Method for producing ferrite-aluminate cement using hydrogen energy

Abstract

The application discloses a method for producing ferrite-aluminate cement by using hydrogen energy, and belongs to the field of low-carbon technologies.The method comprises the following steps: calcining raw material powder to obtain clinker, and grinding the clinker, mixed materials and gypsum powder to obtain ferrite-aluminate cement; the raw material calcination fuel is a mixed gas of hydrogen and natural gas; and the recovered carbon dioxide and hydrogen are combined through a high-efficiency catalyst to synthesize methanol, and the prepared methanol is used in the preparation of the high-efficiency catalyst.Hydrogen energy is selected as the core heat source for raw material calcination, compared with traditional fossil fuels, the carbon emission path is fundamentally reduced, and the negative influence of greenhouse gas emission on global climate can be alleviated.In addition, by accurately adjusting the volume ratio of hydrogen and natural gas, the calcination temperature can be finely adjusted.The carbon dioxide in tail gas is recycled and utilized as a key technical link.The carbon dioxide is separated from the complex components in the tail gas in a high-efficiency manner, and the total carbon emission amount is further reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of low-carbon technology, and in particular to a method for producing ferrite-aluminate cement by using hydrogen energy. BACKGROUND

[0002] The raw cement is mainly calcined by fossil fuels such as coal and heavy oil. When these fuels are burned, a large amount of carbon dioxide is inevitably released. The large-scale cement production has a huge impact on the ecological environment due to the continuous high carbon emission, and aggravates the greenhouse effect, which further intensifies the global warming trend. Although the carbon emission of ferrite-aluminate cement production is about 40% lower than that of ordinary cement, the direct emission of the carbon dioxide-rich tail gas into the atmosphere significantly increases the total carbon emission and further deteriorates the environment. Although some technologies attempt to recover the carbon dioxide in the tail gas, the recovery process is complex and inefficient, and the subsequent utilization approach is extremely limited, which cannot form an efficient resource recycling mode. The energy recycling system is seriously lacking in the entire ferrite-aluminate cement production and related chemical processes, and each link is disconnected, resulting in low resource comprehensive utilization rate, resource waste, and restriction on sustainable development of the industry. SUMMARY

[0003] In view of the above-mentioned shortcomings of the prior art, the present application provides a method for producing ferrite-aluminate cement by using hydrogen energy.

[0004] To achieve the above-mentioned purposes, the present application is realized by the following technical solutions:

[0005] The method for producing ferrite-aluminate cement by using hydrogen energy comprises the following steps: mixing calcium raw material, aluminum raw material, iron raw material and sulfur raw material in a mass ratio of 5:2:3:1, ball milling to obtain raw material powder, calcining the raw material powder to obtain clinker, and grinding the clinker, mixed material (mineral slag and fly ash in a mass ratio of 6:4) and gypsum in a mass ratio of 70:25:10 to obtain ferrite-aluminate cement;

[0006] characterized in that the raw material is sent into a hydrogen sintering furnace, hydrogen and natural gas are mixed in a volume ratio of 1:0.4-0.6, and then gradient calcination is performed for 2-3h;

[0007] The carbon dioxide and hydrogen recovered from the hydrogen sintering furnace are passed into a fixed bed reactor provided with a high-efficiency catalyst at a molar ratio of 1:3.5-4, the reaction temperature is controlled at 200-250℃, the pressure is 1-3MPa, and the gas space velocity is 1000-1500 Meanwhile, the prepared methanol is used in the preparation of the high-efficiency catalyst;

[0008] The preparation of the high-efficiency catalyst comprises the following steps:

[0009] S1 dissolution: copper residue and zinc tailings are crushed and immersed in a methanol solution of sulfuric acid, and copper and zinc are leached by heating and pressurizing, and a mixed metal solution and a filter residue with leached metals are obtained by filtration;

[0010] The filter residue is mixed with the calcium raw material at a mass ratio of 3-5%;

[0011] S2 impurity removal: oxygen is introduced into the mixed metal solution, and the reaction is carried out for 30-40 min to make oxidized to , the pH of the solution is adjusted to 3.8-4.2, precipitated in the form of , the stirring speed is controlled at 100-200 r / min to promote the growth of the floc, and the precipitate is removed by centrifugal separation to obtain a copper-zinc mixed solution;

[0012] S3 crystallization: sodium carbonate solution is added dropwise to the copper-zinc mixed solution, and the pH of the solution is adjusted to make and synchronously generate basic carbonate, and a complexing agent citric acid is added, and the Cu-Zn precursor is obtained by aging;

[0013] S4 washing and drying: the precipitate after aging is separated by centrifugation, washed with 50-60°C deionized water for 2-3 times to remove residual and ions, deionized water is added to the last washing at a mass fraction of 1 / 10 of anhydrous ethanol, the surface moisture of the particles is replaced, and hydrogen bond agglomeration in the drying process is reduced; drying at 50-60°C;

[0014] S5 carrier activation: the boron nitride nanosheet is placed in a sodium hydroxide solution, and the surface impurities and oxides are removed by ultrasonic treatment, and the activated boron nitride nanosheet is obtained by washing and drying;

[0015] S6 precursor-carrier composite: carboxymethyl cellulose with a mass fraction of 2-3% is added to the Cu-Zn precursor as a binder, and the paste with a solid content of 65-75% is formed by stirring to have good plasticity. The paste is prepared into spherical particles with a particle size of 50-100 μm by spray drying method under the conditions of an inlet air temperature of 180-200°C and an outlet air temperature of 90-100°C, so that the precursor is uniformly loaded on the surface of the carrier. The mass ratio of the activated boron nitride nanosheet carrier and the Cu-Zn precursor is 2-4:1;

[0016] S7 crystal form regulation: the spherical particles are placed in a high-temperature tube furnace, and the temperature is increased from room temperature to 300-350℃ at a rate of 3-4℃ / min, and the temperature is maintained for 1-1.5h in an argon and hydrogen mixed atmosphere (hydrogen content 5-8%), and the organic impurities are preliminarily removed; then the temperature is continuously increased to 550-600℃ at a rate of 2-3℃ / min, and calcination is carried out for 30-50min, so as to promote the conversion of basic carbonate into CuO-ZnO composite oxide;

[0017] S8 reduction: the CuO-ZnO composite oxide is placed in an atomic layer deposition device, and an organic precursor of zinc, diethyl zinc, and hydrogen are sequentially introduced, and a layer of zinc atoms is deposited on the surface of the CuO-ZnO composite oxide, and then switched to a methanol-hydrogen mixed gas, and part of the CuO is preliminarily reduced, and the Cu / ZnO active center is formed on the CuO-ZnO composite oxide;

[0018] S9 carbonization: after the temperature of the reactor is reduced, acetylene gas is introduced, and acetylene is pyrolyzed and carbonized on the surface of the CuO-ZnO composite oxide to form a carbon film, thereby obtaining a high-efficiency catalyst.

[0019] Further, after the raw material is sent into the hydrogen sintering furnace, the hydrogen and the natural gas are mixed at a volume ratio of 1:0.4-0.6, and then gradient calcination is carried out;

[0020] First stage: calcination temperature 1250-1280℃ (material temperature), time 40-60min;

[0021] Second stage: calcination temperature 1280-1320℃ (material temperature), time 40-60min;

[0022] Third stage: calcination temperature 1320-1350℃ (material temperature), time 40-60min.

[0023] Further, the carbon dioxide recovery method is specifically as follows: a high-efficiency carbon dioxide absorption tower is installed at the exhaust outlet of the hydrogen sintering furnace, and ethanolamine solution is used as the absorbent, and the absorption tower temperature is controlled at 40-50℃, and the saturated ethanolamine solution is desorbed at 100-120℃ and 0.1-0.2MPa to obtain high-purity carbon dioxide.

[0024] Further, S1 dissolution: the copper slag and zinc tailings are crushed to 100-200 meshes, and immersed in a methanol solution with a sulfuric acid concentration of 20-30%, and the pressure in the sealed reaction kettle is maintained at 0.2-0.5MPa, and the temperature is maintained at 70-80℃ for 1-2h, and the copper and zinc are leached, and the mixed metal solution and the leached metal filter residue are obtained.

[0025] Further, S3 is specifically: adding 1.5-2.0 mol / L sodium carbonate solution preheated to 50-60℃ to the copper-zinc mixed solution at a speed of 6-10 drops / min, adjusting the pH of the solution to 8-10, and adding 0.5-2% of the complexing agent citric acid to the copper-zinc mixed solution to inhibit the excessive growth and agglomeration of the crystal grains through coordination, and aging for 40-60 min to promote the directional growth of the crystal nucleus to obtain the Cu-Zn precursor. and Synchronous generation of basic carbonate, control the stirring speed to 200-400 r / min to avoid local supersaturation leading to uneven particle size, and add 0.5-2% of the complexing agent citric acid to the copper-zinc mixed solution to inhibit the excessive growth and agglomeration of the crystal grains through coordination, and aging for 40-60 min to promote the directional growth of the crystal nucleus to obtain the Cu-Zn precursor.

[0026] Further, S5 is specifically: placing the boron nitride nanosheet in a 0.2-0.3 mol / L sodium hydroxide solution, ultrasonic treatment at 40-50℃ for 1-2 h to remove surface impurities and oxides, then washing with deionized water until neutral, and vacuum drying at 100-150℃ to obtain activated boron nitride nanosheet.

[0027] Further, S6 is specifically: adding 2-3% of carboxymethyl cellulose as a binder to the Cu-Zn precursor, stirring uniformly to form a paste with a solid content of 65-75% and good plasticity, and preparing spherical particles with a particle size of 50-100 μm by spray drying method under the conditions of an inlet air temperature of 180-200℃ and an outlet air temperature of 90-100℃, so that the precursor is uniformly loaded on the carrier surface, and the mass ratio of the activated boron nitride nanosheet carrier and the Cu-Zn precursor is 2-4:1.

[0028] Further, S7 is specifically: placing the spherical particles in a high-temperature tube furnace, heating from room temperature to 300-350℃ at a heating rate of 3-4℃ / min, and heat treating in an argon-hydrogen mixed atmosphere for 1-1.5 h to preliminarily remove organic impurities; then continuing to heat at a heating rate of 2-3℃ / min to 550-600℃, and calcining for 30-50 min to promote the conversion of the basic carbonate to CuO-ZnO composite oxide.

[0029] Further, S8 is specifically: placing the CuO-ZnO composite oxide into an atomic layer deposition device, sequentially introducing the organic precursor diethyl zinc of zinc and hydrogen, and performing atomic layer deposition at 120-130℃ to deposit a layer of zinc atoms on the surface of the CuO-ZnO composite oxide, then switching to a methanol-hydrogen mixed gas, and heat treating at 250-280℃ for 30-50 min, while using the zinc atomic layer deposited by atomic layer deposition to induce the directional growth and dispersion of copper atoms, preliminarily reducing part of the CuO, and forming Cu / ZnO active centers on the CuO-ZnO composite oxide.

[0030] Further, S9 is specifically: when the reactor temperature drops to 150-170 DEG C, acetylene gas is introduced, the flow is controlled at 30-50 mL / min, and the reaction is carried out for 15-20 min, acetylene is pyrolyzed and carbonized on the surface of the CuO-ZnO composite oxide to form a carbon film, thereby obtaining a high-efficiency catalyst.

[0031] Compared with the prior art, the present application has the following beneficial effects:

[0032] 1. The present application selects hydrogen and natural gas as the core heat source for raw material calcination. During the hydrogen combustion process, only water is produced, and almost no carbon emissions are generated. Compared with traditional fossil fuels, the present application effectively reduces the carbon emission path and can alleviate the negative impact of greenhouse gas emissions on the global climate. In addition, by precisely adjusting the volume ratio of hydrogen to natural gas, fine regulation of the calcination temperature can be achieved. In industrial production, different raw materials have strict and subtle requirements for calcination temperature. The temperature regulation method of the present application can accurately match the characteristics of the raw material to ensure that the raw material completes the calcination reaction in the most suitable temperature range. This not only makes the raw material calcination more complete and improves the uniformity of product quality, but also avoids product defects caused by temperature fluctuations, thereby improving production efficiency, reducing the rate of defective products, and effectively ensuring the stability and efficiency of the entire production process, providing strong support for the green upgrade of related industries.

[0033] 2. The present application uses the recovery of carbon dioxide in the tail gas as a key technical link. By efficiently separating carbon dioxide from the complex components of the tail gas, the total amount of carbon emissions is further reduced. Using the specially designed high-efficiency catalyst of the present application, the recovered carbon dioxide can be efficiently converted into high-purity methanol. The catalyst is unique in structure design and active site construction, and can accurately adsorb carbon dioxide molecules and promote their reaction with hydrogen. Compared with the same type of catalyst on the market, in terms of improving the selectivity of methanol, it can significantly inhibit the occurrence of side reactions, making the reaction system more towards the generation of methanol; in terms of carbon dioxide conversion rate, it can significantly increase the amount of carbon dioxide participating in the reaction per unit time; in terms of methanol space-time yield, the amount of methanol generated per unit time and unit mass of catalyst is significantly increased. Most importantly, the synthesized methanol can be used as a high-quality solvent for the preparation of high-efficiency catalysts, which builds a closed-loop system for energy recycling. From the recovery of carbon dioxide in the tail gas to the synthesis of methanol, and then to the preparation of methanol for catalysts, the whole process is closely linked, greatly improving the comprehensive utilization rate of resources and opening up a new path for the sustainable development of the chemical industry.

[0034] 3. In the preparation process of the high-efficiency catalyst of this invention, the waste residue is no longer considered a production burden, but is transformed into a highly valuable secondary resource, thereby successfully improving the strength of cement. This measure not only improves the mechanical properties of cement products and broadens their application fields, but also significantly reduces the emission of waste residue. The proper treatment of waste residue avoids the potential pollution risks to soil, water and air caused by traditional landfill or stockpiling methods, while achieving energy recycling. The waste residue generated from the energy consumption of catalyst preparation can be reused in the cement production process, reducing the demand for other raw materials in cement production and indirectly reducing energy consumption, fully demonstrating the advanced characteristics of this invention in terms of green environmental protection and efficient resource utilization. Attached Figure Description

[0035] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the accompanying drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are merely some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without any creative effort.

[0036] Figure 1 A process flow diagram for producing aluminoferrite cement using hydrogen energy. Detailed Implementation

[0037] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0038] Example 1: This example provides a method for producing aluminoferrite cement using hydrogen energy, comprising the following steps: mixing calcium raw materials, aluminum raw materials, iron raw materials and sulfur raw materials in a mass ratio of 5:2:3:1, ball milling to obtain raw meal powder, calcining the raw meal powder to obtain clinker, and grinding the clinker, mixed materials (slag and fly ash in a mass ratio of 6:4) and gypsum in a mass ratio of 70:25:10 to obtain aluminoferrite cement;

[0039] In this process, after the raw materials are fed into the hydrogen sintering furnace, hydrogen and natural gas are mixed at a volume ratio of 1:0.4-0.6 and then calcined in a gradient.

[0040] Section 1: When the volume ratio of hydrogen to natural gas is 1:0.6, the calcination temperature is 1280℃ and the time is 60min;

[0041] Second stage: hydrogen and natural gas volume ratio 1:0.5, calcination temperature 1320℃, time 60min;

[0042] Third stage: hydrogen and natural gas volume ratio 1:0.4, calcination temperature 1350℃, time 60min;

[0043] Carbon dioxide recovery: install high-efficiency carbon dioxide absorption tower at the outlet of sintering furnace exhaust, use ethanolamine solution as absorbent, control the absorption tower temperature at 50℃, desorb high-purity carbon dioxide from the saturated ethanolamine solution through desorption tower at 120℃, 0.2MPa;

[0044] Pass carbon dioxide and hydrogen into the fixed bed reactor with a molar ratio of 1:4, control the reaction temperature at 250℃, pressure at 3MPa, gas space velocity at 1500 Meanwhile, the prepared methanol can be used in the preparation of high-efficiency catalyst;

[0045] The preparation of high-efficiency catalyst includes the following steps:

[0046] S1 leaching: crush the copper slag and zinc tailings to 200 mesh, immerse in a methanol (synthesized by carbon dioxide and hydrogen through catalyst) solution with a sulfuric acid concentration of 30%, maintain 0.5MPa pressure in a sealed reaction kettle (boosting the boiling point of methanol to above 80℃, ensuring that methanol remains liquid at 70-80℃, promoting copper and zinc leaching, and the polar nature of methanol can promote the uniform dispersion of metal ions), leach copper and zinc at 80℃ for 2h, filter to obtain a mixed metal solution and a filter residue with leached metals;

[0047] The filter residue is mixed with the calcium raw material at a mass ratio of 5%, which plays a role in adjusting the strength;

[0048] S2 impurity removal: pass oxygen into the mixed metal solution, react for 40min, make oxidized to , adjust the solution pH to 4.2, precipitate in the form of , control the stirring speed at 200r / min to promote the growth of flocs, centrifugal separation to remove the precipitate to obtain a copper-zinc mixed solution;

[0049] S3 crystallization: add 2.0mol / L sodium carbonate solution preheated to 60℃ to the copper-zinc mixed solution at a speed of 10 drops / min, adjust the solution pH to 10, make and Synchronous generation of basic carbonate, control stirring speed 400 r / min, avoid local supersaturation leading to uneven particle size, add 2% of copper-zinc mixed solution mass of complexing agent citric acid, inhibit excessive grain growth and agglomeration through coordination, aging 60 min to promote directional growth of crystal nucleus to obtain Cu-Zn precursor;

[0050] S4 washing and drying: after centrifugal separation (8000 r / min, 10 min) of the precipitate after aging, wash 3 times with 60°C deionized water (each time the volume of washing liquid is 3 times the volume of the precipitate), remove residual and ions, add 1 / 10 of the mass of deionized water to anhydrous ethanol at the last washing, replace the moisture on the surface of the particles to reduce hydrogen bond agglomeration during drying; dry at 60°C;

[0051] S5 carrier activation: place the boron nitride nanosheet in a 0.3 mol / L sodium hydroxide solution, ultrasonic treatment at 50°C for 2h, remove surface impurities and oxides, then wash with deionized water to neutral, vacuum drying at 150°C to obtain activated boron nitride nanosheet;

[0052] S6 precursor-carrier composite: add 3% of carboxymethyl cellulose as a binder to the Cu-Zn precursor, stir evenly to form a paste with a solid content of 75% and good plasticity, spray dry the paste at an inlet temperature of 200°C and an outlet temperature of 100°C to obtain spherical particles with a particle size of 100μm, so that the precursor is uniformly loaded on the surface of the carrier, and the mass ratio of the activated boron nitride nanosheet carrier and the Cu-Zn precursor is 4:1;

[0053] S7 crystal shape regulation: place the spherical particles in a high-temperature tube furnace, heat from room temperature to 350°C at a rate of 4°C / min, heat in an argon-hydrogen mixed atmosphere (hydrogen content 8%) for 1.5h to preliminarily remove organic impurities; then continue to heat at a rate of 3°C / min to 600°C, and calcine for 50 min to convert the basic carbonate to CuO-ZnO composite oxide;

[0054] S8 reduction: place the CuO-ZnO composite oxide in an atomic layer deposition device, first purge with nitrogen for 30 min to remove air, then sequentially introduce zinc organic precursor diethyl zinc and hydrogen, and perform atomic layer deposition at 130°C to deposit a layer of zinc atoms on the surface of the CuO-ZnO composite oxide, then switch to methanol-hydrogen mixed gas (H2 / CH3OH=1 / 10) to remove the organic impurities on the surface of the CuO-ZnO composite oxide, and then perform atomic layer deposition again to obtain the Cu-Zn catalyst; Volume fraction 18%), incubated at 280℃ for 50 min, while using atomic layer deposition of zinc atomic layer to induce directional growth and dispersion of copper atoms, and to preliminarily reduce part of CuO, to form Cu / ZnO active centers on the CuO-ZnO composite oxide;

[0055] S9 carbonization: when the reactor temperature drops to 170℃, acetylene gas is introduced, the flow rate is controlled at 50 mL / min, and reaction is carried out for 20 min, acetylene is pyrolyzed and carbonized on the surface of the CuO-ZnO composite oxide to form a carbon film, thereby obtaining a high-efficiency catalyst (the carbon film can not only further stabilize the Cu / ZnO active centers and inhibit the sintering and agglomeration of metal Cu grains, but also can adjust the electron cloud density on the surface of the catalyst to improve the adsorption and activation capacity for methanol molecules);

[0056] The hydrogen is obtained by alkaline water electrolysis, the electrolyte is a 30% potassium hydroxide solution by mass fraction, the electrolytic cell is maintained at a working temperature of 80℃, and the voltage is 2.2V; the obtained hydrogen is compressed to 30MPa by a multi-stage compressor and stored in a high-pressure hydrogen storage tank; and the hydrogen is delivered to the calcination kiln through a pipeline, and the pressure is controlled at 2.0MPa during the delivery process.

[0057] Embodiment 2: The embodiment provides a method for producing ferrite-aluminate cement by using hydrogen energy, comprising the following steps: mixing calcium raw materials, aluminum raw materials, iron raw materials and sulfur raw materials in a mass ratio of 5:2:3:1, ball milling to obtain raw meal powder, calcining the raw meal powder to obtain clinker, and grinding the clinker, mixed materials (mineral slag and fly ash in a mass ratio of 6:4) and gypsum in a mass ratio of 70:25:10 to obtain ferrite-aluminate cement;

[0058] In the embodiment, the raw meal is sent into a hydrogen sintering furnace, hydrogen and natural gas are mixed in a volume ratio of 1:0.4-0.6, and then gradient calcination is performed;

[0059] First stage: when the volume ratio of hydrogen to natural gas is 1:0.6, the calcination temperature is 1250℃, and the time is 40min;

[0060] Second stage: when the volume ratio of hydrogen to natural gas is 1:0.5, the calcination temperature is 1280℃, and the time is 40min;

[0061] Third stage: when the volume ratio of hydrogen to natural gas is 1:0.4, the calcination temperature is 1320℃, and the time is 40min;

[0062] Carbon dioxide recovery: an efficient carbon dioxide absorption tower is installed at the exhaust outlet of the sintering furnace, ethanolamine solution is used as the absorbent, the absorption tower temperature is controlled at 40℃, and the saturated ethanolamine solution is desorbed at 100℃ and 0.1MPa to obtain high-purity carbon dioxide;

[0063] Carbon dioxide and hydrogen gas are passed into a fixed bed reactor with high-efficiency catalyst at a molar ratio of 1:3.5, the reaction temperature is controlled at 200℃, the pressure is 1MPa, and the gas space velocity is 1000 Meanwhile, the prepared methanol can be used in the preparation of high-efficiency catalyst.

[0064] The preparation of high-efficiency catalyst includes the following steps.

[0065] S1 Leaching: Copper residue and zinc tailings are crushed to 100 mesh and immersed in a methanol solution with a sulfuric acid concentration of 20% (prepared by synthesizing carbon dioxide and hydrogen gas through catalyst), and the pressure in the sealed reactor is maintained at 0.2MPa (the boiling point of methanol is raised to above 80℃ by increasing the pressure, ensuring that methanol remains liquid at 70-80℃, promoting the leaching of copper and zinc, and the polar nature of methanol can promote the uniform dispersion of metal ions); leaching copper and zinc at 70℃ for 1h, filtering to obtain a mixed metal solution and a filter residue with leached metals;

[0066] The filter residue is mixed with the calcium raw material at a ratio of 3% of the mass of the calcium raw material to adjust the strength.

[0067] S2 Impurity removal: oxygen is passed into the mixed metal solution for 30min to oxidize to , adjust the pH of the solution to 3.8, precipitate in the form of , control the stirring speed at 100r / min to promote the growth of the floc, and centrifuge to remove the precipitate to obtain a copper-zinc mixed solution;

[0068] S3 Crystallization: 1.5mol / L sodium carbonate solution preheated to 50℃ is added to the copper-zinc mixed solution at a rate of 6 drops / min, the pH of the solution is adjusted to 8, and basic carbonate is generated synchronously and , the stirring speed is controlled at 200r / min to avoid local supersaturation leading to uneven particle size, and 0.5% of the mass of the copper-zinc mixed solution of complexing agent citric acid is added to inhibit excessive grain growth and agglomeration through coordination, and the Cu-Zn precursor is obtained by aging for 40min to promote directional growth of the crystal nucleus;

[0069] S4 Washing and drying: the precipitate after aging is centrifuged (8000r / min, 10min), washed with 50℃ deionized water for 2 times (the volume of each washing liquid is 3 times the volume of the precipitate), and the residual and ions are removed, 1 / 10 of the mass of deionized water is added as anhydrous ethanol during the last washing to replace the water on the surface of the particles and reduce hydrogen bonding agglomeration during drying; and dried at 50℃.

[0070] S5 carrier activation: the boron nitride nanosheet is placed in a sodium hydroxide solution with a concentration of 0.2 mol / L, ultrasonic treatment is carried out at 40°C for 1 h to remove surface impurities and oxides, then washed with deionized water for multiple times until neutral, and vacuum dried at 100°C to obtain activated boron nitride nanosheet;

[0071] S6 precursor-carrier complex: 2% carboxymethyl cellulose by mass fraction is added to the Cu-Zn precursor as a binder, stirred uniformly to form a paste with a solid content of 65% and good plasticity, and the paste is prepared into spherical particles with a particle size of 50 μm by a spray drying method under the conditions of an inlet air temperature of 180°C and an outlet air temperature of 90°C, so that the precursor is uniformly loaded on the surface of the carrier, and the mass ratio of the activated boron nitride nanosheet carrier and the Cu-Zn precursor is 2:1;

[0072] S7 crystal shape regulation: the spherical particles are placed in a high-temperature tube furnace, heated from room temperature to 300°C at a heating rate of 3°C / min, and kept in an argon and hydrogen mixed atmosphere (hydrogen content 5%) for 1 h to preliminarily remove organic impurities; then continue to heat to 550°C at a heating rate of 2°C / min, and calcine for 30 min to promote the conversion of basic carbonate to CuO-ZnO composite oxide;

[0073] S8 reduction: the CuO-ZnO composite oxide is placed in an atomic layer deposition device, nitrogen is first introduced to purge for 30 min to exclude air, then zinc organic precursor diethyl zinc and hydrogen are sequentially introduced, atomic layer deposition is carried out at 120°C, a layer of zinc atomic layer is deposited on the surface of the CuO-ZnO composite oxide, then switch to methanol-hydrogen mixed gas (volume fraction 12%) at 250°C for 30 min, and at the same time, the zinc atomic layer is used to induce the directional growth and dispersion of copper atoms, and preliminarily reduce part of CuO to form Cu / ZnO active centers on the CuO-ZnO composite oxide;

[0074] S9 carbonization: when the reactor temperature drops to 150°C, acetylene gas is introduced, the flow rate is controlled at 30 mL / min, and the reaction is carried out for 15 min, acetylene is pyrolyzed and carbonized on the surface of the CuO-ZnO composite oxide to form a carbon film, and a high-efficiency catalyst is obtained (the carbon film not only can further stabilize the Cu / ZnO active center and inhibit the sintering and agglomeration of metal Cu grains, but also can adjust the electron cloud density of the catalyst surface to improve the adsorption and activation ability of methanol molecules);

[0075] ​The hydrogen is obtained by alkaline water electrolysis, the electrolyte is a 20% potassium hydroxide solution, the electrolytic cell is maintained at a working temperature of 70 DEG C, and the voltage is 1.8V; the obtained hydrogen is compressed to 20MPa by a multi-stage compressor and stored in a high-pressure hydrogen storage tank; and the hydrogen is transported to the calcining kiln through a pipeline, and the pressure is controlled at 1.5MPa during the transportation.

[0076] In this embodiment, a method for producing ferrite-aluminate cement by using hydrogen energy is provided, which comprises the following steps: mixing calcareous raw materials, aluminous raw materials, ferruginous raw materials and sulfurous raw materials in a mass ratio of 5:2:3:1, ball milling to obtain raw meal powder, calcining the raw meal powder to obtain clinker, and grinding the clinker, mixed materials (mineral slag and fly ash in a mass ratio of 6:4) and gypsum in a mass ratio of 70:25:10 to obtain ferrite-aluminate cement;

[0077] In this embodiment, the raw meal is sent into a hydrogen sintering furnace, hydrogen is mixed with natural gas in a volume ratio of 1:0.4-0.6, and then gradient calcination is performed;

[0078] In the first stage, the volume ratio of hydrogen to natural gas is 1:0.6, the calcination temperature is 1260 DEG C, and the time is 42min;

[0079] In the second stage, the volume ratio of hydrogen to natural gas is 1:0.5, the calcination temperature is 1310 DEG C, and the time is 48min;

[0080] In the third stage, the volume ratio of hydrogen to natural gas is 1:0.4, the calcination temperature is 1340 DEG C, and the time is 55min;

[0081] Carbon dioxide recovery: a high-efficiency carbon dioxide absorption tower is installed at the exhaust outlet of the sintering furnace, ethanolamine solution is used as the absorbent, the absorption tower is controlled at a temperature of 48 DEG C, and the saturated ethanolamine solution is desorbed at a temperature of 106 DEG C and a pressure of 0.15MPa to obtain high-purity carbon dioxide;

[0082] Carbon dioxide and hydrogen are passed into a fixed-bed reactor containing a high-efficiency catalyst at a molar ratio of 1:3.8, the reaction temperature is controlled at 230 DEG C, the pressure is 2MPa, the gas space velocity is 1200 Meanwhile, the obtained methanol can be used in the preparation of a high-efficiency catalyst;

[0083] The preparation of the high-efficiency catalyst comprises the following steps:

[0084] S1 leaching: Copper residue and zinc tailings residue were crushed to 180 mesh, immersed in a methanol solution with a sulfuric acid concentration of 22% (synthesized by carbon dioxide and hydrogen gas through a catalyst), and maintained at a pressure of 0.4 MPa in a sealed reactor (the pressure increased the boiling point of methanol to above 80°C, ensuring that methanol remained liquid at 70-80°C, while promoting copper and zinc leaching, and the polar nature of methanol could promote the uniform dispersion of metal ions), and leached at 72°C for 1.2 h, and then filtered to obtain a mixed metal solution and a filter residue with leached metals;

[0085] The filter residue was mixed with the calcium raw material at a mass ratio of 4%, which played a role in adjusting the strength;

[0086] S2 impurity removal: oxygen was introduced into the mixed metal solution, and reacted for 34 min to make oxidized to , the pH of the solution was adjusted to 4.1, precipitated in the form of , the stirring speed was controlled at 160 r / min to promote the growth of the floc, and the precipitate was removed by centrifugal separation to obtain a copper-zinc mixed solution;

[0087] S3 crystallization: 1.7 mol / L sodium carbonate solution preheated to 54°C was added to the copper-zinc mixed solution at a rate of 8 drops / min, the pH of the solution was adjusted to 9, and basic carbonate was generated synchronously, and , the stirring speed was controlled at 300 r / min to avoid local supersaturation leading to uneven particle size, and 1% of the mass of the copper-zinc mixed solution of complexing agent citric acid was added to inhibit excessive grain growth and agglomeration through coordination, and the Cu-Zn precursor was obtained by directional growth of the crystal nucleus after aging for 52 min;

[0088] S4 washing and drying: the precipitate after aging was separated by centrifugation (8000 r / min, 10 min), washed with 55°C deionized water for 3 times (the volume of each washing solution was 3 times the volume of the precipitate), and the residual and ions were removed, 1 / 10 of the mass of deionized water was added as anhydrous ethanol during the last washing to replace the water on the surface of the particles and reduce hydrogen bond agglomeration during drying; and dried at 56°C;

[0089] S5 carrier activation: the boron nitride nanosheet was placed in a 0.22 mol / L sodium hydroxide solution and ultrasonically treated at 47°C for 1 h to remove surface impurities and oxides, then washed with deionized water until neutral, and vacuum dried at 120°C to obtain activated boron nitride nanosheet;

[0090] S6 precursor-support complex: 2.5% carboxymethyl cellulose by mass was added to the Cu-Zn precursor as a binder, and stirred uniformly to form a paste with a solid content of 72% and good plasticity. The paste was prepared into spherical particles with a particle size of 80 μm by spray drying at an inlet temperature of 190 ℃ and an outlet temperature of 98 ℃, so that the precursor was uniformly loaded on the surface of the support. The mass ratio of activated boron nitride nanosheet support to Cu-Zn precursor was 3:1;

[0091] S7 crystal shape regulation: the spherical particles were placed in a high-temperature tube furnace, and heated from room temperature to 330 ℃ at a rate of 3 ℃ / min in an argon and hydrogen mixed atmosphere (hydrogen content 7%) for 1.5 h to preliminarily remove organic impurities; then heated to 580 ℃ at a rate of 2 ℃ / min, and calcined for 40 min to promote the conversion of basic carbonate to CuO-ZnO composite oxide;

[0092] S8 reduction: the CuO-ZnO composite oxide was placed in an atomic layer deposition device, and nitrogen was first introduced to purge for 30 min to remove air, and then diethyl zinc, an organic precursor of zinc, and hydrogen were introduced in sequence. Atomic layer deposition was carried out at 128 ℃ to deposit a layer of zinc atoms on the surface of the CuO-ZnO composite oxide. Then, the device was switched to a methanol-hydrogen mixed gas (volume fraction 16%) at 270 ℃ for 40 min, while the zinc atomic layer induced the directional growth and dispersion of copper atoms, and preliminarily reduced part of the CuO to form Cu / ZnO active centers on the CuO-ZnO composite oxide;

[0093] S9 carbonization: when the reactor temperature dropped to 160 ℃, acetylene gas was introduced at a flow rate of 40 mL / min, and reacted for 18 min. Acetylene was pyrolyzed and carbonized on the surface of the CuO-ZnO composite oxide to form a carbon film, thereby obtaining a high-efficiency catalyst (the carbon film not only further stabilizes the Cu / ZnO active centers and inhibits the sintering and agglomeration of metal Cu grains, but also adjusts the electron cloud density on the surface of the catalyst to improve the adsorption and activation capacity of methanol molecules);

[0094] The hydrogen was obtained by alkaline water electrolysis, and the electrolyte was a 25% potassium hydroxide solution by mass. The working temperature of the electrolytic cell was maintained at 77 ℃, and the voltage was 2.1 V. The obtained hydrogen was compressed to 24 MPa by a multi-stage compressor and stored in a high-pressure hydrogen storage tank. The hydrogen was transported to the calcination kiln through a pipeline, and the pressure was controlled at 1.8 MPa during the transportation process.

[0095] Comparative Example 1: The difference between this comparative example and Example 3 is that the filter residue is not added to the mixed material.

[0096] ​Comparative Example 2: The difference between this comparative example and Example 3 is that, in the preparation of the high-efficiency catalyst, the S1 dissolution is selected to be a 20-30% sulfuric acid aqueous solution instead of a methanol solution.

[0097] Comparative Example 3: The difference between this comparative example and Example 3 is that, in the preparation of the high-efficiency catalyst, the S8 reduction step is not performed.

[0098] Comparative Example 4: The difference between this comparative example and Example 3 is that, in the preparation of the high-efficiency catalyst, the S9 carbonization step is not performed.

[0099] Comparative Example 5: The difference between this comparative example and Example 3 is that, in the preparation of the high-efficiency catalyst, 1, the S1 dissolution is selected to be a 20-30% sulfuric acid aqueous solution instead of a methanol solution; 2, the S8 reduction step is not performed; and the S9 carbonization step is not performed.

[0100] Control Example: The CuZnAl catalyst doped with 5% Ce is selected.

[0101] The preparation method of the above catalyst is selected from Li Xuan, Wang Bin, Li Jing, etc. Influence of Ce-doped CuZnAl catalyst on catalytic performance of methanol synthesis by hydrogenation [J / OL]. Low-carbon chemistry and chemical industry, 1-9 [2025-04-25]. http: / / kns.cnki.net / kcms / detail / 51.1807.tq.20250416.1602.002.html.

[0102] Experimental Example 1: The cement mechanical properties of Examples 1-3 and Comparative Example 1 are detected according to "Cement Mortar Strength Test Method (ISO Method)" (GB / T 17671-2021);

[0103] Preparation of test pieces: The cement, Chinese ISO standard sand, and water are mixed into plastic cement mortar according to the specified ratio and method. The mass ratio of cement to standard sand is 1:3, and the water-cement ratio is 0.5. The mixed mortar is divided into two layers and placed in a 40mm×40mm×160mm three-punch test mold, each layer is vibrated with a vibration table, and then placed in a standard curing box for curing.

[0104] Curing conditions: The test pieces are cured in water at (20±1)℃ for 28 days.

[0105] Flexural strength test: The test pieces cured to the specified age are taken out, the surface moisture and sand particles are wiped off, and placed on the two supporting cylinders of the flexural testing machine. The load is uniformly applied at a specified rate until the test piece breaks, and the failure load and flexural strength are recorded.

[0106] ​Compressive strength test: After the bending test, the two half prism bodies are placed on the compression testing machine for compression test, the load is uniformly applied at a specified rate until the test piece is destroyed, the destruction load is recorded, and the compressive strength is calculated.

[0107] The results are shown in Table 1:

[0108] Table 1

[0109]

[0110] From the above table, by adding copper residue and zinc tailing residue which have leached out metals into the clinker, the invention realizes a slight increase in the strength of cement.

[0111] Experimental Example 2: The catalytic performance of the catalysts prepared in Examples 1-3, Comparative Examples 2-5 and the control example was detected;

[0112] Carbon dioxide conversion rate: The concentration change of carbon dioxide before and after the reaction was analyzed by gas chromatograph, and the conversion rate of carbon dioxide was calculated, the formula was:

[0113]

[0114] The higher the conversion rate, the stronger the activation and conversion ability of the catalyst for carbon dioxide.

[0115] Methanol selectivity: The content of methanol and other by-products (such as carbon monoxide, methane, etc.) in the reaction product was analyzed by gas chromatograph, and the methanol selectivity was calculated, the formula was:

[0116]

[0117] High methanol selectivity means that the catalyst can more effectively promote the target reaction to generate methanol and reduce the occurrence of side reactions.

[0118] Methanol space-time yield:

[0119] It refers to the mass of methanol generated per unit time and per unit mass (or volume) of catalyst, usually in gMeOH This index takes into account the activity and reaction rate of the catalyst, and can more comprehensively reflect the performance of the catalyst in actual production:

[0120]

[0121] In addition, the space-time yield of the control example needs to be converted, the mass concentration of the prepared catalyst c=0.1g / mL, 1mg / (mL·h)=0.01gMeOH .

[0122] The results are shown in Table 2:

[0123] Table 2

[0124]

[0125] From the above table, it can be seen that the present application effectively improves the selectivity of methanol by replacing the metals in the copper residue and zinc tailing residue with methanol; improves the conversion rate of carbon dioxide by forming Cu / ZnO active centers on the CuO-ZnO composite oxide through diethyl zinc; significantly improves the space-time yield of methanol by forming a carbon film on the surface of the CuO-ZnO composite oxide through pyrolysis and carbonization of acetylene; and the above three technical solutions are compounded to produce a synergistic effect for improving the selectivity of methanol, improving the conversion rate of carbon dioxide, and improving the space-time yield of methanol.

[0126] The above examples are only used to illustrate the technical solutions of the present application, and not to limit it; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that the technical solutions recorded in the foregoing examples can still be modified, or some technical features can be replaced by equivalents; and these modifications or replacements will not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A method for producing aluminoferrite cement using hydrogen energy, comprising the following steps: Raw meal powder is calcined to obtain clinker, and clinker, admixtures and gypsum powder are ground to obtain aluminoferrite cement; characterized in that the fuel for calcining the raw meal is a mixture of hydrogen and natural gas; The recovered carbon dioxide and hydrogen are used to synthesize methanol through a highly efficient catalyst, and the resulting methanol is used in the preparation of the highly efficient catalyst. The preparation of highly efficient catalysts includes the following steps; S1 leaching: The copper slag and zinc tailings slag are crushed, immersed in a sulfuric acid-methanol solution, and filtered to obtain a mixed metal solution and filter residue; The filter residue is added to the mixed material at a ratio of 3-5% by weight of the calcium raw material; S2 impurity removal; S3 crystallization: Add sodium carbonate solution dropwise to the copper-zinc mixture to adjust the pH of the solution. and Basic carbonates are generated simultaneously, and citric acid, a complexing agent, is added. After aging, Cu-Zn precursors are obtained. S4 Washing and Drying: After centrifugation, the aged precipitate is washed 2-3 times with deionized water at 50-60℃ to remove residual impurities. and For the final washing, add anhydrous ethanol at a concentration of 1 / 10 the mass of deionized water to replace the surface moisture of the particles and reduce hydrogen bond aggregation during the drying process; dry at 50-60℃. S5 carrier activation: Boron nitride nanosheets were placed in sodium hydroxide solution, ultrasonically treated to remove surface impurities and oxides, and washed and dried to obtain activated boron nitride nanosheets; S6 precursor-carrier composite: The precursor is uniformly loaded onto the surface of the carrier to form spherical particles; S7 Crystal Form Control: Heat the spherical particles to remove impurities; continue heating to obtain CuO-ZnO composite oxide; S8 reduction: Diethylzinc and hydrogen are introduced into the CuO-ZnO composite oxide, and then switched to a methanol-hydrogen mixture to form Cu / ZnO active centers. S9 carbonization: Acetylene gas is introduced, and pyrolysis carbonization is carried out on the surface of CuO-ZnO composite oxide to form a carbon film, thus obtaining a highly efficient catalyst.

2. The method for producing aluminoferrite cement using hydrogen energy according to claim 1, characterized in that, After the raw materials are fed into the hydrogen sintering furnace, hydrogen and natural gas are mixed at a volume ratio of 1:0.4-0.6 and then calcined in a gradient. First stage: calcination temperature 1250-1280℃, time 40-60min; Second stage: calcination temperature 1280-1320℃, time 40-60min; Three stages: calcination temperature 1320-1350℃, time 40-60min.

3. The method for producing aluminoferrite cement using hydrogen energy according to claim 1, characterized in that, The specific method for carbon dioxide recovery is as follows: a high-efficiency carbon dioxide absorption tower is installed at the exhaust gas outlet of the hydrogen sintering furnace, using ethanolamine solution as the absorbent. The temperature of the absorption tower is controlled at 40-50℃. The saturated ethanolamine solution is desorbed into high-purity carbon dioxide through a desorption tower at 100-120℃ and 0.1-0.2MPa.

4. The method for producing aluminoferrite cement using hydrogen energy according to claim 1, characterized in that, S1 leaching: The copper slag and zinc tailings are crushed to 100-200 mesh and immersed in a methanol solution with a sulfuric acid concentration of 20-30%. The pressure is maintained at 0.2-0.5 MPa in a closed reactor and kept at 70-80℃ for 1-2 hours to leach out the copper and zinc. The mixture is then filtered to obtain a mixed metal solution and filter residue from which the metal has been leached.

5. The method for producing aluminoferrite cement using hydrogen energy according to claim 1, characterized in that, S3 specifically involves adding a preheated (50-60℃) 1.5-2.0 mol / L sodium carbonate solution to the copper-zinc mixture at a rate of 6-10 drops / min, adjusting the pH of the solution to 8-10. and Basic carbonates are generated simultaneously. The stirring speed is controlled at 200-400 r / min to avoid local oversaturation that could lead to uneven particle size. At the same time, 0.5-2% of the complexing agent citric acid is added to the copper-zinc mixture to inhibit excessive grain growth and agglomeration through coordination. After aging for 40-60 min, the directional growth of crystal nuclei is promoted to obtain Cu-Zn precursors.

6. The method for producing aluminoferrite cement using hydrogen energy according to claim 1, characterized in that, S5 specifically involves placing boron nitride nanosheets in a sodium hydroxide solution with a concentration of 0.2-0.3 mol / L, ultrasonically treating them at 40-50℃ for 1-2 hours to remove surface impurities and oxides, washing them repeatedly with deionized water until neutral, and then vacuum drying them at 100-150℃ to obtain activated boron nitride nanosheets.

7. The method for producing aluminoferrite cement using hydrogen energy according to claim 1, characterized in that, S6 specifically involves adding 2-3% by mass of carboxymethyl cellulose as a binder to the Cu-Zn precursor, stirring until a paste with good plasticity and a solid content of 65-75% is formed. The paste is then spray-dried at an inlet air temperature of 180-200℃ and an outlet air temperature of 90-100℃ to form spherical particles with a particle size of 50-100μm, ensuring that the precursor is uniformly loaded onto the carrier surface. The mass ratio of activated boron nitride nanosheet carrier to Cu-Zn precursor is 2-4:

1.

8. The method for producing aluminoferrite cement using hydrogen energy according to claim 1, characterized in that, S7 specifically involves placing spherical particles in a high-temperature tube furnace and heating them from room temperature to 300-350°C at a heating rate of 3-4°C / min. The temperature is then maintained in a mixed atmosphere of argon and hydrogen for 1-1.5 hours to initially remove organic impurities. The temperature is then further increased to 550-600°C at a heating rate of 2-3°C / min, and calcined for 30-50 minutes to promote the conversion of basic carbonates into CuO-ZnO composite oxides.

9. The method for producing aluminoferrite cement using hydrogen energy according to claim 1, characterized in that, S8 specifically involves placing the CuO-ZnO composite oxide in an atomic layer deposition (ALD) apparatus, sequentially introducing diethylzinc, an organic precursor of zinc, and hydrogen gas, and performing ALD at 120-130°C to deposit a zinc atomic layer on the surface of the CuO-ZnO composite oxide. The process is then switched to a methanol-hydrogen mixture and held at 250-280°C for 30-50 minutes. The zinc atomic layer deposited by ALD induces the directional growth and dispersion of copper atoms, initially reducing some of the CuO and forming Cu / ZnO active centers on the CuO-ZnO composite oxide.

10. The method for producing aluminoferrite cement using hydrogen energy according to claim 1, characterized in that, S9 specifically involves: when the reactor temperature drops to 150-170℃, acetylene gas is introduced at a flow rate of 30-50 mL / min, and the reaction is carried out for 15-20 min. Acetylene undergoes pyrolysis and carbonization on the surface of CuO-ZnO composite oxide to form a carbon film, thus obtaining a highly efficient catalyst.

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