CN107930579B - Adsorbent for removing arsenic from flue gas and arsenic removing method thereof - Google Patents
Adsorbent for removing arsenic from flue gas and arsenic removing method thereof Download PDFInfo
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Abstract
The invention discloses an adsorbent for flue gas dearsenification and a dearsenification method thereof, and belongs to the technical field of flue gas dearsenification. The invention comprises calcium oxide, metallurgical slag, zeolite and fly ash; the addition amount of the fly ash is M4 ═ gamma (M1+ alpha M2-M3) -beta/(1-alpha) M2, wherein: m1 is the mass of calcium oxide, M2 is the mass of metallurgical slag, and M3 is the mass of zeolite; gamma is 0.15-0.25, and 1.5-2, wherein alpha is the mass percentage of CaO and MgO in the metallurgical slag; beta is Fe in metallurgical slag2O3And MnO by mass percentage. The invention prolongs the retention time of the arsenic and the oxide thereof on the surface of the adsorbent, provides longer reaction time for the reaction of the adsorbent and the arsenic and the oxide thereof, and promotes the reaction process of calcium oxide and arsenic; the coal ash and the converter slag act together to promote the decomposition of iron oxide, promote the reaction of arsenic and oxides thereof with iron oxide or active calcium oxide of the converter slag, and improve the adsorption effect of the adsorbent on arsenic.
Description
Technical Field
The invention belongs to the technical field of flue gas pollution removal, and particularly relates to an adsorbent for flue gas dearsenification and a dearsenification method thereof.
Background
Large amount of SO in flue gas2，NOxAnd the like, because of large discharge amount and high concentration, people have long carried out relevant research work on the pollutants and have obtained remarkable achievement. With the increasing environmental protection pressure, researchers find trace elements enriched in flue gasAfter entering the atmosphere, the trace elements also cause serious damage to human bodies and the environment, mainly because the trace elements have precipitability and mobility and are easily enriched on the surfaces of micron-level and submicron-level particles, sol is formed in the atmosphere and is suspended in the particles for a long time, and the trace elements enter the lungs of human bodies to cause serious respiratory diseases.
Wherein, arsenic is a global pollutant with great harm, has strong biological accumulation and carcinogenic teratogenicity, and is a great environmental problem threatening the health and ecological safety of human beings. Trace arsenic oxide in the atmosphere can poison people (the content of arsenic in the air is not more than 0.003mg/L), and the nervous system is damaged, and serious people even die. 60% to 75% of the total arsenic load in the atmosphere is caused by human activity factors. Wherein, the metal smelting occupies most of the metal smelting, and is about 35 to 65 percent. Therefore, research on arsenic removal of flue gas is urgently needed, and reasonable arsenic pollution control measures are explored.
Through searching, similar schemes are disclosed; for example: a device for removing arsenic and mercury in flue gas and a method for removing arsenic and mercury (application number: 201310750980.2, application date: 2013.12.31) comprise a denitration system, a dust remover, a magnetic separation machine, a mechanical screening machine and an injection system, wherein the denitration system is connected with a hearth, an outlet of the denitration system is connected with an inlet of the dust remover, the dust remover is connected with the magnetic separation machine and the mechanical screening machine, and the magnetic separation machine and the mechanical screening machine are connected with a pipeline in front of the inlet of the denitration system through the injection system. The device can effectively remove gaseous arsenic in the flue gas and can catalyze and oxidize elemental mercury in the flue gas. Although the technology can simultaneously reduce the emission of two pollutants of arsenic and mercury, no special adsorbent for arsenic removal exists, so that the emission reduction effect of arsenic needs to be further improved.
In addition, the integrated dedusting, desulfurizing and dearsenifying process for industrial fume includes absorbing SOx with inorganic sulfide while trapping dust particle in fume, reacting inorganic sulfide with mercury, arsenic and other toxic heavy metals in fume to produce insoluble sulfide salt, absorbing NOx with complexed ferrous iron, and regenerating absorbent with inorganic sulfide as reductant. Is favorable for removing toxic substances such as dust, SOx, NOx, mercury, arsenic and the like. Although the technology can simultaneously reduce emission of various pollutants, no special adsorbent for arsenic removal exists, so that the emission reduction effect of arsenic needs to be further improved.
Disclosure of Invention
1. Technical problem to be solved by the invention
The invention aims to solve the problem that the arsenic removal effect of flue gas is limited because no special adsorbent for removing arsenic from flue gas exists in the prior art, and provides an adsorbent for removing arsenic from flue gas and an arsenic removal method thereof.
2. Technical scheme
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the invention relates to an adsorbent for removing arsenic from flue gas, which comprises calcium oxide, metallurgical slag, zeolite and fly ash.
Preferably, the fly ash is added in an amount of M4 ═ γ (M1+ α M2-M3) - β/(1- α) M2, wherein: m1 is the mass of calcium oxide, M2 is the mass of metallurgical slag, and M3 is the mass of zeolite; gamma is 0.15-0.25, and 1.5-2, wherein alpha is the mass percentage of CaO and MgO in the metallurgical slag; beta is Fe in metallurgical slag2O3And MnO by mass percentage.
Preferably, the mass ratio of the calcium oxide to the metallurgical slag is 2.2 to 4.0.
Preferably, the metallurgical slag is converter slag, and Fe in the converter slag2O3The mass percentage content of (A) is more than 4.5%.
Preferably, the percentage of converter slag with a grain size of 0.074-5.0mm is more than 50%.
Preferably, the fly ash is modified by a modifier.
Preferably, the additive also comprises additives, wherein the additives comprise blast furnace ash, chromium slag and mullite.
Preferably, the additive is added in an amount of 2-5% of the adsorbent.
Preferably, the composite material further comprises an accelerant, wherein the accelerant is an organic substance with the length-diameter ratio of more than 1000.
According to the method for removing arsenic from flue gas by using the adsorbent, the flue gas passes through the adsorbent at the temperature of 400-900 ℃, and arsenic in the flue gas is adsorbed and removed by the adsorbent.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) the invention relates to an adsorbent for removing arsenic from flue gas, which can prolong the retention time of arsenic and oxides thereof on the surface of the adsorbent, provide longer reaction time for the reaction of the adsorbent, the arsenic and the oxides thereof, promote the electronic migration of calcium oxide by alkali metal in fly ash under high temperature condition, promote arsenic atoms to enter into vacancy or bridge position of O or top position of Ca, promote the reaction process of calcium oxide and arsenic, and form Ca-As compound: ca (AsO)2)2、Ca3(AsO4)2、Ca2As2O7And Ca3As2O8(ii) a Meanwhile, the coal ash and the converter slag act together to promote the decomposition of the iron oxide, and a large amount of metal in the coal ash promotes the formation of a large amount of reaction contact positions on the surface of the converter slag, promotes the reaction of arsenic and oxides thereof with the iron oxide or active calcium oxide of the converter slag, and improves the adsorption effect of the adsorbent on arsenic;
(2) according to the adsorbent for removing arsenic from flue gas, a large number of active ingredients in converter slag can promote the combination of arsenic and oxides thereof with calcium oxide and converter slag, and can directly react with arsenic, so that the adsorption effect of chemical adsorption is improved; the chemical adsorption fixes arsenic and oxides thereof, so that the arsenic content on the surface of the adsorbent is reduced, the physical adsorption is promoted, and the adsorption effect of the adsorbent on arsenic is improved.
Detailed Description
Exemplary embodiments of the invention are described in detail below, and although these exemplary embodiments are described in sufficient detail to enable those skilled in the art to practice the invention, it should be understood that other embodiments may be realized and that various changes to the invention may be made without departing from the spirit and scope of the invention. The following more detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is presented for purposes of illustration only and not limitation to describe the features and characteristics of the invention, to set forth the best mode of carrying out the invention, and to sufficiently enable one skilled in the art to practice the invention. Accordingly, the scope of the invention is to be limited only by the following claims.
Example 1
The invention relates to an adsorbent for removing arsenic from flue gas, which comprises calcium oxide, metallurgical slag, zeolite and fly ash. The addition amount of the fly ash is M4 ═ gamma (M1+ alpha M2-M3) -beta/(1-alpha) M2, wherein: m1 is the mass of calcium oxide, M2 is the mass of metallurgical slag, and M3 is the mass of zeolite; gamma is 0.15-0.25, and 1.5-2, wherein the following are noteworthy: alpha is the weight percentage content of CaO and MgO in the metallurgical slag; beta is Fe in metallurgical slag2O3And MnO by mass percentage. The mass ratio of calcium oxide to zeolite is 4 to 8, and 5 is used in this example.
60kg of calcium oxide, 20kg of metallurgical slag and 12kg of zeolite in the embodiment; the mass of the fly ash obtained by calculation is as follows: m4 ═ γ (60+ α 20-12) — (β/(1- α)20 ═ 8.14kg where γ is 0.2 and 1.5, fly ash has a large specific surface area, fly ash and zeolite have a good adsorption effect on arsenic, so that the retention time of arsenic and its oxides on the surface of the adsorbent can be extended, providing a longer reaction time for the reaction of the adsorbent with arsenic and its oxides. Under the combined action of the fly ash and calcium oxide, alkali metal in the fly ash can promote the electronic shift of the calcium oxide under high temperature conditions, promote arsenic atoms to enter vacant sites or bridge sites of O or top sites of Ca, promote the reaction process of the calcium oxide and the arsenic, and form Ca-As compounds: ca (AsO)2)2、Ca3(AsO4)2、Ca2As2O7And Ca3As2O8The calcium arsenate compounds can mutually occur under certain conditionsAnd (4) transformation. Meanwhile, the coal ash and the converter slag act together to promote the decomposition of the iron oxide, and a large amount of metal in the coal ash promotes the formation of a large amount of reaction contact positions on the surface of the converter slag to promote the reaction of arsenic and oxides thereof with the iron oxide or active calcium oxide of the converter slag; in addition, a large number of active ingredients in the converter slag can promote the combination of arsenic and oxides thereof with calcium oxide and the converter slag, and can directly react with arsenic, so that the adsorption effect of chemical adsorption is improved; chemisorption fixes arsenic and its oxide for the arsenic content on adsorbent surface reduces, and then has promoted going on of physisorption, and both complement each other, thereby improved adsorption effect, and then improved the adsorption effect of adsorbent to arsenic, and probably take place following reaction:
As2O3(g)+3CaO+O2(g)＝Ca3(AsO4)2
but on the other hand,because the addition of the fly ash is too large, an adsorption pore channel of the adsorbent is blocked, so that the adsorption effect is poor, and the transfer process from physical adsorption to chemical adsorption is influenced, therefore, the control of the composition in the adsorbent in the process is particularly important, so that the invention designs M4 ═ gamma (M1+ alpha M2-M3) -beta/(1-alpha) M2 through long-term research, and regulates and controls each component; the metallurgical slag is converter slag, and the converter slag comprises the following components in percentage by weight: 43.5% of SiO2：15.5％；Al2O3：3.8％；MgO：3.4％；Fe2O3: 5.2 percent; MnO: 2.4 percent; the balance being impurities.
The metallurgical slag is converter slag, and Fe in the converter slag2O3The mass percentage of (B) is more than 5%. The percentage content of the converter slag with the granularity of 0.074-5.0mm is more than 50 percent. The converter slag granularity is composed of the following components in percentage by mass: the granularity is less than or equal to 0.074 mm: 5%, 0.074-3.0 mm: 25%, 3.0-5.0 mm: 40 percent; 5.0-10.0 mm: 30 percent.
The fly ash of the embodiment is a fine particle obtained by quenching a fine particle in a vitreous state before a draught fan discharges coal-fired flue gas into the atmosphere, separating and collecting the fine particle through a dust remover, wherein the fly ash comprises the following components in percentage by mass: SiO 22：45.2％，Al2O3：28.6％，Fe2O3：8.7％，CaO：7.4％，MgO：3.6％，Na2O+K2O: 2.5 percent and the balance of impurities. The fly ash is modified by sodium hydroxide or potassium hydroxide, and the modifier is sodium hydroxide or potassium hydroxide; the method for treating the fly ash in the embodiment comprises the following steps: adding the fly ash into a sodium hydroxide solution, heating to 120 ℃ under a high pressure condition (the high pressure is 150-200 KPa) to react for 0.5-1h, and drying at 105 ℃ for 2h after the reaction is finished to obtain the modified fly ash.
The metallurgical slag is converter slag, and Fe in the converter slag2O3The mass percentage of (B) is more than 5%. The percentage content of the converter slag with the granularity of 0.074-5.0mm is more than 50 percent. The converter slag granularity is composed of the following components in percentage by mass: the granularity is less than or equal to 0.074 mm: 5%, 0.074-3.0 mm: 25%, 3.0-5.0 mm: 40 percent; 5.0-10.0 mm: 30 percent.
The fly ash of the embodiment is a fine particle obtained by quenching a fine particle in a vitreous state before a draught fan discharges coal-fired flue gas into the atmosphere, separating and collecting the fine particle through a dust remover, wherein the fly ash comprises the following components in percentage by mass: SiO 22：45.2％，Al2O3：28.6％，Fe2O3：8.7％，CaO：7.4％，MgO：3.6％，Na2O+K2O: 2.5 percent and the balance of impurities. The fly ash is modified by sodium hydroxide or potassium hydroxide, and the modifier is sodium hydroxide or potassium hydroxide; the method for treating the fly ash in the embodiment comprises the following steps: adding the fly ash into a sodium hydroxide solution, heating to 120 ℃ under a high pressure condition (the high pressure is 150-200 KPa) to react for 0.5-1h, and drying at 105 ℃ for 2h after the reaction is finished to obtain the modified fly ash.
The preparation method of the adsorbent of the embodiment comprises the following steps:
the method comprises the following steps: mixing the raw materials uniformly
(1) Preparation of mixture A: weighing calcium oxide, metallurgical slag and zeolite according to the parts by weight, sequentially adding the calcium oxide, the metallurgical slag and the zeolite into a stirrer, and uniformly mixing in the stirrer to obtain a mixture A;
(2) pretreating fly ash: adding the fly ash into a sodium hydroxide solution, heating the solution to 120 ℃ under the condition of 150-200 KPa to react for 0.5-1h, and drying the solution for 2h at 105 ℃ after the reaction is finished to obtain modified fly ash, wherein the concentration of the sodium hydroxide solution is 1.5 mol/L;
(3) calculating the mass of the fly ash according to a formula: m4 ═ γ (M1+ α M2-M3) - β/(1- α) M2, wherein: m1 is the mass of calcium oxide, M2 is the mass of metallurgical slag, and M3 is the mass of zeolite; gamma is 0.15-0.25, and 1.5-2, wherein alpha is the mass percentage of CaO and MgO in the metallurgical slag; beta is Fe in metallurgical slag2O3And MnO mass percentage content; adding the fly ash into the mixture A, and uniformly mixing to obtain a uniformly mixed adsorbent material;
step two: granulating
Adding the uniformly mixed adsorbent material prepared in the step one into a cylindrical mixer, adding water into the mixer, and preparing adsorbent particles after mixing and granulating;
step three: pretreatment of
Placing the adsorbent particles prepared in the second step into a microwave oven, carrying out microwave heating under the protection of nitrogen, heating to 800 ℃, and keeping the temperature for 30 min; the specific heating steps are as follows:
firstly, heating to 250 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 10 min;
secondly, heating to 800 ℃ at a heating rate of 10 ℃/min, and keeping the temperature for 30 min; obtaining an adsorbent after cooling; the adsorbent prepared by the method enables Ca-O, Si-O, Fe-O and Al-O on the surface of the adsorbent to be in a high-energy state, so that the adsorption performance of the adsorbent is improved. The method comprises the following steps that flue gas passes through an adsorbent at 400-900 ℃, the temperature selected in the embodiment is 800 ℃, the material layer thickness of the adsorbent is 500mm, and the flow rate of the flue gas is 0.2L/min; the content of arsenic in the flue gas at the inlet is 3 mg/L; the content of arsenic in the flue gas at the outlet is 0.58mg/L, and the emission reduction efficiency reaches 80.67%.
Example 2
The basic content of this embodiment is different from the embodiment in that: the additive comprises blast furnace ash, chromium slag and mullite; the composition comprises the following components in parts by mass: blast furnace ash: 60 percent, chromium slag: 20%, mullite: 20 percent. The additive is added in an external preparation mode, the addition amount of the additive is 1-2% of the adsorbent, and the addition amount of the additive is 1% in the embodiment, namely the addition amount of the additive is 1-2% of the sum of the mass of the calcium oxide, the metallurgical slag, the zeolite and the fly ash. Under the condition of high temperature, the metal element in the additive promotes electrons in the fly ash and the converter slag to shift under the high temperature condition, thereby promoting arsenic element in the flue gas to enter the vacancy and the bridge site of O in calcium oxide, improving the adsorption effect of the adsorbent on arsenic, and promoting the arsenic in the fly ash to enter the crystal lattice of vitreous aluminosilicate mineral by the metal in the additive to form AsO4 -3Is present in the form of an adsorbent; and the mullite powder in the additive can be attached to the surface of converter slag or calcium oxide, and the converter slag, the calcium oxide and the mullite areUnder the combined action of the components, the mullite crystal lattice is promoted; in addition, the blast furnace dust and the chromium slag contain a large amount of alkali metal elements which can form NaAs with arsenic3O8，KAs3O8，K3AsO4The performance of the compounds, which are generated along with the reaction of the compounds, is not very stable, but the intermediate products are utilized to improve the transient adsorption effect of the adsorbent, so that the arsenic and the oxides thereof can be adsorbed on the surface of the adsorbent, the retention time of the arsenic and the oxides thereof on the surface of the adsorbent is increased, and the chemical adsorption of the adsorbent is provided with a foundation. The method comprises the following steps that flue gas passes through an adsorbent at 400-900 ℃, the temperature selected in the embodiment is 400 ℃, the material layer thickness of the adsorbent is 500mm, and the flow rate of the flue gas is 0.2L/min; the arsenic content in the flue gas at the inlet is 2 mg/L; the content of arsenic in the flue gas at the outlet is 0.35mg/L, and the emission reduction efficiency reaches 82.50%.
The specific preparation method of the adsorbent of the invention is as follows:
the method comprises the following steps: mixing the raw materials uniformly
(1) Preparation of mixture A: weighing calcium oxide, metallurgical slag and zeolite according to the parts by weight, sequentially adding the calcium oxide, the metallurgical slag and the zeolite into a stirrer, and uniformly mixing in the stirrer to obtain a mixture A;
(2) pretreating fly ash: adding the fly ash into a sodium hydroxide solution, heating the solution to 120 ℃ under the condition of 150-200 KPa to react for 0.5-1h, and drying the solution for 2h at 105 ℃ after the reaction is finished to obtain modified fly ash, wherein the concentration of the sodium hydroxide solution is 1.5 mol/L;
(3) weighing blast furnace ash, chromium slag and mullite in parts by weight, uniformly mixing, cleaning in a sodium hydroxide solution, and drying after cleaning to obtain an additive;
(4) calculating the mass of the fly ash according to a formula: m4 ═ γ (M1+ α M2-M3) - β/(1- α) M2, wherein: m1 is the mass of calcium oxide, M2 is the mass of metallurgical slag, and M3 is the mass of zeolite; gamma is 0.15-0.25, and 1.5-2, wherein alpha is the mass percentage of CaO and MgO in the metallurgical slag; beta is Fe in metallurgical slag2O3And MnO mass percentage content; adding fly ash to mixture A, and thenAdding an additive into the mixture, and uniformly mixing to obtain a uniformly mixed adsorbent material;
step two: granulating
Adding the uniformly mixed adsorbent material prepared in the step one into a cylindrical mixer, adding water into the mixer, and preparing adsorbent particles after mixing and granulating;
step three: pretreatment of
Placing the adsorbent particles prepared in the step two into a microwave oven, and carrying out microwave heating under the protection of nitrogen to 800-; the specific heating steps are as follows:
firstly, heating to 300 ℃ at a heating rate of 5 ℃/min, and preserving heat for 10 min;
secondly, heating to 900 ℃ at a heating rate of 10 ℃/min, and preserving heat for 30 min; and obtaining the adsorbent after cooling.
Example 3
The basic content of this example is the same as example 1, and further includes a promoter, and the promoter is an organic substance having an aspect ratio greater than 1000. The accelerant of the embodiment is plant fiber or animal hair fiber or plastic fiber, the accelerant is added in an external preparation mode, the addition amount of the accelerant is 0.05-0.2% of the adsorbent, and the addition amount of the accelerant is 0.1% in the embodiment, namely the addition amount of the accelerant is 0.05-0.2% of the sum of the mass of calcium oxide, metallurgical slag, zeolite and fly ash; the mixture of animal hair fibers and cotton fibers is adopted in the embodiment, and the mass ratio of the hair fibers to the cotton fibers is 2: 1; by adding hair fibers and cotton fibers into the adsorbent, larger mesopores can be distributed in the treated adsorbent, so that the specific surface area of the adsorbent is greatly increased, and the adsorption effect of the adsorbent can be improved; in addition, the pore passages are communicated with each other, so that the conversion from physical adsorption to chemical adsorption is promoted, the chemical adsorption effect is improved, and the continuous performance of the physical adsorption is promoted; thereby improving the adsorption effect of the adsorbent. The method comprises the following steps that flue gas passes through an adsorbent at 400-900 ℃, the temperature selected in the embodiment is 700 ℃, the material layer thickness of the adsorbent is 500mm, and the flow rate of the flue gas is 0.2L/min; the content of arsenic in the flue gas at the inlet is 4 mg/L; the content of arsenic in the flue gas at the outlet is 0.45mg/L, and the emission reduction efficiency reaches 88.75 percent.
Example 4
The basic content of this embodiment is different from the embodiment in that: the additive comprises blast furnace dust, chromium slag, mullite, sepiolite and carbon nitride, wherein the mass percentage of each component is as follows: blast furnace ash: 50 percent, chromium slag: 20 percent; mullite: 10%, sepiolite: 10 percent; carbon nitride: 10 percent of additive is added in an external preparation mode, and the addition amount of the additive is 1.5 percent of that of the adsorbent. The additive can improve the specific surface area of the adsorbent in the physical adsorption process, thereby improving the adsorption effect of the adsorbent; flue gas passes through an adsorbent at 400-900 ℃, the temperature selected in the embodiment is 600 ℃, the material layer thickness of the adsorbent is 500mm, and the flow rate of the flue gas is 0.2L/min; the arsenic content in the flue gas at the inlet is 2 mg/L; the content of arsenic in the flue gas at the outlet is 0.308mg/L, and the emission reduction efficiency reaches 84.60%.
Example 5
The basic content of this embodiment is different from the embodiment in that: the additive comprises blast furnace dust, chromium slag, mullite, sepiolite and iron scale, wherein the mass percentage of each component is as follows: blast furnace ash: 50 percent, chromium slag: 20 percent; mullite: 10%, sepiolite: 5 percent; iron scale: 15 percent of additive is added in an external preparation mode, and the addition amount of the additive is 1.8 percent of that of the adsorbent. The additive can improve the specific surface area of the adsorbent in the physical adsorption process, so that the adsorption effect of the adsorbent is improved, and the iron scale improves the chemical reaction process of adsorption and improves the adsorption effect; the method comprises the following steps that flue gas passes through an adsorbent at 400-900 ℃, the temperature selected in the embodiment is 700 ℃, the material layer thickness of the adsorbent is 600mm, and the flow rate of the flue gas is 0.2L/min; the arsenic content in the flue gas at the inlet is 2 mg/L; the content of arsenic in the flue gas at the outlet is 0.29mg/L, and the emission reduction efficiency reaches 85.50%.
Example 6
The basic content of this embodiment is different from the embodiment in that: the additive comprises blast furnace dust, chromium slag, mullite, sepiolite and attapulgite, wherein the mass percentage of each component is as follows: blast furnace ash: 50 percent, chromium slag: 20 percent; mullite: 10%, iron scale: 10 percent; attapulgite clay: 10 percent of additive is added in an external preparation mode, and the addition amount of the additive is 2 percent of that of the adsorbent. The attapulgite clay mineral containing water and rich in magnesium and aluminum silicate with a chain layer structure is subjected to a series of heating treatments, and the additive can improve the specific surface area in the physical adsorption process of the adsorbent, so that the adsorption effect of the adsorbent is improved, the iron scale improves the chemical reaction process of adsorption, and the adsorption effect is improved; flue gas passes through an adsorbent at 400-900 ℃, the temperature selected in the embodiment is 600 ℃, the material layer thickness of the adsorbent is 500mm, and the flow rate of the flue gas is 0.2L/min; the content of arsenic in the flue gas at the inlet is 3 mg/L; the content of arsenic in the flue gas at the outlet is 0.47mg/L, and the emission reduction efficiency reaches 84.33%.
Example 7
The basic content of this embodiment is different from the embodiment in that: the adsorbent also comprises sintered return ores, the addition amount of the sintered return ores is 5-10% of calcium oxide, the addition amount is 5% in the embodiment, the sintered return ores are sintered return ores with the granularity of 3-5mm, and the sintered return ores are ground into fine powder with the granularity of 1-3 mm; the raw material mixing method of the embodiment comprises the following steps:
(1) preparation of mixture A: weighing calcium oxide, metallurgical slag and zeolite according to the parts by weight, sequentially adding the calcium oxide, the metallurgical slag and the zeolite into a stirrer, and uniformly mixing in the stirrer to obtain a mixture A;
(2) pretreating fly ash: adding the fly ash into a sodium hydroxide solution, heating the solution to 120 ℃ under the condition of 150-200 KPa to react for 0.5-1h, and drying the solution for 2h at 105 ℃ after the reaction is finished to obtain modified fly ash, wherein the concentration of the sodium hydroxide solution is 1.5 mol/L;
(3) calculating the mass of the fly ash according to a formula: m4 ═ γ (M1+ α M2-M3) - β/(1- α) M2, wherein: m1 is the mass of calcium oxide, M2 is the mass of metallurgical slag, and M3 is the mass of zeolite; gamma is 0.15-0.25, and 1.5-2, wherein alpha is the mass percentage of CaO and MgO in the metallurgical slag; beta is Fe in metallurgical slag2O3And MnO mass percentage content; feeding fly ash and sintered return oresAnd mixing, adding the mixture of the fly ash and the sintered return ores into the mixture A, and uniformly mixing to obtain the uniform adsorbent mixture. The sintered return ores provide a large number of reaction pore channels for the adsorbent, and the adsorption surface area of the adsorbent is improved, so that the adsorption effect of the adsorbent is improved; the method comprises the following steps that flue gas passes through an adsorbent at 400-900 ℃, the temperature selected in the embodiment is 500 ℃, the material layer thickness of the adsorbent is 600mm, and the flow rate of the flue gas is 0.2L/min; the content of arsenic in the flue gas at the inlet is 4 mg/L; the content of arsenic in the flue gas at the outlet is 0.72mg/L, and the emission reduction efficiency reaches 81.75 percent.
The invention has been described in detail hereinabove with reference to specific exemplary embodiments thereof. It will, however, be understood that various modifications and changes may be made without departing from the scope of the invention as defined in the appended claims. The detailed description is to be construed as illustrative only and not restrictive, and any such modifications and variations are intended to be included within the scope of the invention as described herein. Furthermore, the background is intended to be illustrative of the state of the art as developed and the meaning of the present technology and is not intended to limit the scope of the invention or the application and field of application of the invention.
More specifically, although exemplary embodiments of the invention have been described herein, the invention is not limited to these embodiments, but includes any and all embodiments modified, omitted, combined, e.g., between various embodiments, adapted and/or substituted, as would be recognized by those skilled in the art from the foregoing detailed description. The limitations in the claims are to be interpreted broadly based the language employed in the claims and not limited to examples described in the foregoing detailed description or during the prosecution of the application, which examples are to be construed as non-exclusive. Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims. The scope of the invention should, therefore, be determined only by the appended claims and their legal equivalents, rather than by the descriptions and examples given above.
Claims (8)
1. Is used forThe adsorbent for removing arsenic from flue gas is characterized in that: the composite material comprises calcium oxide, metallurgical slag, zeolite and fly ash, wherein the mass ratio of the calcium oxide to the metallurgical slag is 2.2-4.0, the addition amount of the fly ash is M4 ═ gamma (M1+ alpha M2-M3) -beta/(1-alpha) M2, and the following components in percentage by mass: m1 is the mass of calcium oxide, M2 is the mass of metallurgical slag, and M3 is the mass of zeolite; gamma is 0.15-0.25, and 1.5-2, wherein alpha is the mass percentage of CaO and MgO in the metallurgical slag; beta is Fe in metallurgical slag2O3And MnO mass percentage content;
the adsorbent is prepared by the following preparation steps, and the preparation steps are as follows:
the method comprises the following steps: the raw materials are mixed evenly
Uniformly mixing calcium oxide, metallurgical slag, zeolite and fly ash to prepare an adsorbent uniformly-mixed material;
step two: granulating
Adding the uniformly mixed adsorbent material prepared in the step one into a mixer, adding water into the mixer, mixing and granulating to obtain adsorbent particles;
step three: pretreatment of
And (3) placing the adsorbent particles prepared in the step two into a microwave oven, carrying out microwave heating under the condition of nitrogen protection, heating to 800-900 ℃, and preserving heat for 30 min.
2. The sorbent for arsenic removal from flue gas as claimed in claim 1, wherein: the metallurgical slag is converter slag, and Fe in the converter slag2O3The mass percentage content of (A) is more than 4.5%.
3. The sorbent for arsenic removal from flue gas as claimed in claim 1, wherein: the percentage content of the converter slag with the granularity of 0.074-5.0mm is more than 50 percent.
4. The sorbent for arsenic removal from flue gas as claimed in claim 1, wherein: the fly ash is modified by a modifier.
5. The sorbent for arsenic removal from flue gas according to any one of claims 1 to 4, wherein: the additive also comprises an additive, wherein the additive comprises blast furnace ash, chromium slag and mullite.
6. The sorbent for arsenic removal from flue gas as claimed in claim 5, wherein: the addition amount of the additive is 2-5% of the adsorbent.
7. The sorbent for arsenic removal from flue gas as claimed in claim 5, wherein: the composite material also comprises an accelerant, wherein the accelerant is an organic matter with the length-diameter ratio larger than 1000.
8. A method for arsenic removal from flue gas using the adsorbent according to any one of claims 1 to 7, wherein: the flue gas passes through the adsorbent at the temperature of 400-900 ℃, and the arsenic in the flue gas is adsorbed and removed by the adsorbent.
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