CN115814580A - Carbide slag modified desulfurizer composition, desulfurizer, preparation method and application thereof - Google Patents
Carbide slag modified desulfurizer composition, desulfurizer, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a desulfurizer composition modified by carbide slag, a desulfurizer, a preparation method and an application thereof. The carbide slag modified desulfurizer composition comprises the following components in parts by weight: 60-90 parts of carbide slag; 50-300 parts of hydrogen peroxide, wherein the concentration of the hydrogen peroxide in the hydrogen peroxide is 10-50%; 10-30 parts of a binder; 180 to 720 portions of water. According to the invention, the acetylene sludge is modified by using hydrogen peroxide, so that the specific surface area and the effective pore volume of the acetylene sludge are increased after modification, and the desulfurization performance of the desulfurizer can be improved.
Description
Technical Field
The invention relates to the fields of chemical industry, energy, environmental protection and the like, in particular to a carbide slag modified desulfurizer composition, a desulfurizer, a preparation method and an application thereof.
Background
SO2 is one of main pollutants of atmospheric pollutants, mainly comes from the utilization of coal, however, the coal cannot be completely replaced in a short time, methods such as coal desulfurization, in-furnace desulfurization and the like are adopted for controlling SO2 emission at present, but a flue gas desulfurization method is a method which is fast in progress and obvious in effect at present, is low in investment and simple in operation and operation, and also becomes the most widely applied desulfurization method at present.
Flue gas desulfurization is also classified into two types: one is wet flue gas desulfurization and the other is called dry flue gas desulfurization. The dry flue gas desulfurization is mainly characterized in that: the desulfurization efficiency is high and stable, the operation flexibility is good, the operation control is easy, the desulfurization process is simple, and the management is easy; the dry flue gas desulfurization and dust removal can be simultaneously completed, the pipeline of the equipment is not easy to corrode, no waste water is discharged, and the corrosion of the equipment and the trouble of waste water treatment are reduced; the smoke temperature in the purification process is reduced, the waste heat is easy to recover, and the smoke is discharged from high altitude. Among dry flue gas desulfurization technologies, dry desulfurization agents are the most important research and development directions.
The carbide slag contains carbide slag and percolate with certain water content, and also contains toxic and harmful substances such as sulfide, phosphide and the like, and shows strong basicity. The main components of the carbide slag comprise calcium hydroxide (the mass fraction is 90.1%), silicon oxide (the mass fraction is 3.5%), aluminum oxide (the mass fraction is 2.5%) and a small amount of impurities such as calcium carbonate, ferric oxide, magnesium oxide, titanium dioxide, carbon slag, calcium sulfide and the like. Carbide slag is grey and associated with a pungent smell. At present, the research on the preparation of the desulfurizer by using carbide slag has been reported, and the desulfurizer is applied to wet desulfurization and dry desulfurization.
In the process of implementing the invention, the applicant finds that the traditional desulfurization product taking carbide slag as a main raw material has low desulfurization efficiency, can not realize the long-term goal of treating wastes with wastes, and can not meet the requirement of actual production.
Disclosure of Invention
Technical problem to be solved
In view of this, the present invention is intended to partially solve the problem of low desulfurization efficiency.
(II) technical scheme
In order to achieve the above object, according to a first aspect of the present invention, there is provided a desulfurizing agent composition. The carbide slag modified desulfurizer composition comprises the following components in parts by weight: 60-90 parts of carbide slag; 50-300 parts of hydrogen peroxide, wherein the concentration of the hydrogen peroxide in the hydrogen peroxide is between 10% and 50%; 10-30 parts of a binder; 180 to 720 portions of water.
In some embodiments of the invention, further comprising: 5-20 parts of an auxiliary agent; wherein the auxiliary agent comprises one or more of the following materials: ferric sulfate, ferrous sulfate, ferric acetate, ferric chloride and ferric nitrate.
In some embodiments of the invention, the binder comprises one or more of the following materials: cement, gypsum, kaolin, attapulgite, bentonite and diatomite.
In order to achieve the above object, according to a second aspect of the present invention, there is also provided a desulfurizing agent preparation method using the above desulfurizing agent composition. The preparation method of the desulfurizer comprises the following steps:
step A, mixing carbide slag and water for pulping to obtain carbide slag slurry;
step B, mixing the carbide slag slurry and hydrogen peroxide for reaction to obtain calcium peroxide slurry;
step C, adding a binder into the calcium peroxide slurry to obtain a wet desulfurizer material;
step D, forming the wet desulfurizer into a desulfurizer semi-finished product;
and E, drying the semi-finished product of the desulfurizer to obtain a finished product of the desulfurizer.
In some embodiments of the invention, step B comprises: under the low-temperature environment of-20 to 0 ℃, the carbide slag slurry and the hydrogen peroxide are mixed by adopting a parallel flow process, and the mixing ratio of the carbide slag slurry and the hydrogen peroxide is controlled by the flow rate.
In some embodiments of the invention, the desulfurization composition further comprises: 5-20 parts of an auxiliary agent; wherein the auxiliary agent comprises one or more of the following materials: ferric sulfate, ferrous sulfate, ferric acetate, ferric chloride and ferric nitrate.
In some embodiments of the invention, in the method of preparation, step C comprises: and adding an auxiliary agent and a binder into the calcium peroxide slurry to obtain the wet desulfurizer material.
In some embodiments of the invention, in step a, the weight ratio of the carbide slag to the water is between 1:3 and 1:8; in the step B, the weight ratio of the carbide slag to the hydrogen peroxide is 1.5-1:3; in the step C, the weight ratio of the carbide slag, the auxiliary agent and the binder is as follows: 1.
In some embodiments of the invention, step E comprises: drying the semi-finished product of the desulfurizer at the temperature of between 50 and 200 ℃ for 1 to 8 hours to obtain a finished product of the desulfurizer.
In order to achieve the above object, according to a third aspect of the present invention, there is also provided a desulfurizing agent prepared by the above desulfurizing agent preparation method. Wherein, the finished product of the desulfurizer is cylindrical, clover-shaped or plum blossom-shaped.
In order to achieve the above object, according to a fourth aspect of the present invention, there is also provided a desulfurizing agent composition as above, and an application of the desulfurizing agent in low temperature flue gas desulfurization. Wherein the low-temperature flue gas is low-temperature heating furnace flue gas, ceramic flue gas and garbage power generation tail gas.
(III) advantageous effects
According to the technical scheme, the invention has at least one of the following beneficial effects:
(1) The hydrogen peroxide is a strong oxidizing liquid and can oxidize the carbide slag to generate calcium peroxide. Calcium peroxide has strong oxidizing property with SO 2 Reacting to obtain 2CaO 2 +2SO 2 ＝2CaSO 3 +O 2 ，CaO 2 +SO 2 ＝CaSO 4 (ii) a And after modification, the specific surface area and the effective pore volume of the carbide slag are increased, and the desulfurization performance of the desulfurizer can be improved.
In addition, the calcium peroxide has the characteristic of slowly releasing oxygen in a damp and hot smoke environment, and 2CaO 2 +2H 2 O＝2Ca(OH) 2 +O 2 The pore volume of the desulfurizer is increased, the vacancy is obvious, more active components can be exposed, and the desulfurization performance is improved. Of even greater importance are the following in harsh flue gas conditions, such as: the existence of strong oxidant calcium peroxide in the environment of low nitrogen oxide and no nitrogen oxide improves SO 2 To SO 3 The conversion efficiency is improved, and the desulfurization efficiency is enhanced.
(2) Compared with other oxidation modes, for example, adding oxygen or ozone into water to oxidize the carbide slag, the method has the advantages that the oxygen or ozone has extremely low solubility in water, so that the oxidation reaction efficiency is extremely low, and the oxidation effect on the carbide slag is limited. In the invention, the hydrogen peroxide is obtained by dissolving hydrogen peroxide in water, and the concentration can be adjusted. The combined use of the parallel flow process can thoroughly oxidize the carbide slag and has better effect.
(3) The method has the advantages that the usage amounts of the carbide slag slurry and the hydrogen peroxide are calculated in advance, different flow rates are controlled respectively, liquid-liquid phase contact is carried out through a parallel flow process, mixed reaction of the carbide slag slurry and the hydrogen peroxide is achieved, the usage amount of the hydrogen peroxide is the minimum, the best effect of oxidation is achieved, raw material cost is saved, and energy consumption is reduced.
(4) The soluble ferric salt auxiliary agent is introduced, so that the uniform distribution of iron ions is facilitated, and the iron ions have a catalytic oxidation effect and can improve the desulfurization efficiency.
(5) The desulfurizer of the invention introduces the industrial byproduct of carbide slag, has cheap and easily available raw materials, simple preparation process and high desulfurization efficiency, can recycle the used waste agent, does not cause harm to the environment, and is energy-saving and environment-friendly.
Drawings
FIG. 1 is a flow chart of a method for preparing a desulfurizing agent according to an embodiment of the present invention.
Detailed Description
The invention utilizes hydrogen peroxide to modify the carbide slag to generate calcium peroxide to SO in the flue gas 2 The desulfurization efficiency of the desulfurizer can be effectively improved by removing the sulfur.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings in combination with the specific embodiments.
According to a first aspect of the present invention, a desulfurization composition is provided. The desulfurizer composition comprises the following components in parts by weight: 60-90 parts of carbide slag; 50-300 parts of hydrogen peroxide; 10-30 parts of a binder; 5-20 parts of an auxiliary agent; a proper amount of water.
Wherein the auxiliary agent comprises one or more of the following materials: ferric sulfate, ferrous sulfate, ferric acetate, ferric chloride and ferric nitrate. It can be seen that iron ions are introduced into the adjuvant. The soluble ferric salt auxiliary agent is introduced, so that the uniform distribution of iron ions is facilitated, and the iron ions have a catalytic oxidation effect and can improve the desulfurization efficiency.
Wherein the binder comprises one or more of the following materials: cement, gypsum, kaolin, attapulgite, bentonite and diatomite. Of course, the above are only examples, and other binder materials commonly used in the art can be used in the desulfurizing agent composition of the present invention, and are not described herein again.
Wherein, the water is used for mixing the carbide slag to prepare the carbide slag slurry, and the dosage of the water can be adjusted according to the requirement, and the water is not strictly limited here. The reference amount of water is 180 to 720 parts by weight.
According to a second aspect of the present invention, there is also provided a desulfurizing agent preparation method using the above desulfurizing agent composition. FIG. 1 is a flow chart of a method for preparing a desulfurizing agent according to an embodiment of the present invention. As shown in FIG. 1, the preparation method of the desulfurizing agent of this example includes:
step A, mixing carbide slag with water for pulping to obtain carbide slag slurry;
specifically, the carbide slag and water are mixed according to the weight ratio of 1:3-1:8 for pulping.
Step B, mixing the carbide slag slurry and hydrogen peroxide for reaction to obtain calcium peroxide slurry;
specifically, hydrogen peroxide with the hydrogen peroxide concentration of 30% is adopted, the carbide slag slurry and the hydrogen peroxide are mixed by adopting a parallel flow process in a low-temperature environment of-20-0 ℃, and the mixing ratio of the carbide slag slurry and the hydrogen peroxide is controlled by the flow rate. And fully stirring the carbide slag and hydrogen peroxide according to the weight ratio of 1.5-1:3 to obtain uniform calcium peroxide slurry.
The oxydol is easy to volatilize and decompose at normal temperature to reduce the oxidability, so the step B is arranged to be carried out in a low-temperature environment of-20 to 0 ℃, the volatilization and decomposition of the oxydol can be reduced, and the effective components of the oxydol and the carbide slag can be favorably kept to react. Although the present invention is described by taking 30% hydrogen peroxide as an example, it will be understood by those skilled in the art that the present invention can be implemented with hydrogen peroxide at a concentration of 10% to 50%.
Step C, adding an auxiliary agent and a binder into the calcium peroxide slurry to obtain a wet desulfurizer material;
in this example, the adjuvant is added to the calcium peroxide slurry first, followed by the binder. The weight ratio of the carbide slag to the auxiliary agent to the binder is as follows: 1. In the process of adding the auxiliary agent and the binder, the stirring is strengthened to ensure that the reaction is complete. And D, reserving the wet desulfurizer material filtrate obtained in the step C as an extruded strip for later use.
Step D, forming the wet desulfurizer into a desulfurizer semi-finished product;
in the step, the cylindrical or clover-shaped material is obtained by extrusion molding on a molding machine. It will be understood by those skilled in the art that, in addition to the above shapes, the wet desulfurization agent can be kneaded into other desired shapes using shaping equipment commonly used in the art, and will not be described herein.
And E, drying the semi-finished product of the desulfurizer to obtain a finished product of the desulfurizer.
In the step, the semi-finished product of the desulfurizer is dried for 1 to 8 hours at a temperature of between 50 and 200 ℃, preferably at a temperature of between 100 and 150 ℃ for 2 to 5 hours, and finally the required finished product of the desulfurizer is obtained.
According to a third aspect of the present invention, there is also provided a desulfurizing agent prepared by the above method for preparing a desulfurizing agent.
According to the fourth aspect of the invention, the desulfurizer composition and the application of the desulfurizer in low-temperature flue gas desulfurization are also provided. Wherein the low-temperature flue gas is low-temperature heating furnace flue gas, ceramic flue gas and garbage power generation tail gas.
Regarding the above four aspects of the present invention, the following five points need to be explained:
1. function of hydrogen peroxide modified carbide slag
The hydrogen peroxide is a strong oxidizing liquid, and the volatilization and decomposition of the hydrogen peroxide can be reduced in a low-temperature environment; oxidizing the carbide slag to generate calcium peroxide. Calcium peroxide has strong oxidizing property with SO 2 Reaction of (a) withObtaining 2CaO 2 +2SO 2 ＝2CaSO 3 +O 2 ，CaO 2 +SO 2 ＝CaSO 4 (ii) a And after modification, the specific surface area and the effective pore volume of the carbide slag are increased, and the desulfurization performance of the desulfurizer can be improved.
The calcium peroxide has the characteristic of slowly releasing oxygen in a damp and hot smoke environment, and 2CaO 2 +2H 2 O＝2Ca(OH) 2 +O 2 The pore volume of the desulfurizer is increased, the vacancy is obvious, more active components can be exposed, and the desulfurization performance is improved. Of even greater importance are, under harsh flue gas conditions, such as: the existence of strong oxidant calcium peroxide in the environment of low nitrogen oxide and no nitrogen oxide improves SO 2 To SO 3 The conversion efficiency is improved, and the desulfurization efficiency is enhanced.
2. Advantages compared with other oxidation modes
Reference 1 (CN 101642674B) provides a wet flue gas desulfurization process for carbide slag slurry pretreatment, and the desulfurizer is modified carbide slag slurry: the method comprises the specific steps of adding manganese sulfate into carbide slag slurry, and oxidizing the mixture by air to obtain Mn which is uniformly distributed and has oxidation activity 4+ The carbide slag slurry;
reference 2 (CN 101816891B) provides an ozone wet flue gas desulfurization process for carbide slag pretreatment, which uses carbide slag as a desulfurizing agent to perform wet flue gas desulfurization, and introduces a mixed gas of ozone and oxygen in the carbide slag slagging process to perform oxidation reaction to oxidize reducing substances in the carbide slag, and then uses the carbide slag after the oxidation reaction as a desulfurizing agent for wet flue gas desulfurization.
With the solutions proposed in references 1 and 2, oxygen or ozone is added into water to oxidize the carbide slag, and because the solubility of oxygen or ozone in water is very low and the stability is very poor, the efficiency of the oxidation reaction is very low, and the oxidation effect on the carbide slag is limited. And oxygen or ozone is continuously introduced for a long time, the process is not easy to control, the cost is high, and the popularization in the industry is difficult. Meanwhile, with the solution proposed in reference 2, ozone that is not dissolved in the carbide slag-melting process overflows from the reaction vessel, causing environmental pollution, and when the concentration reaches a certain level, it causes cough, dyspnea and pulmonary dysfunction, and is also seriously life-threatening, and how to handle it is also a very delicate problem.
In the invention, the calcium carbide slag modified by hydrogen peroxide can generate a stable calcium peroxide product only by using a proper amount of hydrogen peroxide, so that higher desulfurization efficiency is achieved; has stronger oxidability than manganese ions and stable oxidation efficiency than ozone, and the decomposition product of hydrogen peroxide is H 2 O and O 2 Green and environment-friendly, and stronger adaptability. In addition, the hydrogen peroxide is obtained by dissolving hydrogen peroxide in water, the concentration can be adjusted, the reaction is sufficient, and the control is convenient.
3. Parallel flow process
In the invention, in order to improve the utilization efficiency of the hydrogen peroxide, the carbide slag slurry and the hydrogen peroxide are reacted by adopting a parallel flow process. Specifically, the usage amounts of the carbide slag slurry and the hydrogen peroxide are calculated in advance, different flow rates are controlled respectively, liquid-liquid phase contact is carried out through a parallel flow process, and mixed reaction of the carbide slag slurry and the hydrogen peroxide is achieved, so that the usage amount of the hydrogen peroxide is the minimum, the optimal oxidation effect is achieved, the raw material cost is saved, and the energy consumption is reduced.
4. Soluble ferric salt adjuvant
In the invention, the soluble ferric salt auxiliary agent is introduced, which is beneficial to the uniform distribution of ferric ions, and the ferric ions have catalytic oxidation effect and can improve the desulfurization efficiency.
5. Efficiency, cost and product reuse
1. Low cost
The invention introduces the industrial byproduct carbide slag, has cheap and easily obtained raw materials and low implementation cost.
2. No poison, harm and pollution
The introduced hydrogen peroxide can not generate toxic and harmful products except the effective components of the desulfurizer. In addition, unreacted hydrogen peroxide can be reused, and even if a small amount of hydrogen peroxide is volatilized into air, the hydrogen peroxide can be quickly decomposed into water and oxygen by light, so that the hydrogen peroxide cannot damage a human body.
3. High efficiency and wide adaptability
The desulfurizer provided by the invention has low cost and simple preparation process, has the desulfurization efficiency of over 95 percent, and can be used for the desulfurization of medium and low temperature flue gas with large water content in a dry method and a semi-dry method, such as flue gas of a low-temperature heating furnace, ceramic flue gas, garbage power generation tail gas and other working conditions.
The present invention will be described below with reference to specific comparative examples and examples, which will be described below in relation to the desulfurizing agent composition, the desulfurizing agent, the method for producing the desulfurizing agent, the use thereof and the like.
Comparative example 1
The desulfurizing agent composition comprises: 90g of carbide slag, 10g of kaolin and 40g of water
The preparation method of the desulfurizer comprises the following steps: and (3) uniformly mixing the carbide slag and the kaolin, adding water, kneading, extruding and drying to obtain the sample of the comparative example 1.
Comparative example 2
The desulfurizing agent composition comprises: 80g of carbide slag, 10g of ferric sulfate, 10g of diatomite and 40g of water
The preparation method of the desulfurizer comprises the following steps: and (3) uniformly mixing the carbide slag, ferric sulfate and diatomite, adding water, kneading, extruding, and drying to obtain the sample of the comparative example 2.
Comparative example 3
The desulfurizing agent composition comprises: 80g of carbide slag, 1h of ozone (about 1 g), 10g of ferrous sulfate, 10g of kaolin and 300g of water are introduced.
The preparation method of the desulfurizer comprises the following steps: mixing carbide slag and water to prepare 1:4, introducing ozone, and filtering to obtain a wet cake and a filtrate; the wet cake was dried, milled, mixed with ferrous sulfate and kaolin uniformly, added with an appropriate amount of filtrate, extruded into strips, and dried to obtain the sample of comparative example 3.
Comparative example 4
The desulfurizing agent composition comprises: 80g of carbide slag, 2h of ozone (about 2 g), 10g of ferrous sulfate, 10g of kieselguhr and 300g of water are introduced.
The preparation method of the desulfurizer comprises the following steps: mixing the carbide slag with water to prepare 1:4, introducing ozone, and filtering to obtain a wet cake and a filtrate; the wet cake was dried and ground, mixed well with ferrous sulfate and diatomaceous earth, added with an appropriate amount of filtrate, extruded into strips, and dried to give the sample of comparative example 4.
Example 1
The desulfurizing agent composition comprises: 80g of carbide slag, 50g of 30 percent (hydrogen peroxide concentration) of hydrogen peroxide, 10g of ferrous sulfate, 10g of bentonite and 300g of water.
The preparation method of the desulfurizer comprises the following steps: mixing carbide slag and water to prepare 1:4, adding hydrogen peroxide by adopting a parallel flow process at the temperature of-10 ℃, and filtering to obtain wet cakes and filtrate; the wet cake was dried and ground, mixed well with ferrous sulfate and bentonite, added with an appropriate amount of filtrate, extruded into strips and dried at 150 ℃ for 3h to obtain the sample of example 1.
Example 2
The desulfurizing agent composition comprises: 80g of carbide slag, 75g of 30% hydrogen peroxide, 10g of ferrous sulfate, 10g of attapulgite and 300g of water.
The preparation method of the desulfurizer comprises the following steps: mixing carbide slag and water to prepare 1:4, adding hydrogen peroxide by adopting a parallel flow process at the temperature of-10 ℃, and filtering to obtain wet cakes and filtrate; the wet cake was dried and ground, mixed well with ferrous sulfate and attapulgite, added with an appropriate amount of filtrate, extruded into strips, and dried at 150 ℃ for 3h to obtain the sample of example 2.
Example 3
The desulfurizing agent composition comprises: 80g of carbide slag, 100g of 30% hydrogen peroxide, 10g of ferrous sulfate, 10g of bentonite and 300g of water.
The preparation method of the desulfurizer comprises the following steps: mixing carbide slag and water to prepare 1:4, adding hydrogen peroxide by adopting a parallel flow process at the temperature of-10 ℃, and filtering to obtain wet cakes and filtrate; the wet cake was dried and ground into powder, mixed with ferrous sulfate and bentonite uniformly, added with an appropriate amount of filtrate, extruded into strips, and dried to obtain the sample of example 3.
Example 4
The desulfurizing agent composition comprises: 80g of carbide slag, 100g of 30% hydrogen peroxide, 10g of ferrous sulfate, 10g of diatomite and 300g of water.
The preparation method of the desulfurizer comprises the following steps: mixing the carbide slag with water to prepare 1:4, stirring with a proper amount of hydrogen peroxide, and filtering to obtain a wet cake and a filtrate; the wet cake was dried and ground, mixed well with ferrous sulfate and diatomaceous earth, added with the appropriate amount of filtrate, extruded into strips, and dried to give the sample of example 4.
Example 5
The desulfurizing agent composition comprises: 80g of carbide slag, 50g of 30% hydrogen peroxide, 10g of ferric chloride, 10g of bentonite and 300g of water.
The preparation method of the desulfurizer comprises the following steps: mixing carbide slag and water to prepare 1:4, adding hydrogen peroxide by adopting a parallel flow process at the temperature of-10 ℃, and filtering to obtain wet cakes and filtrate; the wet cake was dried and ground, mixed well with ferric chloride and bentonite, added with an appropriate amount of filtrate, extruded into strips and dried at 150 ℃ for 3h to give the sample of example 5.
Example 6
The desulfurizing agent composition comprises: 80g of carbide slag, 50g of 10 percent (hydrogen peroxide concentration) of hydrogen peroxide, 10g of ferrous sulfate, 10g of kaolin and 300g of water.
The preparation method of the desulfurizer comprises the following steps: mixing carbide slag and water to prepare 1:4, adding hydrogen peroxide by adopting a parallel flow process at the temperature of-10 ℃, and filtering to obtain wet cakes and filtrate; the wet cake was dried and ground, mixed well with ferrous sulfate and kaolin, added with an appropriate amount of filtrate, extruded into strips, and dried at 150 ℃ for 3h to give the sample of example 6.
Example 7
The desulfurizing agent composition comprises: 80g of carbide slag, 50g of 30 percent (hydrogen peroxide concentration) of hydrogen peroxide, 10g of ferrous sulfate, 10g of kieselguhr and 300g of water.
The preparation method of the desulfurizer comprises the following steps: mixing carbide slag and water to prepare 1:4, adding hydrogen peroxide by adopting a parallel flow process at the temperature of 0 ℃, and filtering to obtain wet cakes and filtrate; the wet cake was dried and ground, mixed well with ferrous sulfate and diatomaceous earth, added with an appropriate amount of filtrate, extruded into strips, and dried at 150 ℃ for 3h to give the sample of example 7.
The following tests were conducted on the performance of each comparative example and example of the present invention. The performance indexes of the flue gas desulfurizer are as follows: specific surface area, desulfurization efficiency. The detection method of each index is as follows:
(1) Specific surface area detection methods refer to: GB/T19587-2017
(2) The calculation method of the sulfur capacity is as follows:
desulfurization agent sulfur capacity = m 1 ×n/m×100％
m: mass of the desulfurizing agent, g;
m 1 : mass g of the desulfurizer after passing through sulfur-containing flue gas;
n: SO of desulfurizer after passing through sulfur-containing flue gas 2 Content,%.
SO in flue gas 2 The concentration is monitored on line by adopting a flue gas analyzer, and the inlet SO 2 The concentration was 2000ppm, and the exit 100ppm (i.e., desulfurization efficiency of 95%) was the end point of the experiment.
The test results are shown in table 1.
TABLE 1 flue gas desulfurization agent Performance test data
Remarking:
1. the air quantity of the laboratory ozone generator is fixed, the common unit is g/h or mg/h, and the maximum solubility of the ozone generator in 100ml of water is 49.4ml at the temperature of 20 ℃;
2. pure hydrogen peroxide is light blue viscous liquid and can be mixed and dissolved with water in any proportion, and the water solution is commonly called hydrogen peroxide. In the series of experiments, due to the limitation of conditions, only hydrogen peroxide with the hydrogen peroxide concentration of 10% and 30% is adopted for experiments, but the hydrogen peroxide with the hydrogen peroxide concentration of 10% to 50% can be adopted by the technicians in the field to realize the method.
According to the comparative example and the embodiment, the effect of modifying the carbide slag by using the hydrogen peroxide is obviously superior to that of modifying the carbide slag by using oxidation modes such as ozone and the like, and the desulfurization effect of the desulfurizer can be effectively improved.
So far, the embodiments of the present invention have been described in detail with reference to the accompanying drawings. The present invention should be clearly recognized by those skilled in the art from the above description.
In conclusion, the invention utilizes hydrogen peroxide to modify the carbide slag, improves the oxidation efficiency, and greatly improves the desulfurization efficiency through the generated calcium peroxide, thereby providing the desulfurizer with high desulfurization efficiency, low cost, simple process and environmental protection, and having better popularization and application prospects.
It is noted that for some implementations, if not essential to the invention and well known to those of ordinary skill in the art, they are not illustrated in detail in the drawings or in the text of the description, as they may be understood with reference to the relevant prior art.
Further, the foregoing examples are provided merely to enable the invention to meet the requirements of law, and the invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Furthermore, the above definitions of the various elements and methods are not limited to the specific structures, shapes or arrangements of parts mentioned in the examples, which may be easily modified or substituted by those skilled in the art. 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.
Unless expressly indicated to the contrary, the numerical parameters set forth in the specification and claims of this invention may be approximations that may vary depending upon the teachings of the invention. 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," which is intended to be interpreted to mean including within the meaning of a specified amount, in some embodiments, a variation of ± 10%, in some embodiments, a variation of ± 5%, in some embodiments, a variation of ± 1%, and in some embodiments, a variation of ± 0.5%.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention, 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, equivalent substitutions, 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 (10)
1. The carbide slag modified desulfurizer composition is characterized by comprising the following components in parts by weight:
60-90 parts of carbide slag;
50-300 parts of hydrogen peroxide, wherein the concentration of the hydrogen peroxide in the hydrogen peroxide is 10-50%;
10-30 parts of a binder;
180 to 720 portions of water.
2. The desulfurization composition of claim 1, further comprising:
5-20 parts of an auxiliary agent;
wherein the auxiliary agent comprises one or more of the following materials: ferric sulfate, ferrous sulfate, ferric acetate, ferric chloride and ferric nitrate.
3. The desulfurizing agent composition according to claim 1,
the binder comprises one or more of the following materials: cement, gypsum, kaolin, attapulgite, bentonite and diatomite.
4. A method for preparing a desulfurizing agent using the desulfurizing agent composition according to claim 1, comprising:
step A, mixing carbide slag and water for pulping to obtain carbide slag slurry;
b, mixing the carbide slag slurry and hydrogen peroxide for reaction to obtain calcium peroxide slurry;
step C, adding a binder into the calcium peroxide slurry to obtain a wet desulfurizer material;
step D, forming the wet desulfurizer material into a semi-finished desulfurizer product;
and E, drying the semi-finished product of the desulfurizer to obtain a finished product of the desulfurizer.
5. The desulfurization agent preparation method according to claim 4, wherein the step B comprises:
under the low-temperature environment of-20 to 0 ℃, the carbide slag slurry and the hydrogen peroxide are mixed by adopting a parallel flow process, and the mixing ratio of the carbide slag slurry and the hydrogen peroxide is controlled by the flow rate.
6. The desulfurizing agent preparation method according to claim 4,
the desulfurizing agent composition further comprises: 5-20 parts of an auxiliary agent; wherein the auxiliary agent comprises one or more of the following materials: ferric sulfate, ferrous sulfate, ferric acetate, ferric chloride, ferric nitrate;
in the preparation method, the step C comprises the following steps: and adding an auxiliary agent and a binder into the calcium peroxide slurry to obtain the wet desulfurizer material.
7. The desulfurizing agent preparation method according to claim 6,
in the step A, the weight ratio of the carbide slag to the water is 1:3-1:8;
in the step B, the weight ratio of the carbide slag to the hydrogen peroxide is 1.5-1:3;
in the step C, the weight ratio of the carbide slag, the auxiliary agent and the binder is as follows: 1.
8. The method of claim 4, wherein the step E comprises:
and drying the semi-finished product of the desulfurizer at the temperature of between 50 and 200 ℃ for 1 to 8 hours to obtain a finished product of the desulfurizer.
9. The desulfurizer is characterized by being prepared by the desulfurizer preparation method as claimed in any one of claims 4 to 8, wherein the finished product of the desulfurizer is cylindrical, clover-shaped or plum blossom-shaped.
10. A desulphurating agent composition according to any one of claims 1 to 3 or a desulphurating agent according to claim 9 for use in low temperature flue gas desulphurisation;
wherein the low-temperature flue gas is low-temperature heating furnace flue gas, ceramic flue gas and garbage power generation tail gas.
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