CN115040998B - Desulfurizing agent and desulfurizing method for flue gas - Google Patents
Desulfurizing agent and desulfurizing method for flue gas Download PDFInfo
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- CN115040998B CN115040998B CN202210972780.0A CN202210972780A CN115040998B CN 115040998 B CN115040998 B CN 115040998B CN 202210972780 A CN202210972780 A CN 202210972780A CN 115040998 B CN115040998 B CN 115040998B
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- steel slag
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/507—Sulfur oxides by treating the gases with other liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The invention belongs to the technical field of flue gas separation treatment, and particularly relates to a flue gas desulfurizer and a desulfurization method, which can replace the traditional lime-gypsum method of lime or limestone to realize wet desulfurization, wherein steel slag with the glass phase content of more than or equal to 85wt% is used as the desulfurizer of the flue gas, so that the effect of metal components in the steel slag can be fully exerted, higher sulfur capacity of flue gas desulfurization is obtained, and the high-efficiency treatment of sulfur-containing flue gas is realized; meanwhile, the steel slag is used as a desulfurizer of the flue gas, so that the resource utilization rate of the steel slag is improved, more obvious social benefits, environmental protection benefits and economic benefits are realized, and the industrial popularization and application are easy.
Description
Technical Field
The invention relates to the technical field of flue gas separation treatment, in particular to a flue gas desulfurizing agent and a desulfurizing method.
Background
The steel slag is a main waste produced in the steel production process, and because free calcium oxide and other harmful substances exist in the steel slag, the steel slag is difficult to be recycled. The basic chemical composition of the steel slag comprises 40 to 60 percent of CaO and 15 to 25 percent of Fe 2 O 3 And a small amount of MgO and MnO, theoretically having desulfurization performance. The steel slag is used for flue gas desulfurization, SO that SO can be solved 2 The problem of discharge, on the other hand, can solve the stability of the steel slag, and possibly become a new way for recycling the steel slag. However, there is a problem in that the consumption of steel slag is large under the condition of ensuring desulfurization efficiency of steel slag as compared with the conventional limestone/lime-gypsum method, and the consumption thereof is much larger than the amount of steel slag required by calculation based on its basic components. In order to use the steel slag to replace limestone and lime for flue gas desulfurization in a large scale, the desulfurization capability of the steel slag must be improved. Under the background, a great deal of research work is done by related scholars on improving the desulfurization capacity of the steel slag flue gas.
Chinese patent CN102614772A discloses a method for strengthening steel slag flue gas desulfurization by organic acid, which is to add acetic acid, citric acid, adipic acid, benzoic acid, humic acid or waste liquid generated in the production of acetic acid, furfural, lactic acid and citric acid with the concentration of 0.2 to 10 percent (wt) into a steel slag flue gas desulfurization dissolving tank. The organic acid is added in the method, so that the desulfurization cost is increased, and the treatment difficulty of the desulfurization solution is increased.
Chinese patent CN113930554A discloses an "integrated treatment method for grinding and desulfurizing steel slag" which directly crushes after the steel slag is formed and then is used for flue gas desulfurization. This patent illustrates the feasibility of steel slag for flue gas desulfurization but does not focus on steel slag flue gas desulfurization efficiency.
Chinese patent CN102671519A discloses a method for fixing carbon dioxide by mineralizing reinforced steel slag, which strengthens calcium oxide component and CO in steel slag by adding catalyst containing alkali metal salt 2 And reacting to improve the conversion rate of calcium oxide components in the steel slag and the carbon fixation efficiency of the steel slag. The method adds the alkali metal salt to improve the resource utilization cost of the steel slag.
In conclusion, the main problem restricting the large-scale application of steel slag flue gas desulfurization is the desulfurization efficiency of steel slag, namely the desulfurization rate and the sulfur capacity of the steel slag. At present, many researches on the improvement of the desulfurization and denitrification rate of the steel slag are carried out, but the researches on the improvement of the sulfur capacity of the steel slag are less.
Disclosure of Invention
The invention mainly aims to provide a desulfurizer and a desulfurization method for flue gas, which can improve the sulfur capacity of steel slag flue gas desulfurization, namely increase the SO content of steel slag 2 The fixing ability, and more obvious social benefit, environmental protection benefit and economic benefit are realized.
To solve the above technical problem, according to an aspect of the present invention, the present invention provides the following technical solutions:
the desulfurizer for the flue gas is steel slag with the glass phase content of more than or equal to 85wt percent.
As a preferred scheme of the desulfurizer for flue gas, the invention comprises the following steps: the steel slag can be prepared by adopting a steel slag cooling process commonly used in the field, and the steel slag only needs to meet the condition that the glass phase content of the steel slag is more than or equal to 85 wt%.
The preferable scheme of the desulfurizer for flue gas in the invention is as follows: the steel slag can be discharged and cooled by adopting a water quenching method, an air quenching method or a centrifugal granulation method and the like.
The preferable scheme of the desulfurizer for flue gas in the invention is as follows: the grain size of the steel slag is not specially required, for example, the grain size is not more than 200 meshes, not more than 230 meshes and the like, the steel slag does not need to be crushed in an ultramicro mode, the steel slag can be used after being crushed and sieved, and the preparation process is simple and easy to operate.
In order to solve the above technical problem, according to another aspect of the present invention, the present invention provides the following technical solutions:
the desulfurization method is to adopt the desulfurizer to carry out wet desulfurization. Can completely replace the traditional lime-gypsum wet desulphurization method adopting lime or limestone.
As a preferable embodiment of the method for desulfurizing flue gas according to the present invention, wherein: the wet desulphurization comprises a bubbling method and a spraying method.
As a preferable embodiment of the method for desulfurizing flue gas according to the present invention, wherein: the flue gas can be one or more of waste heat flue gas of a coal-fired power plant, waste heat flue gas of a lime kiln, sintering flue gas of an iron and steel plant, waste heat flue gas of a chemical plant and waste heat flue gas of a cement plant.
As a preferable embodiment of the method for desulfurizing flue gas according to the present invention, wherein: SO of the flue gas 2 The concentration is 500 to 20000ppm.
The application of the desulfurizer for the flue gas or the desulfurization method for the flue gas in the field of flue gas treatment.
The invention has the following beneficial effects:
the invention provides a desulfurizer and a desulfurization method for flue gas, which can replace the traditional lime-gypsum method of lime or limestone to realize wet desulfurization, and steel slag with the glass phase content of more than or equal to 85wt% is used as the desulfurizer for the flue gas, so that the effect of metal components in the steel slag can be fully exerted, higher sulfur capacity of flue gas desulfurization is obtained, and the high-efficiency treatment of sulfur-containing flue gas is realized; meanwhile, the steel slag is used as a desulfurizer of the flue gas, so that the resource utilization rate of the steel slag is improved, more obvious social benefits, environmental protection benefits and economic benefits are realized, and the industrial popularization and application are easy.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is an XRD pattern of water quenched steel slag and furnace cooled steel slag.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
The invention provides a desulfurizer of flue gas and a desulfurization method, wherein steel slag with a glass phase content of more than or equal to 85wt% is used as the desulfurizer of the flue gas, the steel slag is used as the desulfurizer of the flue gas, so that the resource utilization rate of the steel slag is improved, the steel slag can replace the traditional lime-gypsum method of lime or limestone to realize wet desulfurization, the effect of metal components in the steel slag is fully exerted, the higher sulfur capacity of flue gas desulfurization is obtained, the high-efficiency treatment of sulfur-containing flue gas is realized, and the more obvious social benefit, environmental protection benefit and economic benefit are obtained, so that the desulfurizer of the flue gas is easy to industrially popularize and apply.
According to one aspect of the invention, the invention provides the following technical scheme:
the desulfurizer for the flue gas is steel slag with the glass phase content of more than or equal to 85wt percent. The inventor finds that the metal component in the glass phase of the steel slag is easier to dissociate and fix SO 2 The higher sulfur capacity of the flue gas desulfurization can be obtained by controlling the glass phase content of the steel slag. Specifically, the glass phase content of the steel slag is any one of, for example but not limited to, 85wt%, 88wt%, 90wt%, 92wt% and 95 wt%.
The steel slag can be prepared by adopting a steel slag cooling process commonly used in the field, and the steel slag can meet the condition that the content of a glass phase of the steel slag is more than or equal to 85 wt%. For example, water quenching, air quenching, centrifugal granulation, or the like can be used, and the phase analysis of the steel slag after treatment is shown in FIG. 1. Preferably, the steel slag can be prepared by adopting the following treatment process: and discharging the molten steel slag, controlling the cooling speed of the steel slag to be more than 10 ℃/s within the temperature range from the molten state temperature to 1000 ℃, and then cooling the steel slag to room temperature to obtain the steel slag with the glass phase content of more than or equal to 85 wt%. Specifically, the cooling rate of the steel slag from the molten state temperature to the temperature range of 1000 ℃ can be any one of, but not limited to, more than 15 ℃/s, more than 20 ℃/s, more than 25 ℃/s, more than 30 ℃/s, more than 35 ℃/s, more than 40 ℃/s, more than 45 ℃/s, and more than 50 ℃/s, and the cooling rate of the steel slag below 1000 ℃ is not required.
The grain size of the steel slag is not specially required, the grain size of the steel slag can be any one of, but not limited to, 200 meshes or less, 230 meshes or less, 270 meshes or less, 300 meshes or less, 325 meshes or less and 400 meshes or less, the steel slag does not need to be subjected to superfine grinding, the steel slag can be used after being crushed and screened, and the preparation process is simple and easy to operate.
According to another aspect of the invention, the invention provides the following technical scheme:
the desulfurization method is to adopt the desulfurizer to carry out wet desulfurization. Can completely replace the traditional lime-gypsum wet desulphurization method adopting lime or limestone.
The wet desulphurization comprises a bubbling method and a spraying method. The flue gas can be one or more of waste heat flue gas of a coal-fired power plant, waste heat flue gas of a lime kiln, sintering flue gas of an iron and steel plant, waste heat flue gas of a chemical plant and waste heat flue gas of a cement plant. SO of the flue gas 2 The concentration is 500 to 20000ppm, specifically, the SO of the flue gas 2 The concentration is, for example, but not limited to, a range consisting of any one or any two of 500ppm, 1000ppm, 3000ppm, 5000ppm, 10000ppm, 15000ppm, 20000ppm.
The invention also protects the application of the desulfurizer for flue gas or the desulfurization method for flue gas in the field of flue gas treatment.
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1
Taking a certain amount of steel slag obtained by remelting and then carrying out centrifugal granulation (the cooling speed is about 11.8 ℃/s, and the particle size is<74 mu m) and deionized water into a mixed solution with a solid-to-liquid ratio of 1 -1 . Hydrolyzing the steel slag powder for 10min, and introducing SO after the pH value is stable 2 Mixed gas (flow rate 600 mL/min) -1 ) Carrying out bubbling flue gas desulfurization, and recording the tail gas SO once at intervals of 10min 2 And (4) stopping introducing the mixed gas after the concentration value reaches a set value (the end point of the desulfurization rate is set as 90%), and ending the reaction. And directly drying the reaction liquid to obtain a desulfurization product, and testing the sulfur content of the desulfurization product to obtain the sulfur capacity of the steel slag. Tested the desulfurization rate>95 percent, and the sulfur capacity of the desulfurized flue gas is 0.632.
Example 2
The present embodiment is different from embodiment 1 in that,
the added steel slag is the steel slag obtained by water quenching after remelting (the cooling speed is about 13.3 ℃/s), and the components of the steel slag are consistent with those of the steel slag obtained by centrifugal granulation. The test shows that the desulfurization rate is more than 95 percent, and the sulfur capacity is 0.649 after the flue gas is desulfurized.
Comparative example 1
The comparative example is different from example 1 in that,
the added steel slag is steel slag cooled along with the furnace after remelting (the cooling speed is about 0.05 ℃/s), and the components of the steel slag are consistent with those of the steel slag obtained by centrifugal granulation. The desulfurization rate is more than 95% by test, and the sulfur capacity is 0.404 by test after the flue gas is desulfurized.
Comparative example 2
This comparative example differs from example 1 in that,
the added steel slag is air-cooled steel slag which is blown and cooled by a fan after remelting (the cooling speed is about 0.4 ℃/s), and the components of the steel slag are consistent with those of the steel slag obtained by centrifugal granulation. The desulfurization rate is over 95 percent through testing, and the sulfur capacity is 0.435 percent through testing after the flue gas is desulfurized.
Comparative example 3
The comparative example is different from example 1 in that,
the added steel slag is naturally cooled in the air after remelting (the cooling speed is about 0.15 ℃/s), and the components of the steel slag are consistent with those of the steel slag obtained by centrifugal granulation. The test shows that the desulfurization rate is more than 95 percent, and the sulfur capacity is 0.442 after the flue gas is desulfurized.
Comparative example 4
This comparative example differs from example 1 in that,
the added desulfurizer is CaCO 3 And (3) a reagent. Tested for its desulfurization rate>92% and the sulfur capacity after flue gas desulfurization is 0.647.
Comparative example 5
This comparative example differs from example 1 in that,
the added desulfurizer is CaO reagent. The desulfurization rate is over 98 percent through testing, and the sulfur capacity is 1.106 through testing after the flue gas is desulfurized.
XRD analysis (as shown in figure 1) is carried out on the water-quenched steel slag and the furnace-cooled steel slag thereof, so that the fundamental difference of the desulfurization performance of the steel slag is the composition of the phase thereof, the composition of the phase of the water-quenched steel slag (example 2) is mainly glass phase, the content of the glass phase is 90wt% through testing, and the content of the glass phase of the steel slag (example 1) obtained through centrifugal granulation is 85%; from the analysis results of the sulfur capacity of each example and comparative example, it can be seen that the sulfur capacity of the water-quenched steel slag is the conventional desulfurizing agent CaCO 3 The sulfur capacity of the slag is 97.7%, the sulfur capacity of the water-quenched steel slag (example 2) is improved by 60.64% compared with the sulfur capacity of the furnace-cooled steel slag (comparative example 1), the sulfur capacity of the steel slag obtained by centrifugal granulation (example 1) is improved by 56.44% compared with the sulfur capacity of the furnace-cooled steel slag (comparative example 1), and thus the steel slag with the glass phase content of more than 85wt% improves the sulfur capacity of the steel slag, has excellent desulfurization performance, and can obtain the steel slag with higher glass phase content by rapid cooling, so the desulfurization performance of the steel slag obtained by rapid cooling can be improved.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields within the spirit of the present invention are included in the scope of the present invention.
Claims (4)
1. The application of the desulfurizer for the flue gas in the field of flue gas treatment is characterized in that the desulfurizer is steel slag with the glass phase content of more than or equal to 85 wt%.
2. The application of the desulfurizer for flue gas in the field of flue gas treatment according to claim 1, wherein the particle size of the steel slag is not more than 200 meshes.
3. The application of the desulfurizer for flue gas in the field of flue gas treatment according to claim 1, wherein the steel slag is prepared by a water quenching method, a wind quenching method or a centrifugal granulation method.
4. The application of the desulfurizer for flue gas in the field of flue gas treatment according to claim 1, wherein the steel slag is prepared by the following process: the molten steel slag is discharged, the cooling speed is more than 10 ℃/s within the temperature range from the molten state temperature to 1000 ℃, and then the molten steel slag is cooled to the room temperature.
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