and the strength of the concrete are enhanced. Before carbonization and maintenance, the drying pretreatment of the concrete containing the recycled aggregate can obviously increase CO₂The mineralization curing degree is higher than that of 6h autoclaved curing, and the strength can be higher after 2h carbonization curing. CO to recycled concrete₂Mineralization maintenance can be regarded as a carbon sequestration process, CO₂The mineralization curing can improve the early strength of the concrete and reduce the drying shrinkage of the concrete. Rapid CO treatment of concrete blocks₂Mineralized maintenance, the building blocks containing 13% of cement can absorb 24% of CO of the cement mass₂If a CO2 mineralization curing system is adopted in the production of concrete prefabricated parts such as building blocks, bricks and the like, the carbon fixation rate of the products is kept at 24% of the cement quality, and then the carbon emission of the cement industry can be reduced by 2.5%. Thus using CO₂The mineralizing curing mode can utilize concrete to absorb CO₂Reduction of carbon emissions, and on the other hand CO₂The reaction with cement hydration products can promote early hydration and improve early strength, and the generated products can optimize the pore structure, thereby improving the durability of concrete.

Compared with the traditional maintenance mode, the CO of the aminated ceramsite filter ball₂The time of the catching agent curing technology is shorter, the achieved effect is better, and the method is a better concrete curing method for assisting the traditional curing method. Traditional steam curing concrete energy consumption is high, and a ordinary concrete block steam curing needs about 2300kJ of energy, and light concrete block steam curing also needs about 2500kJ of energy, and the crack that too big temperature gradient arouses is prevented to control temperature rise and cooling rate in the maintenance process moreover. Table 1 shows natural curing, steam curing, CO₂And (3) comparing parameters of the mineralization curing and the amination modified fly ash filter material ball catching agent curing process.

TABLE 1 Natural curing, steam curing, CO₂Technological parameters of pressure curing and amination modified fly ash filter material ball curing

Detailed Description

The principles and features of this invention are described below in conjunction with embodiments, which are included to explain the invention and not to limit the scope of the invention.

The saturated carbon dioxide adsorption filter ball can adopt a carbon dioxide trapping agent fixed bed absorption tower device provided with amination fly ash ceramsite filter balls, factory chimney gas is introduced into the carbon dioxide trapping agent fixed bed absorption tower device provided with the fly ash ceramsite filter balls, a multi-stage fixed bed is arranged in the tower, the ceramsite filter balls are arranged on the fixed bed, and the bottom of each fixed bed is provided with a layer of porous plate. After the flue gas passes through the porous plate, the airflow distribution is more uniform, meanwhile, the fixed bed is an automatic turning bed, the aminated fly ash ceramsite filter ball catching agent after adsorption saturation falls to the bottom of the absorption tower through the automatic turning bed under the control system, and the aminated fly ash ceramsite filter ball after adsorption saturation is obtained through the conveying system.

After the conventional dust removal and desulfurization treatment, the factory flue gas enters the lower part of the pretreatment tower through a chimney via a control valve and a pressurization induced draft fan; the flue gas goes upward to pass through the fixed bed and is fully contacted with the aminated fly ash ceramsite filter ball catching agent arranged on the fixed bed; according to CO in the flue gas₂The content and the flow rate of the aminated fly ash ceramsite filter ball catching agent are selected, the number of layers of the fixed bed is selected, and CO in the flue gas₂The temperature may preferably be in the range of 20-130 deg.C and the pressure is preferably 1-atm. At this time, CO in the flue gas₂The gas and the amination fly ash ceramsite filter ball catching agent are in full reverse contact in the tower, the reaction is rapidly carried out and the catching agent is absorbed, the residual flue gas continuously flows upwards, the first mode is that the fog drops are removed by the defogging device, and the clean flue gas is directly discharged into the atmosphere, and the first mode is suitable for the projects that the concentration of carbon dioxide in the flue gas is low and the carbon emission index requirement of a factory is met; the second mode is that the upper part of the absorption tower enters the lower part of the pretreatment tower through a circulating system consisting of a control valve, a pressurization induced draft fan and a mass and volume flow meter, and then enters the fixed bed system of the absorption tower again for circularly capturing carbon dioxide according to the above, and the second mode is suitable for projects with higher carbon dioxide concentration in flue gas and factory carbon emission indexes or carbon sink requirements; the aminated fly ash ceramsite filter ball catching agent after being saturated in adsorption automatically turns over the bed and falls to the bottom of the absorption tower under a control systemAnd finally, obtaining the aminated fly ash ceramsite filter ball after saturated adsorption. Determining the capture amount of carbon dioxide and determining the mass ratio of the capture amount of carbon dioxide to the capture agent of the aminated fly ash ceramsite filter ball and various parameter indexes through mass flow meters and mass and volume differences of inlets and outlets of volume flow meters.

The cement mortar concrete comprises cement, construction waste reclaimed sand, common sand water, anti-cracking fibers and a water reducing agent, the concrete formula of the novel fast-hardening self-curing lightweight concrete can adopt the weight part and volume proportion relation shown in table 2, corresponding raw materials are weighed according to the formula shown in table 2, and the raw materials are added into a concrete mixer to be uniformly mixed. The formula of the rapid self-curing hollow block can adopt the following weight part and volume proportion relation in table 3, a plurality of groups of blocks are manufactured by a block forming machine in a block manufacturing factory according to the selected mixing proportion, and a performance test is carried out after curing; the external dimension of the building block is 390mm multiplied by 190mm, the wall thickness is 30mm, the rib thickness is 25mm, and the hollow rate is 55%.

TABLE 2 fast hardening self-curing novel lightweight concrete formulation

TABLE 3 quick self-curing hollow block formulation

Detection of mechanical properties of mineralized concrete

1. Manufacturing a mineralized light concrete test piece: according to the formula and the process of the novel rapid hardening self-curing lightweight concrete, the concrete is molded into a cube test block with the size of 100mm multiplied by 100mm according to the standard;

a cylindrical neat paste test piece with the size of ∅ 27.5.5 mm multiplied by 50mm is molded according to the formula design of the quick self-curing hollow block.

2. And setting CK1 as a filter ball which adsorbs saturated carbon dioxide in the formula and is replaced by a filter ball which does not adsorb saturated carbon dioxide, performing natural curing, performing conventional steam pressurization carbon dioxide curing on CK2, and setting the formula of the filter ball which adsorbs saturated carbon dioxide in the formula in an experimental group under the same other conditions.

The (CK 1) and (example set) test blocks were placed at 20 ± 2 ℃ and pre-cured in a standard curing chamber (temperature 20 ± 2 ℃, humidity = 60%) for 24h demolding. And (3) maintaining the mixture in a standard maintenance room (the temperature is 20 +/-2 ℃, and the humidity is more than 95%) until the mixture reaches the age of 3d, 7d and 28d, and performing mechanical property tests. And (3) placing the test piece (CK2) in a carbonization box for carbonization and maintenance, keeping the temperature in the carbonization box at 20 +/-2 ℃, and changing the humidity and the carbonization and maintenance time. And placing the test piece after carbonization and maintenance in a standard maintenance room (the temperature is 20 +/-2 ℃, and the humidity is more than 95%) and maintaining the test piece to the age of 3d, 7d and 28d for mechanical property test.

3. Mechanical testing

The mechanical property of the concrete is mainly the cubic compressive strength of a test piece, and the test process is carried out according to GB/T50081-2002< < test method standard of the mechanical property of the common concrete >.

4. Testing of the degree of carbonation

Preparing test pieces according to the material mixing proportion design, and adopting respective CO₂And (5) maintaining the degree. The carbonization depth is judged by measuring the content of calcium carbonate by a carbonate titration method.

The carbonate titration method determines the calcium carbonate content to judge the carbonization depth basic principle:

the initial volume V1 (ml) and the post-test volume V2 (ml) of the trachea were read, and CO was calculated according to the formula (4.5)₂The volume V, then the calcium carbonate content mCaCO of the 0.5g sample powder was calculated by combining the reaction equation (4.4) and the equations (4.5) to (4.7)₃And the calcium carbonate content wCaCO in the wafer₃The carbonization degree is expressed by the proportion of calcium carbonate.

4.1 slicing and drying

The carbonized test piece was cut into circular slices having a diameter of 27.5mm with a nearly uniform thickness by layers, the thickness of each slice was measured 3 times with a digital caliper, and the average value was taken (the depth of each disc was the sum of the thickness of the preceding disc and one-half of the thickness of the preceding disc). The cut discs were placed in a vacuum oven at 105 ℃ to remove free water, dried for 12h, and then weighed out for each disc.

4.2 carbonate content determination

And grinding the dried test piece, and passing through a square-hole sieve of 0.16 mm. 0.5g +/-0.001 g of powder is weighed by an electronic analytical balance, and the carbonate content of each test piece is measured by a carbonate quantitative determination device.

Example 1

1. Preparation of fly ash ceramsite filter ball

The raw materials were weighed according to the ratio in Table 4, superfinely powdered by Raymond mill, ground

Respectively adding 210.5kg of water and 50kg of hexadecyl trimethyl ammonium bromide in the process, grinding the mixture into fine powder, sieving the fine powder by a 15-micron sieve, adding the rest 50kg of hexadecyl trimethyl ammonium bromide and 210.5kg of water, uniformly mixing, adding a foaming agent to form balls, aging the filter ball raw materials, standing at room temperature for 2 hours, transferring the filter ball raw materials into a drying chamber, heating and drying at 120 ℃ for 3 hours, and naturally cooling for 0.5 hour to obtain the fly ash ceramsite filter ball with the particle size of 1-4 mm.

TABLE 4 formulation of fly ash ceramsite filter ball raw material

2. Preparing aminated haydite filter ball

Tetramethylammonium glycine ([ N1111] s][Gly])1250kg of the extract is dissolved in 100m of absolute ethyl alcohol³Magnetically stirring the mixture at room temperature for 10mim under a nitrogen atmosphere to obtain tetramethylammonium glycine ([ N1111] of][Gly]) Ionic liquid ethanol solution;

taking 68800kg of tetramethylammonium glycine ([ N1111] [ Gly ]) ionic liquid ethanol solution and 3440kg of fly ash ceramsite filter ball, stirring for 3h under nitrogen at room temperature by magnetic stirring, drying and evaporating to obtain the carbon dioxide trapping agent of the tetramethylammonium glycine ([ N1111] [ Gly ]) aminated fly ash ceramsite filter ball.

3. Preparation of filter ball for adsorbing saturated carbon dioxide

The carbon dioxide trapping agent for the tetramethylammonium glycine ([ N1111] [ Gly ]) aminated fly ash ceramsite filter ball is used for absorbing saturated carbon dioxide, the fixed bed absorption tower device is provided with an upper fixed bed and a lower fixed bed, each fixed bed is provided with 500kg of the tetramethylammonium glycine ([ N1111] [ Gly ]) aminated fly ash ceramsite filter ball carbon dioxide trapping agent, and the system operation detection obtains the aminated fly ash ceramsite filter ball trapping agent saturated in absorbed saturated carbon dioxide.

4. The aminated fly ash ceramsite filter ball catching agent mineralized concrete after absorbing saturated carbon dioxide is formed into a cube test block with the size of 100mm multiplied by 100mm according to the formula shown in the table 5.

TABLE 5 formulation of fast hardening self-curing novel lightweight concrete

Example 1 results of testing the carbonization degree of the concrete sections prepared and cured by the methods of adsorbing saturated carbon dioxide filter balls and CK1 and CK2 are shown in Table 6.

TABLE 6 maintenance test results of the experimental group and the control group (CK 1, CK2) of example 1

Example 2

1. Preparation of fly ash ceramsite filter ball

Weighing various raw materials according to the proportion in the table 7, carrying out ultrafine pulverization on the materials by adopting a Raymond mill, respectively adding 210.5kg of water and 50kg of tetradecyl trimethyl ammonium bromide during the grinding process, sieving the ground powder by a 15-micron sieve, then adding the rest 50kg of tetradecyl trimethyl ammonium bromide and 210.5kg of water, uniformly mixing, then adding a foaming agent to form balls, aging the raw materials of the filter balls, standing for 2h at room temperature, then moving the raw materials into a drying chamber, heating and drying for 3h at 120 ℃, and then naturally cooling for 0.5h to obtain the ceramsite filter balls with the particle size of 3 mm.

TABLE 7 formulation of fly ash ceramsite filter ball raw material

2. Preparing aminated haydite filter ball

1L (2 mol) of amino acid waste liquid generated in industrial production of amino acid is adopted to react with 2mol of potassium hydroxide for 60min to prepare 318g/L of potassium amino acid solution; 1L (2 mol) of amino acid waste liquid and 2mol of ethanolamine are adopted to react for 60min to prepare 330g/L of amino acid amine solution; two amino acid salt solutions by mass 1: 1 configuration impregnation liquid.

68800kg of amino acid salt dipping solution and 3440kg of fly ash (solid waste) ceramsite filter ball are taken, stirred for 3 hours at room temperature under the condition of nitrogen by magnetic stirring, dried and evaporated to obtain the carbon dioxide trapping agent of the amino acid salt aminated fly ash ceramsite filter ball.

3. Preparation of filter ball for adsorbing saturated carbon dioxide

The carbon dioxide trapping agent of the amino acid salt aminated fly ash ceramsite filter ball is used for absorbing saturated carbon dioxide by adopting the fixed bed absorption tower device, an upper fixed bed and a lower fixed bed are arranged, and each fixed bed is provided with 500kg of the carbon dioxide trapping agent of the amino acid salt aminated fly ash ceramsite filter ball.

4. The prescription of the aminated fly ash ceramsite filter ball trapping agent mineralized concrete after carbon dioxide saturation absorption is shown in the table 8, and the concrete is molded into cube test blocks of 100mm multiplied by 100mm according to the prescription.

TABLE 8 formulation of fast-hardening self-curing lightweight concrete

The results of testing the carbonization degree of the concrete sections prepared and cured by the methods of example 2, CK1 and CK2 and the filter balls adsorbing saturated carbon dioxide are shown in Table 9.

TABLE 9 maintenance test results of the experimental group and the control group (CK 1, CK2) of example 2

Example 3

1. Preparation of fly ash ceramsite filter ball

Weighing various raw materials according to the proportion in the table 10, weighing various inorganic materials, performing ultrafine pulverization on the materials by adopting a Raymond mill, respectively adding 210.5kg of water, 25kg of hexadecyl trimethyl ammonium bromide and 25kg of dodecyl dimethyl benzyl ammonium chloride in the grinding process, grinding the materials into fine powder, sieving the fine powder by a 15-micron sieve, then adding the rest 25kg of hexadecyl trimethyl ammonium bromide, 25kg of dodecyl dimethyl benzyl ammonium chloride and 210.5kg of water, uniformly mixing, then adding a foaming agent to form balls, aging the raw materials of the filter balls, standing the materials at room temperature for 2 hours, then moving the materials into a drying chamber, heating and drying the materials at 120 ℃ for 3 hours, and naturally cooling the materials for 0.5 hour to prepare the ceramsite filter balls with the particle size of 1-4 mm.

TABLE 10 formulation of fly ash ceramsite filter ball raw material

2. Preparing aminated haydite filter ball

350kg of ethylenediamine tetra-fluoroborate ([ EDTAH ] [ BF4]), 300kg of diethylenetriamine tetrafluoroborate ([ DETAH ] [ BF4]), 300kg of triethylenetetramine tetrafluoroborate ([ TETAH ] [ BF4]), 300kg of tetraethylenepentamine tetrafluoroborate ([ TEPAH ] [ BF4]) are dissolved in 100m3 of absolute ethyl alcohol, and the mixture is magnetically stirred for 10mim at room temperature in a nitrogen atmosphere to obtain a composite organic amine salt ionic liquid ethanol solution;

68800kg of composite organic amine salt ionic liquid ethanol solution and 3440kg of fly ash (solid waste) ceramsite filter ball are obtained, the mixture is magnetically stirred at room temperature under nitrogen for continuously stirring for 3 hours, and the mixture is dried and evaporated to obtain the composite organic amine salt ionic liquid ethanol solution aminated fly ash ceramsite filter ball carbon dioxide capture agent.

3. Preparation of filter ball for adsorbing saturated carbon dioxide

The carbon dioxide trapping agent for the composite organic amine salt ionic liquid ethanol solution aminated fly ash ceramsite filter ball adopts the fixed bed absorption tower device described above, an upper fixed bed and a lower fixed bed are arranged, and each fixed bed is provided with 500kg of the carbon dioxide trapping agent for the composite organic amine salt ionic liquid ethanol solution aminated fly ash ceramsite filter ball.

4. The carbon dioxide trapping agent mineralized concrete of the composite organic amine salt ionic liquid ethanol solution aminated fly ash ceramsite filter ball has the formula shown in table 11, and the concrete is formed into a cube test block with the size of 100mm multiplied by 100mm according to the formula.

TABLE 11 formulation of novel fast-hardening self-curing lightweight concrete

Example 3 test results of the carbonization degree of the concrete sections prepared and cured by the adsorption saturated carbon dioxide filter ball and the methods of CK1 and CK2 are shown in Table 12.

TABLE 12 maintenance test results of the experimental group and the control group (CK 1, CK2) of example 3

Example 4

1. Preparation of fly ash ceramsite filter ball

Weighing various raw materials according to the proportion shown in Table 13, carrying out ultrafine pulverization on the materials by adopting a Raymond mill, respectively adding 210.5kg of water and 12.5kg of octyl sunflower dimethyl ammonium chloride, 12.5kg of hexadecyl trimethyl ammonium bromide, 12.5kg of tetradecyl trimethyl ammonium bromide and 12.5kg of octadecyl trimethyl ammonium bromide during the grinding process, grinding the materials into fine powder, sieving the fine powder by a sieve of 15 mu m, then adding the rest of 12.5kg of octyl sunflower dimethyl ammonium chloride, 12.5kg of hexadecyl trimethyl ammonium bromide, 12.5kg of tetradecyl trimethyl ammonium bromide, 12.5kg of octadecyl trimethyl ammonium bromide and 210.5kg of water, uniformly mixing, then adding a foaming agent into the mixture to form a ball, aging a raw material of the filter ball, placing the mixture at room temperature for 2 hours, then transferring the mixture into a drying chamber, heating and drying the mixture at the temperature of 120 ℃ for 3 hours, and naturally cooling the mixture for 0.5 hour to obtain the ceramsite with the particle size of 1-4 mm.

TABLE 13 formulation of raw materials for haydite filter balls made from fly ash

2. Preparing aminated haydite filter ball

1L (2 mol) of amino acid waste liquid generated in industrial production of amino acid is adopted to react with 2mol of potassium hydroxide for 60min to prepare 318g/L of amino acid potassium solution; 1L (2 mol) of amino acid waste liquid generated in industrial production of amino acid is adopted to react with 2mol of ethanolamine for 60min to prepare 330g/L of amino acid amine solution; two amino acid salt solutions by mass 1: 1 preparing a composite amino acid salt impregnation liquid.

400kg of 1-aminopropyl-3-methylimidazolium glycinate ([ APMim ] [ Gly ]), 450kg of 1-aminopropyl-3-methylimidazolium alaninate ([ APMim ] [ Ala ]), and 400kg of 1-aminopropyl-3-methylimidazolium lysine ([ APMim ] [ Lys ]) were dissolved in 100m3 of absolute ethanol, and the mixture was magnetically stirred at room temperature for 10min under a nitrogen atmosphere to obtain an ionic liquid ethanol solution of the complex amino acid salt.

And taking 34400kg of composite amino acid salt ionic liquid ethanol solution, 34400kg of composite amino acid salt dipping liquid and 3440kg of fly ash (solid waste) ceramsite filter ball, magnetically stirring at room temperature under nitrogen for continuously stirring for 3 hours, drying and evaporating to obtain the carbon dioxide trapping agent for the aminated fly ash ceramsite filter ball.

3. Preparation of filter ball for adsorbing saturated carbon dioxide

The carbon dioxide trapping agent for the aminated fly ash ceramsite filter ball of the composite organic amine salt ionic liquid ethanol solution adopts the fixed bed absorption tower device described above, an upper fixed bed and a lower fixed bed are arranged, and each fixed bed is provided with 500kg of the carbon dioxide trapping agent for the aminated fly ash ceramsite filter ball.

4. The carbon dioxide trapping agent mineralized concrete of the aminated fly ash ceramsite filter ball has the formula shown in table 14. According to the formula, the concrete is molded into a cube test block with the size of 100mm multiplied by 100mm according to the standard.

TABLE 14 formulation of novel fast-hardening self-curing lightweight concrete

The results of testing the carbonization degree of the concrete sections prepared and cured by the methods of example 4, CK1 and CK2 and the filter balls adsorbing saturated carbon dioxide are shown in Table 15.

TABLE 15 maintenance test results of the experimental group and the control group (CK 1, CK2) of example 4

Example 5

1. Preparation of fly ash ceramsite filter ball

Weighing various raw materials according to the proportion shown in Table 16, carrying out ultrafine pulverization on the materials by adopting a Raymond mill, respectively adding 210.5kg of water, 25kg of hexadecyl trimethyl ammonium bromide, 15kg of tetradecyl trimethyl ammonium bromide and 10kg of octadecyl trimethyl ammonium bromide in the grinding process, sieving the ground powder by a 15-micron sieve, then adding the rest 25kg of hexadecyl trimethyl ammonium bromide, 15kg of tetradecyl trimethyl ammonium bromide, 10kg of octadecyl trimethyl ammonium bromide and 210.5kg of water, uniformly mixing, then adding a foaming agent to form balls, aging the filter ball raw materials, placing the filter ball raw materials for 2 hours at room temperature, then transferring the filter ball raw materials into a drying chamber, heating and drying the filter ball raw materials for 3 hours at 120 ℃, and then naturally cooling the filter ball raw materials for 0.5 hour to obtain the ceramsite filter ball with the particle size of 1-4 mm.

TABLE 16 formulation of fly ash ceramsite filter ball raw material

2. Preparing aminated haydite filter ball

1-aminopropyl-3-methylimidazolium glycinate ([ APMim ] [ Gly ])312.5kg, 1-aminopropyl-3-methylimidazolium alaninate ([ APMim ] [ Ala ])312.5kg, 1-aminopropyl-3-methylimidazolium lysine ([ APMim ] [ Lys ])312.5kg and 1-aminopropyl-3-methylimidazolium hexafluorophosphate ([ NH2p-mim ] [ PF6])312.5kg were dissolved in anhydrous ethanol 100m3 and magnetically stirred at room temperature for 10min under a nitrogen atmosphere to obtain a complex amino acid salt ionic liquid ethanol solution.

68800kg of composite amino acid salt ionic liquid ethanol solution and 3440kg of fly ash (solid waste) ceramsite filter ball are taken, stirred under magnetic stirring at room temperature for 3 hours under nitrogen, dried and evaporated to obtain the carbon dioxide trapping agent of the aminated fly ash ceramsite filter ball of the composite amino acid salt ionic liquid ethanol solution.

3. Preparation of filter ball for adsorbing saturated carbon dioxide

The carbon dioxide trapping agent for the composite amino acid salt ionic liquid ethanol solution aminated fly ash ceramsite filter ball adopts the fixed bed absorption tower device described above, an upper fixed bed and a lower fixed bed are arranged, and each fixed bed is provided with 500kg of the carbon dioxide trapping agent for the composite amino acid salt ionic liquid ethanol solution aminated fly ash ceramsite filter ball;

4. the carbon dioxide trapping agent for the composite amino acid salt ionic liquid ethanol solution aminated fly ash ceramsite filter ball mineralizes the concrete. The concrete was formed into a cube of 100mm × 100mm × 100mm according to the standard formulation shown in table 17.

TABLE 17 formulation of fast hardening self-curing novel lightweight concrete

The results of the test of the carbonization degree of the concrete sections prepared and cured by the methods of example 5, CK1 and CK2 and saturated carbon dioxide adsorbing filter balls are shown in Table 18.

TABLE 18 maintenance test results of the experimental group and the control group (CK 1, CK2) of example 5

Tables 6, 9, 12, 15 and 18 show that the products of the examples 1 to 5 of the invention have no shrinkage and the 2h compressive strength can reach 16.8mpa, thereby effectively shortening the forming and curing time and reducing the curing equipment and pressure cost.

The performance indexes of the products obtained in the respective steps of examples 1 to 5 above are shown in tables 19 to 23.

TABLE 19 physicochemical indices of the fly ash ceramsite balls in the steps of examples 1 to 5

TABLE 20 Performance index of aminated ceramsite filter ball catcher in examples 1-5

TABLE 21 adsorption of CO by aminated ceramsite filter balls in the procedure of examples 1 to 5₂Performance index

TABLE 22 absorption of CO obtained in examples 1 to 5₂Performance of mineralized light concrete with saturated aminated flyash catcherIndex (I)

TABLE 23 absorbed CO obtained in the procedures of example 1 to example 5₂Performance index of mineralized concrete building block with saturated aminated flyash catcher

The fly ash ceramsite filter balls prepared in the step 1 in the examples 1 to 5 shown in the table 19 are uniform in void distribution and 1-4mm in particle size; table 20 shows the performance indexes of the aminated ceramsite filter balls in the step 2 of examples 1 to 5, and the specific surface area of the aminated ceramsite filter balls can reach 58.31m³(g) adsorption of CO by aminated ceramsite Filter balls of examples 1 to 5 shown in Table 21₂The performance index, the adsorption capacity can be 179.8g/kg, and the adsorption performance is excellent.

The compression strength of 2h can reach more than 16.8, the compression strength of 28d is more than 20mpa when the mineralized lightweight concrete is applied to the saturated carbon dioxide adsorption filter balls in the step 3 in the examples 1 to 5 shown in the table 22, the compression strength of 2h can reach more than 5.5, the compression strength of 28d is more than 5.8mpa when the mineralized lightweight concrete block is applied to the saturated carbon dioxide adsorption filter balls in the step 3 in the examples 1 to 5 shown in the table 23, the normal-temperature curing speed is high, no shrinkage exists, the freeze-thaw quality loss is small, and the product performance meets the performance requirements of the national standard GB/T15229-2002 'lightweight aggregate concrete small hollow block' on compression strength, frost resistance and the like.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims

1. A method for storing carbon dioxide by mineralizing concrete with inorganic solid waste ceramsite is characterized by comprising the following steps of (1) preparing an inorganic solid waste ceramsite filter ball;

the amino ionic liquid is formed by dissolving amino plasma in absolute ethyl alcohol, wherein the amino plasma is one or more than two of 1-aminopropyl-3-methylimidazole glycinate, 1-aminopropyl-3-methylimidazole alanate, 1-aminopropyl-3-methylimidazole lysine salt, tetramethylammonium glycine, tetramethylammonium lysine, 1-aminopropyl-3-methylimidazole hexafluorophosphate, ethylene diamine tetra fluoroborate, diethylenetriamine tetrafluoroborate, triethylene tetramine tetrafluoroborate and tetraethylenepentamine tetrafluoroborate;

soaking the inorganic solid waste ceramsite filter ball in the step (1) by adopting an amino acid salt solution and/or an amino ionic liquid, wherein the mass ratio of the amino acid salt solution and/or the amino ionic liquid to the inorganic solid waste ceramsite filter ball is (15-25): 1.

fully absorbing carbon dioxide by the aminated ceramsite filter ball to obtain an adsorption saturated carbon dioxide filter ball;

and (4) mixing and uniformly stirring the adsorption saturated carbon dioxide filter ball prepared in the step (3) and the cement mortar concrete to prepare the mineralized lightweight concrete test piece.

2. The method for sequestration of carbon dioxide in inorganic solid waste ceramsite mineralized concrete according to claim 1, wherein the inorganic solid waste ceramsite filter ball in step (1) is a fly ash ceramsite filter ball.

3. The method for sequestering carbon dioxide in the inorganic solid waste ceramsite mineralized concrete according to claim 2, wherein the preparation of the fly ash ceramsite filter ball comprises the following raw materials in parts by weight: 1500 parts of fly ash, 450 parts of slag cement 350-.

4. The method for sequestering carbon dioxide in concrete mineralized by inorganic solid waste ceramsite according to claim 3, wherein the fly ash ceramsite filter ball is obtained by the following method:

5. The method for sequestration of carbon dioxide for mineralization of ceramsite concrete with inorganic solid waste according to claim 3, wherein the mineral soil is one or more of clay mineral, kaolinite, montmorillonite, illite and illite mixed layer in shale; the cation interface modification modifier is one or more of dodecyl dimethyl benzyl ammonium chloride, bis-decyl dimethyl ammonium chloride, octyl decyl dimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide.

6. The method for sequestering carbon dioxide in inorganic solid waste ceramsite mineralization concrete according to claim 5, wherein said ceramsite is selected from the group consisting of calcium carbonate,

the amino acid in the amino acid salt solution in the step (2) is one or more than two of alanine, glycine, sarcosine, L-ornithine, arginine and L-proline;

the cement mortar concrete in the step (4) comprises cement, construction waste reclaimed sand, common sand water, anti-crack fibers and a water reducing agent, wherein the mass volume ratio of the cement to the filter ball absorbing saturated carbon dioxide is 300-800kg/m 3.

7. The method for sequestering carbon dioxide in inorganic solid waste ceramsite mineralized concrete according to claim 5, wherein the amino acid salt solution is obtained by reacting an amino acid waste liquid generated in the production of industrial amino acid or an amino acid solution with an organic base or an inorganic base.

8. The method of claim 7, wherein the inorganic base comprises one or more of potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and trisodium phosphate; the organic alkali comprises one or more than two of monoethanolamine, diethanolamine, triethanolamine, 3-methylaminopropylamine, N-methyldiethanolamine, piperazine, tetraethylenepentamine, diethylenetriamine, triethylenetetramine and 2-amino-2-methyl-1-propanolamine.

9. The method for sequestering carbon dioxide in inorganic solid waste ceramsite mineralized concrete according to claim 7, wherein the mass volume concentration of the amino group plasma dissolved in absolute ethyl alcohol is 12-13g/L, and the amino group ionic liquid is obtained by magnetic stirring at room temperature for 8-15min under nitrogen atmosphere.