阅读说明：本技术 一种工业尾气深度脱硫剂及其制备方法 (Deep desulfurizer for industrial tail gas and preparation method thereof ) 是由 郝子全 曲晓龙 苏少龙 钟读乐 孙彦民 于 2021-06-29 设计创作，主要内容包括：本发明公开了一种工业尾气深度脱硫剂的制备方法,包括以下步骤：将干电石渣球磨破碎、过筛,得到电石渣粉末,取电石渣粉末与络合剂溶液充分剪切混合,抽滤、清洗、干燥得到电石渣活性组分；将所述电石渣活性组分、改性剂通过立磨粉碎、风选得到工业尾气深度脱硫剂粉末成品。本发明以干电石渣为原料,并掺杂改性剂,制备的脱硫剂具有多孔、高活性、分散性好的优点,比表面积可达34～38m～(2)/g,而且可在1000～1800℃环境中实现工业尾气深度脱硫,适用于工业高温生产环境。(The invention discloses a preparation method of an industrial tail gas deep desulfurizing agent, which comprises the following steps: carrying out ball milling, crushing and sieving on the dry carbide slag to obtain carbide slag powder, taking the carbide slag powder, fully shearing and mixing the carbide slag powder and a complexing agent solution, and carrying out suction filtration, cleaning and drying to obtain an active component of the carbide slag; and crushing and winnowing the carbide slag active component and the modifier through a vertical mill to obtain a finished product of the industrial tail gas deep desulfurizing agent powder. According to the invention, the dry carbide slag is used as a raw material and is doped with a modifier, the prepared desulfurizer has the advantages of porosity, high activity and good dispersibility, and the specific surface area can reach 34-38 m 2 The catalyst can realize deep desulfurization of industrial tail gas in an environment of 1000-1800 ℃, and is suitable for industrial high-temperature production environment.)

1. The preparation method of the industrial tail gas deep desulfurizing agent is characterized by comprising the following steps:

1) carrying out ball milling, crushing and sieving on the dry carbide slag to obtain carbide slag powder, taking the carbide slag powder, fully shearing and mixing the carbide slag powder and a complexing agent solution, and carrying out suction filtration, cleaning and drying to obtain an active component of the carbide slag;

2) crushing and winnowing the carbide slag active component and the modifier through a vertical mill to obtain a finished product of industrial tail gas deep desulfurizing agent powder;

the complexing agent solution consists of 0.1-1.2% of diethylenetriamine pentaacetic acid pentasodium, 1.5-5% of citric acid, 0.3-2.5% of diethyl triamine pentaacetic acid and 93-98% of water;

the modifier is at least one of cerium dioxide, magnesium hydroxide, titanium dioxide, zinc nitrate, barium hydroxide, lanthanum oxide, antimony nitrate and manganese hydroxide, and the addition amount of the modifier is 2-6% of the total mass of the deep desulfurization agent for industrial tail gas.

2. The method of claim 1, wherein: the shearing and mixing time of the step of taking the carbide slag powder and the complexing agent solution to be fully sheared and mixed in the step 1) is 25-35 min, and the rotating speed of a rotor is 15-35 r/min.

3. The method of claim 1, wherein: the modifier is a mixture of cerium dioxide, titanium dioxide, zinc nitrate and lanthanum oxide, and the mass ratio of the modifier to the modifier is 1 (0.5-2) to 1-3 to 0.5-5.

4. The industrial tail gas deep desulfurization agent prepared by the preparation method according to claim 1, characterized in that: the specific surface area of the industrial tail gas deep desulfurizing agent powder finished product is 34-38 m²And/g, and stable deep desulfurization is realized in an environment of 1000-1800 ℃.

Technical Field

The invention belongs to the technical field of industrial tail gas desulfurization, and particularly relates to a preparation method of an industrial tail gas deep desulfurizing agent.

Background

In industrial production of waste incineration, building materials, glass, ceramics and the like, a large amount of SO is often discharged to the atmosphere₂These SO₂On the one hand, the product can be regarded as a valuable chemical raw material, and on the other handOn one hand, the method can aggravate atmospheric pollution and acid rain and strictly control SO in industrial tail gas₂The emission has great significance for industry development and environmental protection.

In the gradually mature dry desulfurization, calcium hydroxide is widely used in the industrial tail gas desulfurization industry as a common desulfurizer, and the performance of the calcium hydroxide directly affects the desulfurization effect. Industrial Ca (OH)₂The preparation method mainly comprises a lime digestion method, a diffusion method, a calcium chloride alkali-adding precipitation method and the like, but the specific surface area of the calcium hydroxide prepared by the methods is limited, and the calcium hydroxide has the problems of low utilization rate and poor effect when being used for deep desulfurization of industrial tail gas, and cannot meet the market demand. In addition, because the industrial tail gas desulfurization working condition temperature is generally higher, the desulfurization product CaSO₃、CaSO₄The decomposition starts at the temperature of over 1000 ℃, and sulfur-containing pollutants are generated again, so that the desulfurization effect is influenced. Therefore, only by seeking breakthrough in process technology and developing an industrial tail gas deep desulfurizing agent which has a large specific surface area, is suitable for a high-temperature production environment and has high desulfurization efficiency, the healthy development of the whole industry can be realized.

The carbide slag is an industrially produced solid waste which is obtained by hydrolyzing calcium carbide to obtain acetylene gas and is Ca (OH)₂Waste residue of Ca (OH) as a main component₂The content is 50-60%. The preparation of acetylene has two modes of dry method and wet method, wherein the dry method process is to add water into calcium carbide to produce Ca (OH)₂The waste slag (the water content is less than or equal to 8 percent) is discharged from the reactor in powder form. The dry acetylene method has the advantages of low water consumption and low comprehensive utilization cost of carbide slag, gradually becomes the mainstream process of acetylene production, and the resource utilization of the dry carbide slag generated by the production also becomes a research hotspot of industrial development. At present, the yield of the calcium carbide in China is thousands of tons, each ton of calcium carbide generates about 1.2 tons of dry calcium carbide slag, long-term accumulation of the dry calcium carbide slag not only occupies land resources, but also has serious erosion effect on soil and water, and compared with the huge yield of the calcium carbide slag in China, the comprehensive treatment and disposal technology is limited.

Disclosure of Invention

Aiming at the defects of the existing industrial tail gas desulfurizer production technology and aiming at effectively utilizing waste generated in the acetylene production process, the invention provides a preparation method of an industrial tail gas deep desulfurizer, the method takes dry carbide slag as a raw material and is doped with a modifier, the prepared desulfurizer has the advantages of porosity, high activity, good dispersibility and high specific surface area, and the stable deep desulfurization of the industrial tail gas can be realized in the environment of 1000-1800 ℃, thereby having great significance for industry development and environmental protection.

The technical scheme of the invention is as follows:

the invention relates to a preparation method of an industrial tail gas deep desulfurizing agent, which comprises the following steps:

1) carrying out ball milling, crushing and sieving on the dry carbide slag to obtain carbide slag powder, taking the carbide slag powder, fully shearing and mixing the carbide slag powder and a complexing agent solution, and carrying out suction filtration, cleaning and drying to obtain an active component of the carbide slag;

2) crushing and winnowing the carbide slag active component and the modifier through a vertical mill to obtain a finished product of industrial tail gas deep desulfurizing agent powder;

wherein the complexing agent solution consists of 0.1-1.2% of diethylenetriamine pentaacetic acid pentasodium, 1.5-5% of citric acid, 0.3-2.5% of diethyl triamine pentaacetic acid and 93-98% of water;

the modifier is at least one of cerium dioxide, magnesium hydroxide, titanium dioxide, zinc nitrate, barium hydroxide, lanthanum oxide, antimony nitrate and manganese hydroxide, and the addition amount of the modifier is 2-40% of the total mass of the deep desulfurization agent for industrial tail gas.

Preferably, the modifier is a mixture of cerium dioxide, titanium dioxide, zinc nitrate and lanthanum oxide, and the mass ratio of the modifier to the lanthanum oxide is 1 (0.5-2) to 1-3 to 0.5-5.

In the preparation method of the industrial tail gas deep desulfurization agent, in the step 1), the step of taking the carbide slag powder and fully shearing and mixing the carbide slag powder with the complexing agent solution preferably comprises the shearing and mixing time of 25-35 min and the rotor rotating speed of 15-35 r/min.

The invention also provides the industrial tail gas deep desulfurizer prepared by the preparation method, and the specific surface area of the industrial tail gas deep desulfurizer powder finished product reaches 34-38 m²A/g and is stable in an environment of 1000 to 1800 DEG CAnd (5) desulfurization at a fixed depth.

Compared with the prior art, the preparation method and the desulfurizer of the invention have the advantages that:

(1) the preparation method takes the dry carbide slag as a raw material to prepare the industrial tail gas deep desulfurizer, and realizes the treatment of pollution by waste and the recycling of waste while obtaining a high-performance desulfurizer product; heavy metal lead, strontium, metalloid arsenic and other impurities in the carbide slag are removed by complexing with a complexing agent solution, so that the purity and the activity of a desulfurizer product can be effectively improved; the stability of the desulfurizer in a high-temperature production environment at 1000-1800 ℃ can be effectively improved by doping the modifier, and the regulation mechanism is that the modifier component in the desulfurizer can form a heat-resistant glassy substance at high temperature to wrap a desulfurization product, so that CaSO is inhibited₃、CaSO₄Decomposing at high temperature. The specific surface area of the prepared desulfurizing agent reaches 34-38 m²The desulfurizer has the advantages of porosity, high activity and high dispersibility, is suitable for deep desulfurization of industrial tail gas, and can meet the market demand of industrial tail gas desulfurizer.

(2) The preparation process is simple and feasible, and the process is pollution-free.

Drawings

FIG. 1 is a flow chart of the process for preparing the industrial tail gas deep desulfurization agent of the present invention.

Detailed Description

In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

Fully grinding the dry carbide slag in a ball mill for 2 hours, and then sieving to obtain carbide slag powder; continuously and uniformly introducing the carbide slag powder into a shear mixer, taking a complexing agent solution consisting of 0.1 percent of diethylenetriamine pentaacetic acid pentasodium, 1.5 percent of citric acid, 0.4 percent of diethyl triamine pentaacetic acid and 98 percent of water as a fast flowing phase of the shear mixer, and fully mixing the carbide slag powder in a shear cavity for 25min, wherein the rotating speed of a rotor is 15 r/min; after the reaction is finished, performing suction filtration on the obtained mixed slurry by using filter cloth with the diameter of 1-3 mu m, then cleaning filter mud by using water, repeatedly performing suction filtration and cleaning for three times, and drying the filter mud in a drying furnace at 150 ℃ for 24 hours to obtain a dried carbide slag active component;

mixing 70% of dry carbide slag active components, 10% of cerium dioxide, 5% of titanium dioxide, 10% of zinc nitrate and 5% of lanthanum oxide according to mass percentage, crushing the mixture by using a vertical mill, removing heavier components by air separation, and controlling the air volume to be 11700m³And obtaining a finished product of desulfurizer powder.

Example 2

Fully grinding the dry carbide slag in a ball mill for 2 hours, and then sieving to obtain carbide slag powder; continuously and uniformly introducing the carbide slag powder into a shear mixer, taking a complexing agent solution consisting of 1.2 percent of diethylenetriamine pentaacetic acid pentasodium, 5 percent of citric acid, 0.3 percent of diethyl triamine pentaacetic acid and 93.5 percent of water as a fast flowing phase of the shear mixer, and fully mixing the complexing agent solution with the carbide slag powder in a shear cavity for 35min, wherein the rotating speed of a rotor is 35 r/min; after the reaction is finished, performing suction filtration on the obtained mixed slurry by using filter cloth with the diameter of 1-3 mu m, then cleaning filter mud by using water, repeatedly performing suction filtration and cleaning for three times, and drying the filter mud in a drying furnace at 150 ℃ for 24 hours to obtain a dried carbide slag active component;

mixing 78% of dry carbide slag active component, 2% of cerium dioxide, 4% of titanium dioxide, 6% of zinc nitrate and 10% of lanthanum oxide according to mass percentage, crushing the mixture by using a vertical mill, removing heavier components in the mixture by air separation, and controlling the air volume to be 11700m³And obtaining a finished product of desulfurizer powder.

Example 3

Fully grinding the dry carbide slag in a ball mill for 2 hours, and then sieving to obtain carbide slag powder; continuously and uniformly introducing the carbide slag powder into a shear mixer, taking a complexing agent solution consisting of 1% of diethylenetriaminepentaacetic acid pentasodium, 3.5% of citric acid, 2.5% of diethyltriaminepentaacetic acid and 93% of water as a fast flowing phase of the shear mixer, and fully mixing the carbide slag powder in a shear cavity for 30min, wherein the rotor speed is 25 r/min; after the reaction is finished, performing suction filtration on the obtained mixed slurry by using filter cloth with the diameter of 1-3 mu m, then cleaning filter mud by using water, repeatedly performing suction filtration and cleaning for three times, and drying the filter mud in a drying furnace at 150 ℃ for 24 hours to obtain a dried carbide slag active component;

mixing 98% of dry carbide slag active component, 0.5% of cerium dioxide, 0.5% of titanium dioxide, 0.5% of zinc nitrate and 0.5% of lanthanum oxide according to mass percent, crushing the mixture by a vertical mill, removing heavier components in the mixture by air separation, and controlling the air flow to be 11700m³And obtaining a finished product of desulfurizer powder.

Example 4

Fully grinding the dry carbide slag in a ball mill for 2 hours, and then sieving to obtain carbide slag powder; continuously and uniformly introducing the carbide slag powder into a shear mixer, taking a complexing agent solution consisting of 0.5 percent of diethylenetriamine pentaacetic acid pentasodium, 1.5 percent of citric acid, 2 percent of diethyl triamine pentaacetic acid and 96 percent of water as a fast flowing phase of the shear mixer, and fully mixing the carbide slag powder in a shear cavity for 30min, wherein the rotating speed of a rotor is 20 r/min; after the reaction is finished, performing suction filtration on the obtained mixed slurry by using filter cloth with the diameter of 1-3 mu m, then cleaning filter mud by using water, repeatedly performing suction filtration and cleaning for three times, and drying the filter mud in a drying furnace at 150 ℃ for 24 hours to obtain a dried carbide slag active component;

mixing 60% of dry carbide slag active components, 10% of cerium dioxide, 10% of titanium dioxide, 10% of zinc nitrate and 10% of lanthanum oxide according to mass percentage, crushing the mixture by using a vertical mill, removing heavier components by air separation, and controlling the air volume to be 11700m³And obtaining a finished product of desulfurizer powder.

Comparative example

Industrial tail gas desulfurizer produced by Zhejiang company.

BET representation is carried out on the industrial tail gas deep desulfurizer powder prepared in the examples 1 to 4 and the comparative example desulfurizer, so as to obtain the specific surface area, the pore volume and the pore diameter of the sample. Wherein, the specific surface area of the desulfurizing agent powder is measured by a BET multipoint method, the pore volume and the pore diameter are measured by a BJH method desorption, and the test conditions are as follows:the environment temperature is 22 deg.C, the constant bath temperature is-195.8 deg.C, and the adsorbate is N₂. The test results are shown in table 1 below.

The industrial tail gas deep desulfurization agents prepared in examples 1 to 4 and the comparative example desulfurization agent were subjected to desulfurization performance testing by using a fixed bed evaluation apparatus with controlled air flow rate of 16L/h and SO₂Flow 4L/h, SO₂The inlet concentration is 1200ppm, the reaction temperature is 300 ℃, the gas collection bag is used for taking out an outlet sample every 1h, each sampling is carried out for 30min, the time node is recorded, and the comprehensive flue gas analyzer is used for detecting SO after sampling₂The concentrations, test results are shown in table 2 below.

TABLE 1 BET characterization results

TABLE 2 comparison of desulfurizing agent Performance