CN111841295B - Deacidifying agent, preparation method and application thereof - Google Patents
Deacidifying agent, preparation method and application thereof Download PDFInfo
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Abstract
A deacidification agent, and its preparation method and application are provided. Wherein the deacidification agent composition comprises: 60-90 parts by weight of a first component; 6-20 parts by weight of a second component; 4-16 parts of a third component; wherein the first component is the fly ash of a lime rotary kiln, fly ash and/or active lime powder; the second component is water slag of the ore smelting furnace and/or dust removed from the ore smelting furnace; the third component is copperas. The deacidification agent provided by the invention has the advantages that all raw materials are derived from common solid wastes, the raw materials are easy to obtain and low in cost, the field and direction are expanded for the reutilization of wastes, and meanwhile, the deacidification agent provided by the invention has greater advantages in the aspects of deacidification effect, secondary pollution and the like than the traditional deacidification agent.
Description
Technical Field
The invention relates to a deacidification process in the fields of chemical industry, energy, environmental protection and the like, in particular to a deacidification agent composition, a deacidification agent, a preparation method and application thereof.
Background
The requirement of our country on environmental protection is higher and higher, and SO generated by industrial production activities2Acid gases such as HCl and the like have great harm to the environment and human beings. At present, the desulfurization technology of domestic coal-fired power plants mostly adopts mature wet desulfurization technology to remove SO2And HCl and the like, but the wet desulphurization technology can bring about the problems of equipment corrosion, wastewater discharge, white smoke, white mist and other secondary pollution, and more technologies and equipment are needed to solve the new problems. For the flue gas discharged by some non-electric power industries, the flue gas volume, the component composition and the working condition are different from those of a coal-fired power plant, so the flue gas treatment technology suitable for the power plant is not suitable for other non-electric power industries.
At present, some non-electric power industries begin to process flue gas under the environment-friendly pressure, and a dry-process/semi-dry-process desulfurization technology is preferably selected according to the characteristics of industrial production per se, but the existing industrialized dry-process/semi-dry-process desulfurization technology basically adopts a fluidized bed technology and a powdery desulfurizer, and has the problems of complex equipment, high investment, large occupied area, high equipment failure rate, unstable removal efficiency, difficult waste treatment and the like. For example:
(1) in the prior art, a calcium-based desulfurizer loaded by fly ash is prepared by using fly ash and Ca (OH)2The activator is a main raw material, and the fly ash-loaded high-efficiency calcium-based desulfurizer is prepared through a solid-phase reaction/hydrothermal combination reaction process.
(2) In the prior art, a moving layer of a desulfurizer is formed in a desulfurization tower, and when flue gas is contacted with the moving layer to desulfurize the flue gas, the desulfurization with stable efficiency can be carried out; the technique uses a desulfurizing agent comprising hydrated lime, an active source supplying material for supplying silica and alumina such as lime, gypsum for a gypsum source using the desulfurizing agent after desulfurization treatment as a new desulfurizing agent; and secondly, measuring the hardness of the desulfurizing agent, and when the hardness is evaluated to be lower than a preset value, increasing the used desulfurizing agent by a preset amount and reducing the hydrated lime by an amount corresponding to the increase to obtain the desulfurizing agent.
(3) In the prior art, alkaline Al (OH) is also adopted3Or Fe (OH)3The deacidification agent is used for removing HCl or HF gas in the flue gas or the coal gas, and the deacidification agent cannot be mixed with CO in the flue gas or the coal gas2Side reactions occur, and the high-efficiency utilization of the deacidification agent is ensured; the method mainly comprises first-stage absorption and second-stage absorption, wherein the first-stage absorption is mainly water absorption, and Al (OH) is filled in a second-stage absorption device3Or Fe (OH)3As an absorbent to react with the acid gas.
Based on the above, the inventors of the present invention found that in the existing deacidification scheme, either the removal efficiency is low, the applicability is poor, or SO cannot be removed simultaneously2Acid gases such as HCl and HF can not be used for a granular dry deacidification agent of a fixed bed or a moving bed technology, or the method for preparing the desulfurizer or the deacidification agent is complex and has high cost and the like.
Disclosure of Invention
In view of the above, the main objective of the present invention is to provide a deacidification agent composition, a deacidification agent, a preparation method and applications thereof, which are intended to at least partially solve at least one of the above-mentioned technical problems.
In order to achieve the above object, according to a first aspect of the present invention, there is provided an acid scavenger composition. The deacidification agent composition comprises: 60-90 parts by weight of a first component; 6-20 parts by weight of a second component; 4-16 parts of a third component; wherein the first component is the fly ash of a lime rotary kiln, fly ash and/or active lime powder; the lime rotary kiln fly ash refers to dust collected by a dust collector together after lime rotary kiln coal-fired flue gas passes through a rotary kiln and a preheater; wherein the second component is the water slag of the ore smelting furnace and/or the dust removed from the ore smelting furnace; the water granulated slag of the ore smelting furnace is solid residue formed by placing molten slag in water and rapidly cooling the molten slag when a blast furnace or an electric furnace is used for smelting alloy; the dust removal ash of the ore smelting furnace is dust collected by a dust removal and collection device when a blast furnace or an electric furnace is used for smelting alloy; wherein the third component is Melanteritum
According to a second aspect of the present invention, there is also provided a process for the preparation of a deacidification agent. The preparation method comprises the following steps: preparing 6-20 parts by weight of a second component and 4-16 parts by weight of copperas into powder, wherein the second component is ore smelting furnace water slag and/or ore smelting furnace dust; the water granulated slag of the ore smelting furnace is solid residue formed by placing molten slag in water and rapidly cooling the molten slag when a blast furnace or an electric furnace is used for smelting alloy; the dust removal ash of the ore smelting furnace is dust collected by a dust removal and collection device when a blast furnace or an electric furnace is used for smelting alloy; adding 60-90 parts by weight of a first component into the powder to form a powdery dry powder material, wherein the first component is lime rotary kiln fly ash, fly ash and/or active lime powder; the lime rotary kiln fly ash refers to dust collected by a dust collector together after lime rotary kiln coal-fired flue gas passes through a rotary kiln and a preheater; adding water to the dry powder to form a bulk material; molding the bulk material; and sealing and insulating the formed material, and then cooling to normal temperature to obtain the deacidification agent.
According to a third aspect of the present invention, there is also provided a deacidification agent. The deacidification agent is prepared by the preparation method.
According to a fourth aspect of the present invention, there is also provided a deacidification agent composition as described above, or a deacidification agent as described above, for use in a fixed bed reactor or a moving bed reactor; or the deacidification agent composition or the deacidification agent is applied to the purification treatment of industrial smoke or waste gas, wherein the environmental temperature range of the deacidification agent is 20-280 ℃; the acid component content of the industrial flue gas or waste gas is as follows: SO (SO)2The content is less than 1000ppm, or the HCl content is less than1000ppm, or an HF content of less than 1000 ppm.
Compared with the prior art, the deacidification agent composition, the deacidification agent, the preparation method and the application thereof have at least one of the following beneficial effects:
(1) the deacidification agent provided by the invention has the advantages that all raw materials are derived from common solid wastes, are easy to obtain and cheap, and expand the field and direction for the reutilization of wastes;
(2) the deacidification agent of the present invention contains calcium-based substances such as calcium silicate, calcium aluminate, and calcium alumino silicate as active ingredients. The calcium-based substances have stronger alkalinity, can rapidly generate chemical reaction with acid gas, and have good deacidification effect;
(3) the deacidification agent and the product of the acid gas are stable, are not easy to decompose, are harmless to the environment, do not generate secondary pollution and new environmental protection problems in the application process, and do not cause harm to the environment in the waste agent treatment process after being used;
(4) the deacidification agent of the invention also comprises the following auxiliary components: calcium sulfate, iron hydroxides, manganese oxides, and the like. The calcium sulfate can increase the specific surface area of the deacidification agent, the iron hydroxide and the manganese oxide can be dispersed more uniformly under the preparation method, and a more effective redox effect can be realized on sulfur dioxide, so that the deacidification effect of the deacidification agent is indirectly increased;
(5) the deacidification agent is granular, and has good crushing strength and adsorption performance;
(6) in the preparation method of the deacidification agent, the proportion of the water adding amount to the dry material amount is controlled, and the process conditions of sealing and heat preservation at the temperature of 80-200 ℃ are matched, so that the drying step and the roasting step are omitted, the equipment investment and the production cost are saved, the gas emission in the preparation process is reduced, and the deacidification agent has higher economic benefit, environmental benefit and application prospect.
Drawings
FIG. 1 is a flow chart of a method for producing a deacidification agent according to a preferred embodiment of the present invention.
Detailed Description
The invention discloses a deacidification agent composition, which comprises the following components in parts by weight: 60-90 parts by weight of a first component; 6-20 parts by weight of a second component; 4-16 parts of a third component.
The first component is lime rotary kiln fly ash, fly ash and/or active lime powder, preferably the first component is lime rotary kiln fly ash, or the first component is a combination of fly ash and active lime powder. The lime rotary kiln fly ash refers to dust collected by a dust collector together after lime rotary kiln coal-fired flue gas passes through a rotary kiln and a preheater. The dust removal means comprise, for example, a cyclone and/or a bag-type dust remover.
The lime rotary kiln fly ash is powdery, usually contains 40-70% of active lime, is mainly used as road-repairing lime at present, has low removal efficiency if being directly used for desulfurization and deacidification reactions, is difficult to form, and cannot be directly used in a moving bed or fixed bed reactor, so that no literature data indicates that the lime rotary kiln fly ash is used for producing and manufacturing deacidification agents at present.
Wherein the second component is the water slag of the ore smelting furnace and/or the dust removed from the ore smelting furnace. The granulated slag of the ore smelting furnace is solid residue formed by rapidly cooling molten slag in water when a blast furnace or an electric furnace is used for smelting alloy, such as silicon-manganese alloy smelting granulated slag. The dust removed from the ore smelting furnace is dust collected by a dust collecting device when the alloy is smelted by a blast furnace or an electric furnace, such as silicon-manganese alloy smelting dust removed.
The water slag and the fly ash of the ore smelting furnace belong to waste slag in the ore smelting process, have complex components, contain a certain amount of CaO in view of composition analysis, but the calcium oxide belongs to crystals formed after high-temperature melting, have no activity on deacidification reaction, cannot be directly used for deacidification reaction, but contain SiO with hardening activity in complex components2、Al2O3And various transition metal elements can be activated under proper conditions to promote the main component substances to more effectively play the roles of desulfurization and deacidification, and no literature data indicates that the transition metal elements are used for producing and manufacturing deacidification agents at present.
Wherein the third component is copperas. The copperas are obtained by crystallizing ferrous sulfate solution, such as by-products of titanium dioxide production by a sulfuric acid method, wherein the ferrous sulfate content is more than 40%.
The deacidification agent composition prepared by the method comprises active ingredients and auxiliary ingredients. Wherein the active components mainly comprise calcium-based substances such as calcium silicate, calcium aluminate and calcium aluminosilicate; the auxiliary components mainly comprise calcium sulfate, iron manganese oxide and the like.
The calcium-based substance in the active ingredients has strong alkalinity, can rapidly generate chemical reaction with the acid gas, and the product of the calcium-based substance and the acid gas is stable, is not easy to decompose, is harmless to the environment and can be recycled. Meanwhile, calcium silicate, calcium aluminate and calcium aluminosilicate have certain crushing strength and adsorption performance, so that the deacidification agent is more convenient to form and use.
In the auxiliary components, calcium sulfate can increase the specific surface area of the deacidification agent, and the iron-manganese oxide has oxidizability, can play a role in dispersing in the deacidification agent and can enhance the SO of the deacidification agent2The absorption reaction of (1).
The invention also discloses a preparation method of the deacidification agent, which comprises the following steps: adding 6-20 parts by weight of ore smelting furnace water slag and 4-16 parts by weight of copperas into a grinding machine, grinding the materials to be more than 120 meshes, adding 60-90 parts by weight of lime rotary kiln fly ash into mixing equipment, uniformly mixing, adding 40-120 parts by weight of water relative to 100 parts by weight of dry powder, putting the materials into a kneading machine, kneading for 15-45 minutes to form a bulk material, extruding and molding by adopting pressure equipment, transferring the molded material into a sealed heat preservation box, carrying out sealed heat preservation for 2-12 hours, carrying out heat preservation at the temperature of 80-200 ℃, taking out the molded material after the heat preservation time is up, and airing the molded material to normal temperature to prepare the granular dry deacidification agent. The appearance of the prepared finished product is cylindrical or clover, and the radial crushing strength is 80-280N/cm.
The method for producing the deacidification agent according to the preferred embodiment of the present invention will be described in detail in steps.
The deacidification agent of the preferred embodiment is prepared from the following raw materials: the water slag of the ore smelting furnace, the fly ash of the lime rotary kiln and the copperas. Wherein the water granulated slag of the ore smelting furnace is waste after ore smelting, in particular to silicomanganese smelting water granulated slag. The fly ash of the lime rotary kiln is waste after lime refining. The copperas are the by-products of the production of titanium dioxide by a sulfuric acid process. Therefore, the preparation raw materials of the deacidification agent are all derived from common solid wastes, are easy to obtain and cheap, and expand the field and direction for waste recycling.
FIG. 1 is a flow chart of a method for producing a deacidification agent according to a preferred embodiment of the present invention. Referring to fig. 1, the preparation method of the deacidification agent comprises:
step A: preparing the water granulated slag of the ore smelting furnace and the copperas into powder;
the weight portion of the mineral smelting furnace granulating slag is 6-20, and the weight portion of the copperas is 4-16. The powder is prepared by grinding with ball mill to below 120 mesh.
It should be noted that the granulated slag of the ore smelting furnace can also be replaced by the dust removed from the ore smelting furnace.
The deacidification agent of the embodiment is particularly suitable for ore smelting plants, so that waste residues generated in ore smelting can be fully utilized, and the material cost and the transportation cost can be basically ignored.
And B: adding fly ash of a lime rotary kiln to form dry powder;
wherein the added lime rotary kiln fly ash is 60-90 parts by weight.
It should be noted that fly ash or active lime powder can be used to replace the fly ash in the lime rotary kiln.
And C: adding water to the dry powder to form a bulk material;
and adding 40-120 parts by weight of water relative to 100 parts by weight of the dry powder. And after water is added, kneading the mixture in a kneading machine for 15 to 45 minutes to form bulk materials.
Firstly, the fly ash of the lime rotary kiln and the water granulated slag of the ore smelting furnace are ground, added with water, stirred and kneaded, and can release water-soluble SiO simultaneously2And Al2O3In aUnder the condition of sealing and heat preservation, the calcium silicate, the calcium aluminate and the calcium aluminosilicate can be generated through the hardening reaction with the calcium hydroxide.
Ca(OH)m+SiO2+H2O＝(CaO)x(SiO2)y(H2O)z (1)
Ca(OH)m+Al2O3+H2O＝(CaO)x(Al2O3)y(H2O)z (2)
Ca(OH)m+SiO2+Al2O3+H2O＝(CaO)x(SiO2)y(Al2O3)z(H2O)w (3)
These products, as above: calcium silicate, calcium aluminate and calcium aluminosilicate, all have very good adsorption performance and crushing strength. Firstly, the calcium-based substances have stronger alkalinity and can rapidly generate chemical reaction with acid gas, thereby ensuring the effectiveness of the deacidification agent. Second, these calcium-based materials ensure the overall crush strength of the deacidification agent.
Secondly, the water slag of the ore smelting furnace and the dust of the ore smelting furnace contain 10-15% of manganese oxide, and copperas contain a large amount of ferrous sulfate and a small amount of sulfuric acid. Manganese oxide and ferrous sulfate can firstly undergo an oxidation-reduction reaction in the grinding process to generate soluble sulfate, and then the soluble sulfate is mixed with lime rotary kiln fly ash by adding water, active lime in the lime rotary kiln fly ash is reacted by adding water to generate calcium hydroxide, and the calcium hydroxide, manganese sulfate, ferric sulfate and oxygen in the air undergo a chemical reaction to generate calcium sulfate, ferric hydroxide and manganese oxide. The chemical reaction that takes place is shown below:
2FeSO4+MnO2+2H2SO4＝Fe2(SO4)3+MnSO4+2H2O (4)
Fe2(SO4)3+3Ca(OH)2＝2 Fe(OH)3+3CaSO4 (5)
MnSO4+Ca(OH)2＝Mn(OH)2+CaSO4 (6)
2Mn(OH)2+O2＝MnO2(Brown black precipitate) +2H2O (7)
Ca(OH)2+FeSO4＝Fe(OH)2+CaSO4 (8)
4Fe(OH)2+2H2O+O2＝4Fe(OH)3 (9)
The calcium sulfate can increase the specific surface area of the desulfurizing agent. The iron-manganese oxide has oxidability, and can be better dispersed and form a nano-grade dispersion effect in the deacidification agent compared with a form of directly adding a solid oxide because the production process of the iron-manganese oxide is generated by reacting soluble sulfate, SO that the effect of enhancing the deacidification agent on SO can be achieved2The absorption reaction of (1).
Step D: molding the bulk material;
the process of forming the bulk material adopts pressure equipment.
Step E: sealing and insulating the formed material, and then cooling to normal temperature to obtain the deacidification agent.
And (3) placing the formed material into a sealed heat-preserving box, wherein the temperature of heat preservation and sealing is 80-200 ℃. The time for heat preservation and sealing is 2-12 hours. The deacidification agent formed after extrusion molding, sealing and heat preservation is granular, cylindrical or clover strip.
Preferably, during the sealing and heat preservation period, the humidity is kept to be more than 85 percent so as to achieve the purposes of promoting the deacidification agent to react completely, ensuring the components to be uniform and preventing the deacidification agent from drying and cracking. Preferably, the temperature and the humidity are increased by introducing steam with the steam pressure of 0.1-1.6 Mpa.
In the embodiment, the acid removing agent product can ensure the performance and reduce the preparation process operation by controlling the proportion of the water adding amount to the dry material amount and matching with the process conditions of sealing and heat preservation at 80-200 ℃.
Experiments prove that the radial crushing strength of the deacidification agent prepared by the method can reach 80-280N/cm. The strong crushing strength ensures that the deacidification agent has strong crushing resistance, difficult pulverization, small gas passing resistance and small load requirement on reactor equipment in the application of a fixed bed and a moving bed.
The deacidification agent prepared by the preparation method can be used in a fixed bed reactor or a moving bed reactor, is suitable for the temperature range of 20-280 ℃, and contains SO2The purification treatment of industrial flue gas or waste gas (less than 1000ppm) and/or HCl (less than 1000ppm) and/or HF (less than 1000ppm) can achieve the simultaneous removal rate of each component above 90%.
From the above preparation processes, it can be known that the deacidification agent of the embodiment does not add any other chemical components belonging to dangerous waste products in the preparation process, and simultaneously applies a large amount of general solid wastes to the raw materials for preparing the deacidification agent, and has the following advantages: firstly, the preparation cost is reduced; the deacidification agent is granular, is applied to the gas dry purification technology, and does not generate other secondary pollution and new environmental protection problems in the application process; and the used waste agent treatment process does not cause harm to the environment.
The technical solution of the present invention is further illustrated by the following specific examples. It is to be understood that these specific embodiments are merely illustrative of the invention that may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
The products obtained in the following examples require radial crush strength tests to obtain radial crush strength parameters. Wherein, the detection method of the radial crushing strength refers to the following steps: the crushing resistance of the HGT 2782-2011 fertilizer catalyst particles is measured.
The products obtained in the following examples were subjected to an acid gas removal test to obtain an acid gas removal rate. The calculation method of the acid gas removal rate is as follows:
acid gas removal rate (c)0-c)/c0×100％；
Wherein, c0Is SO before the industrial gas passes through the deacidification agent2Or HCL or HF concentration in ppm or mg/Nm3(ii) a c is SO obtained after the industrial gas passes through the deacidification agent2Or HCL or HF concentration in ppm or mg/Nm3(ii) a The concentration of the acid gas in the flue gas is detected once per hour by adopting a flue gas analyzer, the concentration of the gas at the inlet and the outlet is calculated by taking the detection data for 24 hours, the concentration of the acid gas in the introduced gas in the test method is 1000ppm respectively, and the contact time of the industrial gas and the deacidification agent is 7.2 s.
Example 1
Adding 20 parts by weight of ore smelting furnace granulated slag and 12 parts by weight of copperas into a grinding machine together, grinding the mixture into powder of 200 meshes, adding 80 parts by weight of lime rotary kiln fly ash into mixing equipment together, and uniformly mixing, wherein the ratio of the dry powder to the water in parts by weight is 100: adding water (namely adding 60 parts by weight of water relative to 100 parts by weight of dry powder) according to the proportion of 60, stirring and kneading the mixture in a kneading machine for 30min, then extruding and molding the mixture by adopting pressure equipment, transferring the molded material into a sealed heat-preservation box, preserving the heat in a sealed manner for 6 hours, preserving the heat at 140 ℃, taking out the molded material after the heat-preservation standing time is up, and airing the molded material to the normal temperature to prepare the granular dry-method deacidification agent. The appearance of the prepared finished product is cylindrical and bar-shaped.
The radial crushing strength of the product is 185N/cm through experimental tests; at a service temperature of 220 ℃, the acid gas removal rate is 93.4%.
Example 2
The specific steps are the same as those in the embodiment 1, and the differences are as follows: firstly, sealing and preserving heat for 2 hours, wherein the heat preservation temperature is 200 ℃; and secondly, the appearance of the finished product prepared is clover strip-shaped.
The radial crushing strength of the product is 143N/cm through experimental tests; at a service temperature of 220 ℃, the acid gas removal rate is 92.6 percent.
Example 3
The specific procedure is similar to example 1, except that: sealing and preserving heat for 12 hours, wherein the heat preservation temperature is 80 ℃.
The radial crushing strength of the product is 164N/cm through experimental tests; at a service temperature of 160 ℃, the acid gas removal rate is 94.1%.
Example 4
The specific procedure is similar to example 1, except that: grinding the water slag and the copperas of the ore smelting furnace in a grinding machine to 120 meshes; ② sealing, preserving heat and placing for 6 hours, wherein the preserving temperature is 140 ℃.
Through experimental tests, the radial crushing strength of the product is 85N/cm; at the service temperature of 160 ℃, the acid gas removal rate is 91.1 percent.
Example 5
The specific procedure is similar to example 4, except that: grinding the water granulated slag and the copperas of the ore smelting furnace in a grinding machine to 400 meshes.
Through experimental tests, the radial crushing strength of the product is 220N/cm; at a service temperature of 80 ℃, the acid gas removal rate is 92%.
Example 6
Adding 20 parts by weight of ore smelting furnace fly ash and 16 parts by weight of copperas into a grinding machine together, grinding the mixture into powder of 200 meshes, adding 30 parts by weight of fly ash and 30 parts by weight of active lime powder into mixing equipment together, and uniformly mixing, wherein the ratio of the dry powder to the water in parts by weight is 100: 40, adding water, placing the mixture into a kneading machine for kneading for 15min, then extruding and molding by adopting pressure equipment, transferring the molded material into a sealed heat-preservation box, sealing and preserving heat for 6 hours, preserving heat at 140 ℃, taking out the molded material after the heat-preservation standing time is up, and airing the molded material to normal temperature to prepare the granular dry-process deacidification agent. The appearance of the prepared finished product is cylindrical and bar-shaped.
Through experimental tests, the radial crushing strength of the product is 280N/cm; at a use temperature of 20 ℃, the acid gas removal rate is 91.5%.
Example 7
Adding 6 parts by weight of ore smelting furnace fly ash and 4 parts by weight of copperas into a grinding machine together, grinding the mixture into powder of 200 meshes, adding 30 parts by weight of fly ash and 60 parts by weight of active lime powder into mixing equipment together, and uniformly mixing, wherein the ratio of the dry powder to the water in parts by weight is 100: adding water according to the proportion of 90, putting the mixture into a kneading machine for kneading for 30min, then extruding and molding by adopting pressure equipment, transferring the molded material into a sealed heat-preservation box, sealing and preserving heat for 6 hours, preserving heat at 140 ℃, taking out after the heat-preservation standing time is up, and airing to normal temperature to prepare the granular dry-process deacidification agent. The appearance of the prepared finished product is cylindrical and bar-shaped.
The radial crushing strength of the product is 166N/cm through experimental tests; at a service temperature of 220 ℃, the acid gas removal rate is 92.3 percent.
Example 8
Adding 20 parts by weight of ore smelting furnace fly ash and 8 parts by weight of copperas into a grinding machine together, grinding the mixture into powder of 200 meshes, adding 10 parts by weight of fly ash and 80 parts by weight of active lime powder into mixing equipment together, and uniformly mixing, wherein the ratio of the dry powder to the water in parts by weight is 100: adding water in a proportion of 120, putting the mixture into a kneading machine for kneading for 45min, then extruding and molding by adopting pressure equipment, transferring the molded material into a sealed heat-preservation box, sealing and preserving heat for 6 hours, preserving heat at 140 ℃, taking out the molded material after the heat-preservation standing time is up, and airing the molded material to normal temperature to prepare the granular dry-process deacidification agent. The appearance of the prepared finished product is cylindrical and bar-shaped.
Through experimental tests, the radial crushing strength of the product is 170N/cm; at a use temperature of 130 ℃, the acid gas removal rate is 95.2%.
Example 9
The specific procedure is similar to example 1, except that: 60 parts by weight of fly ash in the lime rotary kiln; secondly, in the step of adding water into the dry powder, the weight ratio of the dry powder to the water is 100: adding water in a proportion of 50; ③ in the kneading step, the kneading time is 35 minutes; and fourthly, in the step of sealing and preserving the temperature, the time is 8 hours, and the temperature is 120 ℃.
Through experimental tests, the radial crushing strength of the product is 246N/cm; at a service temperature of 220 ℃, the acid gas removal rate is 92.2%.
Example 10
The specific procedure is similar to example 1, except that: the amount of the fly ash of the lime rotary kiln is 90 parts by weight; secondly, in the step of adding water into the dry powder, the weight ratio of the dry powder to the water is 100: adding water in a proportion of 80; ③ in the kneading step, the kneading time is 40 minutes; and fourthly, in the step of sealing and preserving the temperature, the time is 8 hours, and the temperature is 120 ℃.
Through experimental tests, the radial crushing strength of the product is 191N/cm; at a service temperature of 220 ℃, the acid gas removal rate is 93.8 percent.
Example 11
The specific procedure is similar to example 7, except that: 60 parts by weight of fly ash and 30 parts by weight of active lime powder are adopted in the first component.
Through experimental tests, the radial crushing strength of the product is 202N/cm; at a use temperature of 220 ℃, the acid gas removal rate is 91.5%.
Example 12
Adding 6 parts by weight of ore smelting furnace fly ash and 16 parts by weight of copperas into a grinding machine together to be ground into powder of 200 meshes, adding 90 parts by weight of lime rotary kiln fly ash into mixing equipment together to be uniformly mixed, and then adding the dry powder and water according to the weight part ratio of 100: 80, adding water, placing the mixture into a kneading machine for kneading for 30min, then extruding and molding by adopting pressure equipment, transferring the molded material into a sealed heat-preservation box, sealing and preserving heat for 8 hours, preserving heat at 120 ℃, taking out the molded material after the heat-preservation standing time is up, and airing the molded material to normal temperature to prepare the granular dry-process deacidification agent. The appearance of the prepared finished product is cylindrical and bar-shaped.
The radial crushing strength of the product is 157N/cm through experimental tests; at a use temperature of 220 ℃, the acid gas removal rate is 91.2%.
Example 13
The specific procedure is similar to example 12, except that: the water granulated slag of the ore smelting furnace in the second component accounts for 20 parts by weight; ② the copperas of the third component is 4 weight portions.
The radial crushing strength of the product is 142N/cm through experimental tests; at a service temperature of 220 ℃, the acid gas removal rate is 92.3 percent.
Example 14
The specific procedure is similar to example 12, except that: 10 parts of water granulated slag of the ore smelting furnace and 10 parts of dust removed from the ore smelting furnace in the second component; ② the copperas of the third component accounts for 10 weight portions; thirdly, in the step of adding water into the dry powder, the weight ratio of the dry powder to the water is 100: adding water according to the proportion of 60; fourthly, in the step of sealing and preserving heat, the time is 6 hours and the temperature is 140 ℃.
Through experimental tests, the radial crushing strength of the product is 149N/cm; at a service temperature of 220 ℃, the acid gas removal rate is 92.1%.
Example 15
The specific procedure is similar to example 14, except that: in the first component, 30 parts by weight of fly ash and 60 parts by weight of active lime powder are adopted.
Through experimental tests, the radial crushing strength of the product is 165N/cm; at a service temperature of 220 ℃, the acid gas removal rate is 93.4%.
Example 16
The specific procedure is similar to example 1, except that: in the second component, 20 parts by weight of dust removed from an ore smelting furnace is adopted.
Through experimental tests, the radial crushing strength of the product is 183N/cm; at a service temperature of 220 ℃, the acid gas removal rate is 90.8%.
Example 17
The specific procedure is similar to example 1, except that: in the second component, 6 parts by weight of dust removed by an ore smelting furnace is adopted; ② in the third component, 4 weight portions of copperas are adopted.
Through experimental tests, the radial crushing strength of the product is 180N/cm; at a use temperature of 220 ℃, the acid gas removal rate is 90.6%.
Example 18
The specific procedure is similar to example 1, except that: in the first component, 30 parts by weight of fly ash and 60 parts by weight of active lime powder are adopted; ② in the third component, 16 weight portions of copperas are adopted.
Through experimental tests, the radial crushing strength of the product is 133N/cm; at a use temperature of 220 ℃, the acid gas removal rate is 93.0%.
Example 19
The specific procedure is similar to example 18, except that: in the second component, 6 parts by weight of water granulated slag of an ore smelting furnace is adopted; ② in the third component, 4 weight portions of copperas are adopted.
The radial crushing strength of the product is 124N/cm through experimental tests; at a service temperature of 220 ℃, the acid gas removal rate is 92.5 percent.
Example 20
The specific procedure is similar to example 1, except that: in the second and third component grinding steps, grinding to 120 meshes.
Through experimental tests, the radial crushing strength of the product is 85N/cm; at a use temperature of 20 ℃, the acid gas removal rate is 91.0%.
Example 21
The specific procedure was the same as in example 6.
Through experimental tests, the acid gas removal rate is 94.2% at the use temperature of 280 ℃.
Example 22
The specific procedure is similar to example 1, except that: in the first component, 30 parts by weight of lime rotary kiln fly ash, 20 parts by weight of fly ash and 20 parts by weight of active lime powder are adopted; secondly, in the step of adding water into the dry powder, the weight ratio of the dry powder to the water is 100: water was added at a ratio of 50.
Through experimental tests, the radial crushing strength of the product is 201N/cm; at a use temperature of 220 ℃, the acid gas removal rate is 91.8%.
Comparative example 1
Preparing 80 parts by weight of lime rotary kiln fly ash, and then mixing the dry powder material and water according to the weight ratio of 100: adding water according to the proportion of 50, stirring and kneading for 30min, then transferring to a sealed heat preservation box, and standing for 6 hours in a sealed heat preservation way, wherein the heat preservation temperature is 140 ℃.
Through experimental tests, the radial crushing strength of the product is 62N/cm; at a service temperature of 220 ℃, the acid gas removal rate is 61.2%.
Comparative example 2
Adding 20 parts by weight of ore smelting furnace granulated slag into a grinding machine, and grinding the granulated slag into 200 meshes; and then adding 80 parts by weight of lime rotary kiln fly ash into mixing equipment together for uniform mixing, and mixing according to the weight ratio of the dry powder to water of 100: adding water according to the proportion of 50, putting the mixture into a kneading machine for kneading for 30 minutes, then transferring the mixture into a sealed heat preservation box, and placing the mixture for 6 hours in a sealed heat preservation way, wherein the heat preservation temperature is 140 ℃.
The radial crushing strength of the product is 122N/cm through experimental tests; at a service temperature of 220 ℃, the acid gas removal rate is 70.4%.
Comparative example 3
The specific procedure is similar to comparative example 2, except that: firstly, adding 12 parts by weight of copperas when grinding the water slag of the ore smelting furnace; 60 parts by weight of water is added in the stirring and kneading stage based on 100 parts by weight of the dry powder; and thirdly, in the sealing and heat preservation stage, the heat preservation temperature is 60 ℃.
Through experimental tests, the radial crushing strength of the product is 67N/cm; at a use temperature of 220 ℃, the acid gas removal rate is 80.2%.
Comparative example 4
The specific procedure is similar to comparative example 3, except that: grinding the water granulated slag and the copperas of the ore smelting furnace in a grinding machine to 80 meshes; ② in the stage of sealing and heat preservation, the heat preservation temperature is 240 ℃.
Through experimental tests, the radial crushing strength of the product is 32N/cm; at a service temperature of 220 ℃, the acid gas removal rate is 78.6%.
Comparative example 5
The specific procedure is similar to comparative example 4, except that: grinding to 200 meshes in the second and third component grinding steps; ② in the sealing and heat preservation step, the temperature is 60 ℃.
Through experimental tests, the radial crushing strength of the product is 67N/cm; at a use temperature of 20 ℃, the acid gas removal rate is 76.8%.
Comparative example 6
The procedure is as in comparative example 4.
Through experimental tests, the acid gas removal rate is 81.1% at the use temperature of 280 ℃.
Comparative example 7
The specific procedure is similar to comparative example 3, except that: 50 parts by weight of lime rotary kiln fly ash is adopted in the first component; ② in the step of sealing and heat preservation, the temperature is 140 ℃.
Through experimental tests, the radial crushing strength of the product is 56N/cm; at a use temperature of 220 ℃, the acid gas removal rate is 60.4%.
Comparative example 8
The specific procedure is similar to comparative example 3, except that: in the second component, 4 parts by weight of water granulated slag of an ore smelting furnace is adopted; ② in the third component, 2 weight portions of copperas are adopted; and thirdly, in the step of sealing and preserving heat, the temperature is 140 ℃.
The radial crushing strength of the product is 37N/cm through experimental tests; at a service temperature of 220 ℃, the acid gas removal rate is 65.4%.
Comparative example 9
The specific procedure is similar to comparative example 3, except that: in the step of sealing and heat preservation, the temperature is 140 ℃.
The radial crushing strength of the product is 185N/cm through experimental tests; at a use temperature of 320 ℃, the acid gas removal rate is 86.5 percent.
The compositions, proportions and test results of the components in the above examples and comparative experiments are shown in table 1.
So far, the embodiments of the present invention have been described in detail with reference to the accompanying drawings. It is to be noted that, in the attached drawings or in the description, the implementation modes not shown or described are all the modes known by the ordinary skilled person in the field of technology, and are not described in detail. Furthermore, the above definitions of the various elements and methods are not limited to the particular structures, shapes or arrangements of parts mentioned in the examples, which may be easily modified or substituted by one of ordinary skill in the art, for example:
(1) the grinding time, the sealing and heat-insulating time, and the like can be adjusted as required;
(2) besides the ball mill, other grinding equipment can be adopted to grind the materials, and the grinding mesh can be adjusted according to the requirement.
From the above description, those skilled in the art should clearly recognize the deacidification agent composition, the deacidification agent, the preparation method thereof and the application of the deacidification agent composition and the deacidification agent.
In conclusion, the deacidification agent has good deacidification effect, and has the advantages of stable product, high crushing strength and the like. In addition, the deacidification agent is prepared from common wastes, so that the production cost is greatly reduced, the equipment investment and the production cost are reduced, and the deacidification agent has higher economic benefit, environmental benefit and application prospect.
Unless expressly indicated to the contrary, the numerical parameters set forth in this specification and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by the present disclosure. In particular, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". Generally, the expression is meant to encompass variations of ± 10% in some embodiments, 5% in some embodiments, 1% in some embodiments, 0.5% in some embodiments by the specified amount.
Furthermore, the word "comprising" does not exclude the presence of materials or steps not listed in a claim. Ordinal numbers such as "first," "second," "third," and arabic numerals, letters, etc., used in the specification and claims to modify a corresponding element or step do not by itself connote a method of manufacture, and are used merely to clearly distinguish steps.
In addition, unless steps are specifically described or must occur in sequence, the order of the steps is not limited to that listed above and may be changed or rearranged as desired by the desired design. The embodiments described above may be mixed and matched with each other or with other embodiments based on design and reliability considerations, i.e., technical features in different embodiments may be freely combined to form further embodiments.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. The preparation method of the deacidification agent is characterized by comprising the following steps:
preparing 6-20 parts by weight of a second component and 4-16 parts by weight of copperas into powder, wherein the second component is ore smelting furnace water slag and/or ore smelting furnace dust; the water granulated slag of the ore smelting furnace is solid residue formed by placing molten slag in water and rapidly cooling the molten slag when a blast furnace or an electric furnace is used for smelting alloy; the dust removal ash of the ore smelting furnace is dust collected by a dust removal and collection device when a blast furnace or an electric furnace is used for smelting alloy;
adding 60-90 parts by weight of a first component into the powder to form a powdery dry powder material, wherein the first component is lime rotary kiln fly ash, fly ash and/or active lime powder; the lime rotary kiln fly ash refers to dust collected by a dust collector together after lime rotary kiln coal-fired flue gas passes through a rotary kiln and a preheater;
adding water to the dry powder to form a bulk material;
molding the bulk material;
and sealing and insulating the formed material, and then cooling to normal temperature to obtain the deacidification agent.
2. The method of claim 1, wherein:
the water granulated slag of the ore smelting furnace is silicon-manganese alloy smelting water granulated slag; and/or
The copperas are byproducts in the production of titanium dioxide by a sulfuric acid method, and the mass content of ferrous sulfate in the byproducts in the production of titanium dioxide by the sulfuric acid method is more than 40%.
3. The method of claim 1, wherein the step of powdering the second component and copperas comprises grinding the powder to a particle size of 120 mesh or less.
4. The method of claim 1, wherein in the step of adding water to the dry powder to form a bulk material:
adding water in a proportion of 40-120 parts by weight relative to 100 parts by weight of the dry powder;
the bulk material is formed by kneading for 15-45 minutes.
5. The preparation method according to claim 1, wherein the step of sealing and insulating the molded material comprises the steps of:
the temperature of sealing and heat preservation is 80-200 ℃; and/or
The sealing and heat preservation time is 2-12 hours.
6. The preparation method according to claim 1, wherein in the step of sealing and insulating the molded material, the humidity is kept above 85%;
wherein, the temperature and the humidity are maintained by introducing steam, and the steam pressure is 0.1-1.6 Mpa.
7. A deacidification agent, which is produced by the production method according to any one of claims 1 to 6.
8. The deacidification agent according to claim 7, wherein the deacidification agent is in the form of granules, cylindrical bars or clover bars.
9. The use of the deacidification agent of claim 7 or 8 in a fixed bed reactor or a moving bed reactor, wherein the deacidification agent is in an ambient temperature range of 20 to 280 ℃; the acid component content of the waste gas is as follows: SO (SO)2Less than 1000ppm, or less than 1000ppm HCl, or less than 1000ppm HF.
10. Use according to claim 9, wherein the exhaust gas is industrial flue gas.
11. The use of the deacidification agent as claimed in claim 7 or 8 in the purification treatment of exhaust gas, wherein the deacidification agent is used in an environment temperature range of 20-280 ℃; the acid component content of the waste gas is as follows: SO (SO)2Less than 1000ppm, or less than 1000ppm HCl, or less than 1000ppm HF.
12. Use according to claim 11, wherein the exhaust gas is industrial flue gas.
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