WO1999047244A1 - Desulfurizer and the process of making the same - Google Patents

Desulfurizer and the process of making the same Download PDF

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Publication number
WO1999047244A1
WO1999047244A1 PCT/CN1999/000025 CN9900025W WO9947244A1 WO 1999047244 A1 WO1999047244 A1 WO 1999047244A1 CN 9900025 W CN9900025 W CN 9900025W WO 9947244 A1 WO9947244 A1 WO 9947244A1
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Prior art keywords
desulfurizing agent
calcium
iron
molar ratio
hours
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PCT/CN1999/000025
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French (fr)
Chinese (zh)
Inventor
Ke Lin
Jie Zhang
Zhiqiang Wu
Xiaodong Wang
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Ke Lin
Jie Zhang
Zhiqiang Wu
Xiaodong Wang
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Application filed by Ke Lin, Jie Zhang, Zhiqiang Wu, Xiaodong Wang filed Critical Ke Lin
Priority to AU32448/99A priority Critical patent/AU3244899A/en
Publication of WO1999047244A1 publication Critical patent/WO1999047244A1/en

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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
    • B01D53/52—Hydrogen sulfide

Definitions

  • the powder whose main ingredient is iron oxide and / or iron hydroxide and / or iron nitrate is mixed with powder of calcium oxide and / or calcium hydroxide and / or calcium bicarbonate and / or calcium carbonate, wherein iron and calcium
  • the molar ratio is 1: 1 to 1: 5;

Abstract

A desulfurizer comprising Ca2Fe2O5 as active the component and a process of making the same are disclosed. The process comprises the following steps: a) mixing the powder comprising iron oxide and/or hydroxide and/or nitrate with the powder comprising calcium oxide and/or carbonate and/or bicarbonate, where the molar ratio of iron/calcium is between 1:1 to 1:5; b) shaping the mixture obtained in step, a) then drying; and c) sintering the article obtained in step b) under oxidative atmosphere at a temperature 700 to 1100 °C for 0.5 to 24 hours.

Description

脱硫剂及其制备方法 技术领域 本发明涉及一种可在气态物料或液态物料中脱除 H2S的脱硫剂和 制备方法，特别是一种以 Ca2Fe205为有效活性组分的高效脱硫剂及其制 备方法。 背景技术 以煤或石油制取化工原料的过程中含有的 H2S会使后续工段的催化 剂中毒而失活。 很多工业废水废气中也含有大量的 H2S , 直接排放会污 染环境或造成人畜中毒，现有的脱硫剂主要有活性碳及以氧化锌，氧化 铁为主要成份的脱硫剂。 氧化锌是一种高温脱硫剂， 要取得良好的脱硫 效果， 一般使用温度应在 200° (：〜 500°C。 专利文献所称的常温脱硫在低 于 80°C以下时， 效果并不理想， 且硫容量很低 (小于 9%(W/W))。 以氧 化铁为主要成份的脱硫剂是一种古老的脱硫剂，但由于其对温度， 空速 适用范围窄， 反应效率低， 硫容低的缺点， 一般只能用于初级粗脱硫或 与其它剂种配合使用， 实际效果并不理想。 TECHNICAL FIELD The present invention relates to a desulfurizing agent and a preparation method capable of removing H 2 S in a gaseous material or a liquid material, and particularly to a desulfurizing agent using Ca 2 Fe 2 0 5 as an active component. High-efficiency desulfurizing agent and preparation method thereof. BACKGROUND H 2 S contained in the process of preparing chemical raw materials from coal or petroleum may poison and deactivate catalysts in subsequent stages. Many industrial waste water also contains a large amount of H 2 S, which directly pollutes the environment or causes human and animal poisoning. The existing desulfurizers mainly include activated carbon and desulfurizers with zinc oxide and iron oxide as the main components. Zinc oxide is a high-temperature desulfurizing agent. In order to achieve good desulfurization effect, the general use temperature should be 200 ° (: ~ 500 ° C. When the normal temperature desulfurization in the patent literature is below 80 ° C, the effect is not ideal. And the sulfur capacity is very low (less than 9% (W / W)). The desulfurizer with iron oxide as the main component is an ancient desulfurizer, but due to its temperature, narrow space velocity application range, low reaction efficiency, The disadvantage of low sulfur capacity is generally that it can only be used for primary crude desulfurization or used in combination with other agents. The actual effect is not ideal.
CN1067828A公开了一种 "常温精脱有机硫及无机硫新工艺" ， 用 该方法包括用改性活性炭或氧化铁在常温下脱硫， 再在 30-12CTC的温 度下用常温水解有机硫催化剂，常压水解吸收硫，或者最后再用改性活 性炭或氧化铁在常温下脱硫。 其中氧化铁脱硫剂是市售的 TG-1、 SN-1 和 ET-1， 在该专利中没有详细记载这些脱硫剂的组成和制备方法。 脱 硫精度为 O. lppm, 没有提及脱硫精度的检测方法及硫容。 CN1067828A discloses a "new process for finely desulfurizing organic and inorganic sulfur at room temperature". The method includes desulfurizing at room temperature with modified activated carbon or iron oxide, and hydrolyzing the organic sulfur catalyst at room temperature at 30-12CTC. Pressure hydrolysis absorbs sulfur, or finally use modified activated carbon or iron oxide to desulfurize at normal temperature. The iron oxide desulfurizers are commercially available TG-1, SN-1 and ET-1, and the composition and preparation method of these desulfurizers are not described in detail in this patent. The desulfurization accuracy is 0.1 ppm, and the detection method and sulfur capacity of the desulfurization accuracy are not mentioned.
CN1068356A公开了一种 "高温煤气二步脱硫法" ， 该方法包括初 级脱硫和高温第二步脱硫， 第二步脱硫是在 65CTC下进行的。初级脱硫 的脱硫剂是由废铁泥掺混 4-15%氧化钙和 10-40%的膨润土，在 800-1000 °C的高温下焙烧制成的， 脱硫效率>90%， 硫容为 8%。 在该专利中没 有提及第一步脱硫的温度，也没有提及脱硫剂的焙烧气氛。第二步脱硫 的脱硫剂是氧化铁和氧化锌掺混 10-40%膨润土， 在 800-1000°C高温焙 烧制成的， 脱硫效率>90%， 硫容为 8%。 铁泥的组成相当复杂， 来自不 同的加工过程中的铁泥其组成也不相同， 而且铁泥中含有许多的杂质， 如铝、 磷、 硫、 锰、 碳等， 此外， 废泥中可能含有铁， 在该专利中并未 详细描述废铁泥的组成， 当然也就无法判断在铁泥中铁的含量。但从其 文字表述可以看出， 该氧化铁脱硫剂只能用于粗脱硫。 此外， CN1068356A discloses a "high-temperature gas two-step desulfurization method", which includes primary desulfurization and high-temperature second step desulfurization, and the second step desulfurization is performed at 65CTC. The desulfurizing agent for primary desulfurization is made from scrap iron mud mixed with 4-15% calcium oxide and 10-40% bentonite and roasted at a high temperature of 800-1000 ° C. The desulfurization efficiency is> 90% and the sulfur capacity is 8 %. Not in the patent The temperature of the first step desulfurization is mentioned, and the roasting atmosphere of the desulfurizing agent is not mentioned. The desulfurizing agent for the second step of desulfurization is made by mixing iron oxide and zinc oxide with 10-40% bentonite and baking at 800-1000 ° C. The desulfurization efficiency is> 90%, and the sulfur capacity is 8%. The composition of iron slime is quite complicated. The composition of iron slime from different processing processes is different, and the iron slime contains many impurities, such as aluminum, phosphorus, sulfur, manganese, carbon, etc. In addition, the waste slime may contain In this patent, the composition of the scrap iron slime is not described in detail in the patent, and it is of course impossible to judge the iron content in the iron slime. However, it can be seen from the written description that the iron oxide desulfurizing agent can only be used for crude desulfurization. In addition,
CN1094331A中公开了一种 "常温氧化锌脱硫剂和制备方法" 。 一种脱硫剂的性能主要取决于其硫容、 脱硫精度和使用温度， 硫容 越大、 脱硫精度越高， 则脱硫剂的性能越好。 CN1067828A中脱硫剂的 脱硫精度不够高； CN1068356A中脱硫剂的硫容不够大， 脱硫精度也不 够高， 所以需要两步才能脱硫至≤lppm。 在此之前， 尚未公开过硫容超 过 20%的脱硫剂。 发明内容 本发明的一个目的是提供一种硫容大， 脱硫精度高、 反应速度快、 能在较低温度下脱除气态和液态物料中 H2S的脱硫剂。 本发明的另一目的是提供一种硫容大， 脱硫精度高、 能在液态、 气 态物料中低温使用的以 Ca2Fe205为有效活性组分的脱硫剂的制备方法。 本发明的脱硫剂含有特定复合结构的 Ca2Fe205活性组分， Ca2Fe205 活性组分的量大于脱硫剂总重量的 40%。本发明脱硫剂可以含有小于脱 硫剂总重量 40%的 CaO、 Ca(OH)2、 Fe203及 ¾0。 本发明的脱硫剂是这样按如下方法制备的： CN1094331A discloses "a normal temperature zinc oxide desulfurizer and a preparation method". The performance of a desulfurizing agent mainly depends on its sulfur capacity, desulfurization accuracy, and use temperature. The larger the sulfur capacity and the higher the desulfurization accuracy, the better the performance of the desulfurizer. The desulfurization accuracy of the desulfurizer in CN1067828A is not high enough; the sulfur capacity of the desulfurizer in CN1068356A is not large enough, and the desulfurization accuracy is not high enough, so two steps are needed to desulfurize to ≤lppm. Prior to this, no desulfurizing agent with a sulfur capacity exceeding 20% has been disclosed. SUMMARY OF THE INVENTION An object of the present invention is to provide a desulfurizing agent with large sulfur capacity, high desulfurization accuracy, fast reaction speed, and capable of removing H 2 S in gaseous and liquid materials at lower temperatures. Another object of the present invention is to provide a method for preparing a desulfurizing agent with a large sulfur capacity, high desulfurization accuracy, and low-temperature use in liquid and gaseous materials with Ca 2 Fe 2 0 5 as an active component. The desulfurizing agent of the present invention contains a Ca 2 Fe 2 0 5 active component with a specific composite structure, and the amount of the Ca 2 Fe 2 0 5 active component is greater than 40% of the total weight of the desulfurizing agent. The desulfurizing agent of the present invention may contain less than 40% of the total weight of the desulfurizing agent by CaO, Ca (OH) 2 , Fe 2 0 3 and ¾0. The desulfurizing agent of the present invention is prepared as follows:
a. 将主要成份为氧化铁和 /或氢氧化铁和 /或硝酸铁的粉末与氧化 钙和 /或氢氧化钙和 /或碳酸氢钙和 /或碳酸钙的粉末混合， 其中铁 与钙的摩尔比为 1:1至 1 :5;  a. The powder whose main ingredient is iron oxide and / or iron hydroxide and / or iron nitrate is mixed with powder of calcium oxide and / or calcium hydroxide and / or calcium bicarbonate and / or calcium carbonate, wherein iron and calcium The molar ratio is 1: 1 to 1: 5;
b. 将混合料加水搅拌， 成型， 干燥；  b. Mix the mixture with water, stir, shape, and dry;
c 在 700°C〜1100°C温度下的氧化性气氛中焙烧 0.5至 24小时； d. 待冷却后均匀喷洒少量水制得脱硫剂成品。 在步骤 a)中， 可以添加各种合适的结构助剂和造孔剂。 合适的结构 助剂包括氧化硅、 氧化铝， 也可以是澎润土、 高岭土和皂土等。特别合 适的造孔剂是碳粉、 淀粉或纤维素。 原则上讲， 在步骤 a)中可以使用除氧化铁或氢氧化铁外的含铁化合 物， 如硝酸铁等， 以及使用除氧化钙或氢氧化钙外的含钙化合物， 如碳 酸氢钙和碳酸钙等。但氧化铁或氢氧化铁外的含铁化合物和氧化钙或氢 氧化钙外的含钙化合物是优选的。在所有的情形中，要求铁与钙的摩尔 比为 1 :1至 1:5 , 并形成特定的 Ca2Fe205结构。 原则上讲， 在步骤 d)中可以使用某些物质的水溶液来代替水， 如碱 金属或碱土金属的氢氧化物或硝酸盐等的水溶液，例如氢氧化钠、氢氧 化钾、 氢氧化钙、 硝酸钠、 硝酸钾、 硝酸钙、 氯化钠、 氯化钾、 氯化钙 等， 只要这些物质不影响脱硫剂的脱硫效果即可。 步骤 b)成型的脱硫剂可以是任何合适的形状， 如条形、 球形、 颗粒 形或蜂窝形。 本发明的成品脱硫剂 (条型)的抗破碎强度大于 110 N/cm, 比表面积 为 1.8 3 m2/g, 孔隙率为 50%~65%， 表观密度为 1.0~1.5g/cm3。 本发明的脱硫剂可广泛用于煤气、 氢气、 合成气、 氨、 气态烃等各 种含硫化氢气体中脱硫。也可以在液态烃如煤油、汽油、环已垸等液态 物料中使用。 使用温度在 5°C~90°C范围内， 气体空速在小于 100001T 1 时， 液态空速在小于 10 h— 1时一次饱和硫容大于 20%(W/W：)， 出口定性 检测无 H2S存在， 而且可通空气再生使用。 附图的简要说明 图 1所示为按实施例 1的脱硫剂的 X射线衍射图， 经与 X射线卡片 (J. C.P.D.S.卡片)检索对比， 图 1中的数据表明， 该脱硫的主要组分为 Ca2Fe 205； 图 2所示为实施例 1的脱硫剂用于脱除 H2S， 被穿透后的脱硫剂的 X 射线衍射图， 经与 X射线卡片 (J.C.P.D.S.卡片)检索对比， 图 2中的数据 表明， 其主要组分为 Fe7S8和 FeS的混合物 实施本发明的最佳方式 实施例 1 取 Fe203粉末 42克， CaO粉末 58克， 加水， 搅拌， 捏合， 挤条成型， 经 100°C左右干燥约 2小时， 在氧化性气氛中 900°C焙烧 3小时， 冷却后 均匀喷洒约 10克 H20， 得脱硫剂八。 实施例 2 取 Fe203粉末 42克， CaO粉末 58克， 加水， 搅拌， 捏合， 挤条成型， 经 100°C左右干燥约 2小时， 在氧化性气氛中 1000°C焙烧 2小时， 冷却后 均匀喷洒约 10克水， 得脱硫剂^ 实施例 3 取 Fe203粉末 35克， Ca(OH)2粉末 65克， 加水， 搅拌， 捏合， 挤条成 型， 经 100°C左右干燥约 2小时， 在氧化性气氛中 900°C焙烧 3小时， 冷 却后均匀喷洒约 10克 H20， 得脱硫剂 。 实施例 4 取 Fe(OH)3粉末 32.5克， Ca(OH)2粉末 67.5克， 加水， 搅拌， 捏合， 挤条成型， 经 100°C左右干燥约 2小时， 在氧化性气氛中 900°C焙烧 3小 时， 冷却后均匀喷洒约 10克 ¾0， 得脱硫剂0。 实施例 5 取 Fe203粉末 49克， CaO粉末 51克， 加水， 搅拌， 捏合， 挤条成型， 经 100°C左右干燥约 2小时， 在氧化性气氛中 900°C焙烧 3小时， 冷却后 均匀喷洒约 10克 H20， 得脱硫剂£。 实施例 6 取 Fe203粉末 37克， Ca(OH)2粉末 43克， 膨润土 20克， 加水， 搅拌， 捏合， 挤条成型， 经 100°C左右干燥约 2小时， 在氧化性气氛中 900°C焙 烧 3小时， 冷却后均匀喷洒约 10克 H20， 得脱硫剂？。 实施例 7 取 Fe203粉末 35克， Ca(OH)2粉末 65克， 碳粉 1克加水， 搅拌， 捏合， 挤条成型， 经 100°C左右干燥约 2小时， 在氧化性气氛中 900°C焙烧 3小 时， 冷却后均匀喷洒约 10克 H20， 得脱硫剂0。 实施例 8 取 Fe203粉末 30.5克， Ca(OH)2粉末 49.5克， 碳粉 1克， 膨润土 20克， 加水， 搅拌， 捏合， 挤条成型， 经 100 C左右干燥约 2小时， 在氧化性 气氛中 900°C焙烧 3小时， 冷却后均匀喷洒约 10克 ¾0， 得脱硫剂11。 实施例 9 取 Fe203粉末 29.6克， Ca(OH)2粉末 27.5克， Ca(HC03)2粉末 32.9克， 膨润土 10克， 加水， 搅拌， 捏合， 挤条成型， 经 150°C左右干燥约 2小 时， 在氧化性气氛中 1000°C焙烧 2小时， 冷却后均匀喷洒约 10克 H20， 得脱硫剂 I。 实施例 10 取 Fe203粉末 46.2克， (0 2粉末21.4克， CaO粉末 32.4克， 碳粉 2 克， 加水， 搅拌， 捏合， 挤条成型， 经 100°C左右干燥约 2小时， 在氧 化性气氛中 1000°C焙烧 2小时， 冷却后均匀喷洒约 10克 H20， 得脱硫剂c. Baking in an oxidizing atmosphere at a temperature of 700 ° C ~ 1100 ° C for 0.5 to 24 hours; d. After cooling, spray a small amount of water evenly to obtain the finished product of the desulfurizer. In step a), various suitable structural assistants and pore-forming agents may be added. Suitable structural aids include silica, alumina, and can also be pennite, kaolin, bentonite, and the like. Particularly suitable pore formers are carbon powder, starch or cellulose. In principle, in step a) iron-containing compounds other than iron oxide or iron hydroxide, such as iron nitrate, etc., and calcium-containing compounds other than calcium oxide or calcium hydroxide, such as calcium bicarbonate and carbonic acid, can be used Calcium and so on. However, iron-containing compounds other than iron oxide or iron hydroxide and calcium-containing compounds other than calcium oxide or calcium hydroxide are preferred. In all cases, the molar ratio of iron to calcium is required to be 1: 1 to 1: 5, and a specific Ca 2 Fe 2 0 5 structure is formed. In principle, in step d), an aqueous solution of certain substances may be used instead of water, such as an aqueous solution of an alkali metal or alkaline earth metal hydroxide or nitrate, such as sodium hydroxide, potassium hydroxide, calcium hydroxide, Sodium nitrate, potassium nitrate, calcium nitrate, sodium chloride, potassium chloride, calcium chloride, etc., as long as these substances do not affect the desulfurizing effect of the desulfurizing agent. The desulfurizing agent formed in step b) may be any suitable shape, such as a bar shape, a spherical shape, a granular shape, or a honeycomb shape. The crushing strength of the finished desulfurizer (stripe) of the present invention is greater than 110 N / cm, the specific surface area is 1.8 3 m 2 / g, the porosity is 50% to 65%, and the apparent density is 1.0 to 1.5g / cm 3 . The desulfurizing agent of the present invention can be widely used for desulfurization in various hydrogen sulfide-containing gases such as coal gas, hydrogen, synthesis gas, ammonia, and gaseous hydrocarbons. It can also be used in liquid hydrocarbons such as kerosene, gasoline, cyclohexane, and other liquid materials. The operating temperature is in the range of 5 ° C ~ 90 ° C, when the gas space velocity is less than 100001T 1 , and the liquid space velocity is less than 10 h— 1 , the primary saturated sulfur capacity is greater than 20% (W / W :). H 2 S is present and can be regenerated using air. Brief Description of the Drawings Figure 1 shows the X-ray diffraction pattern of the desulfurizing agent according to Example 1, and compared with the X-ray card (JCPDS card) retrieval, the data in Figure 1 shows that the main component of the desulfurization is Ca 2 Fe 2 0 5 ; Figure 2 shows the X-ray diffraction pattern of the desulfurizing agent used in Example 1 to remove H 2 S. The desulfurizing agent was penetrated and compared with an X-ray card (JCPDS card). Data in Figure 2 It is shown that its main component is a mixture of Fe 7 S 8 and FeS. The best mode for carrying out the present invention Example 1 Take 42 grams of Fe 2 0 3 powder and 58 grams of CaO powder, add water, stir, knead, extrude, It is dried at about 100 ° C for about 2 hours, and calcined at 900 ° C for 3 hours in an oxidizing atmosphere. After cooling, about 10 g of H 2 0 is sprayed uniformly to obtain a desulfurizing agent VIII. Example 2 Take 42 grams of Fe 2 0 3 powder and 58 grams of CaO powder, add water, stir, knead, extrude, dry at about 100 ° C for about 2 hours, roast at 1000 ° C in an oxidizing atmosphere for 2 hours, and cool After spraying about 10 grams of water uniformly, a desulfurizing agent was obtained ^ Example 3 35 grams of Fe 2 0 3 powder and 65 grams of Ca (OH) 2 powder were added, water was added, stirred, kneaded, extruded, and dried at about 100 ° C for about After baking for 2 hours at 900 ° C in an oxidizing atmosphere for 3 hours, after cooling, about 10 g of H 2 0 was sprayed uniformly to obtain a desulfurizing agent. Example 4 Take 32.5 grams of Fe (OH) 3 powder and 67.5 grams of Ca (OH) 2 powder, add water, stir, knead, extrude, dry at about 100 ° C for about 2 hours, and 900 ° C in an oxidizing atmosphere After baking for 3 hours, after cooling, about 10 grams of ¾0 were sprayed uniformly to obtain desulfurizing agent 0. Example 5 Take 49 grams of Fe 2 0 3 powder and 51 grams of CaO powder, add water, stir, knead, extrude, dry at about 100 ° C for about 2 hours, roast at 900 ° C for 3 hours, and cool After spraying about 10 g of H 2 0 evenly, a desulfurizing agent was obtained. Example 6 Take 37 g of Fe 2 0 3 powder, 43 g of Ca (OH) 2 powder, 20 g of bentonite, add water, stir, knead, squeeze, and dry at about 100 ° C for about 2 hours. In an oxidizing atmosphere 900 ° C baking Burn for 3 hours, and spray about 10 grams of H 2 0 evenly after cooling. . Example 7 Take 35 g of Fe 2 0 3 powder, 65 g of Ca (OH) 2 powder, 1 g of carbon powder, add water, stir, knead, extrude, and dry at about 100 ° C for about 2 hours. In an oxidizing atmosphere It was calcined at 900 ° C for 3 hours. After cooling, about 10 g of H 2 0 was sprayed uniformly to obtain desulfurizing agent 0. Example 8 Take 30.5 g of Fe 2 0 3 powder, 49.5 g of Ca (OH) 2 powder, 1 g of carbon powder, and 20 g of bentonite, add water, stir, knead, squeeze, and dry at about 100 C for about 2 hours. It was calcined at 900 ° C for 3 hours in an oxidizing atmosphere, and after cooling, about 10 grams of ¾ were sprayed uniformly to obtain a desulfurizing agent 11. Example 9 Take 29.6 grams of Fe 2 0 3 powder, 27.5 grams of Ca (OH) 2 powder, 32.9 grams of Ca (HC0 3 ) 2 powder, 10 grams of bentonite, add water, stir, knead, extrude, and pass through 150 ° C After drying for about 2 hours, baking at 1000 ° C for 2 hours in an oxidizing atmosphere, after cooling, about 10 g of H 2 0 was sprayed uniformly to obtain a desulfurizing agent I. Example 10 Take 46.2 g of Fe 2 0 3 powder, (21.4 g of 2 powder, 32.4 g of CaO powder, 2 g of carbon powder, add water, stir, knead, extrude, and dry at about 100 ° C for about 2 hours. Roasted at 1000 ° C for 2 hours in an oxidizing atmosphere. After cooling, uniformly spray about 10 g of H 2 0 to obtain a desulfurizing agent.
J o 实施例 11 取 Fe203粉末 41.7克， CaO粉末 50克， Ca(HC03)2粉末 8.3克， 膨润土 2 0克， 加水， 搅拌， 捏合， 挤条成型， 经 100°C左右干燥约 2小时， 在氧 化性气氛中 950°C焙烧 3小时，冷却后均匀喷洒约 10克 H20，得脱硫剂！^ 实施例 12 取 Fe203粉末 25.6克， Ca(OH)2粉末 11.9克， CaO粉末 9.0克， Ca(HC 03)2粉末 14.2克， 膨润土 30克， 加水， 搅拌， 捏合， 挤条成型， 经 100° C左右干燥约 3小时， 在氧化性气氛中 100°C焙烧 2小时， 冷却后均匀喷 洒约 15克 H20， 得脱硫剂 。 取上述实施例 1至 12制备的脱硫剂各 5克， 在常温常压下， 空速为 10 OOh"1 ,用含 H2S为 5000ppm的标准气进行评估，采用国产 WLSP~852微量 硫分析测定仪， 该仪器由化工部西南化工研究院生产， 最低检测量为 0. 02ppm或自配硝酸银 (1 溶液作出口定性检测， 未检出 H2S。 实验 1 反应条件常温 20°C， 压力为常压， H2S浓度 5000ppm的混合 气， 空速为 lOOOh-1 , 其检测结果如表 1所示： J o Example 11 Take 41.7 grams of Fe 2 0 3 powder, 50 grams of CaO powder, 8.3 grams of Ca (HC0 3 ) 2 powder, 20 grams of bentonite, add water, stir, knead, squeeze, and dry at about 100 ° C. About 2 hours, roast at 950 ° C for 3 hours in an oxidizing atmosphere, and spray about 10 g of H 2 0 evenly after cooling to obtain a desulfurizing agent! ^ Example 12 Take 25.6 grams of Fe 2 0 3 powder, 11.9 grams of Ca (OH) 2 powder, 9.0 grams of CaO powder, Ca (HC 03) 2 powder 14.2 g, bentonite 30 g, add water, stirring, kneading, extruding molding, by about 100 ° C and dried for about 3 hours, in an oxidizing atmosphere to 100 ° C and calcined for 2 hours, cooled uniformly sprayed about 15 Gram H 2 0 to get desulfurizer. Take 5 grams of each of the desulfurizers prepared in Examples 1 to 12 above. At room temperature and pressure, the space velocity is 100,000 h " 1. Use standard gas containing H 2 S at 5000 ppm for evaluation. Use domestic WLSP ~ 852 trace sulfur analysis. This instrument is produced by the Southwest Chemical Research Institute of the Ministry of Chemical Industry. The minimum detection amount is 0.02 ppm or self-equipped silver nitrate (1 solution for qualitative detection, no H 2 S is detected. Experiment 1 reaction conditions at room temperature 20 ° C, A mixture of atmospheric pressure and 5000 ppm H 2 S concentration at a space velocity of 1000 h- 1 . The test results are shown in Table 1:
表一 1  Table 1 1
Figure imgf000008_0001
Figure imgf000008_0001
分析采用国产 WLSP〜852微量硫分析仪测定 ¾S，该仪器由化工部西 南化工研究院生产， 最低检测量为 0.02ppm。 本发明的脱硫剂较目前市售 ZnO低温脱硫剂活性高效果好，硫容显 著提高， 对比实验如下： 实验 2实验考查 H2S含量为 2000ppm的混合气， 在空速为 1500h- 3 OOOh"1 , 450011-1 , 6000h- 1四个条件下的脱硫情况， 其中本发明的脱硫剂 采用实施例 5制备的脱硫剂， 两种脱硫剂不同空速时硫容量比较如表 2 表一 2
Figure imgf000009_0001
实验 3在双塔串联实验中， 每个反应器中脱硫剂用量为 50g， 空速 为 OOh-1 , 原料气为工业合成气， H2S含量为 5000ppm， 反应温度为 20° C, 压力为常压。 脱硫尾气 H2S控制在 l .Oppm以下， 当出口气 H2S含量超 出 l.Oppm时， 即认为脱硫剂已经被穿透， 实验结束， 用常规方法测定反 应器的硫容。 其中本发明的脱硫剂采用实施例 5制备的脱硫剂， 双塔实 验硫容数据如表 3 表一 3
Figure imgf000009_0002
实验 4 实验考查在 20°C， 压力为常压， 空速为 lh-1条件下， 在 不同 H2S含量的液态物料中脱除 H2S的情况， 其中本发明的脱硫剂采 用实施例 5制备的脱硫剂。 其实验检测结果如表一 4所示。 表一 4 样品 ΛΠ H2S (ppoi) 出口 H2S^1 (ppm) 硫容 环已烷 25.3 < 1 23.1 液体石蜡 30.2 < 1 20.8 航空煤油 133.5 < 1 21.5 航空汽油 216.4 < 1 22.6 加氢焦化汽油 531.5 < 1 23.5 加氢焦化汽油 〉2000 < 1 25.6 实验 5 空速为 51^， 其它条件同实验 4实验结果见表一5。 The analysis uses a domestic WLSP ~ 852 trace sulfur analyzer to determine ¾S. This instrument is produced by the Southwest Chemical Research Institute of the Ministry of Chemical Industry. The minimum detection amount is 0.02ppm. The desulfurizer of the present invention has better activity and higher sulfur capacity than the current commercially available ZnO low-temperature desulfurizers, and the sulfur capacity is significantly improved. The comparison experiment is as follows: Experiment 2 The experiment examines a mixture gas with an H 2 S content of 2000 ppm at a space velocity of 1500h- 3 OOOh " 1, 450011-1 desulfurization case of four conditions 6000h- 1, wherein the desulfurizing agent of the present invention employs a desulfurizing agent prepared in Example 5 embodiment, when two kinds of different sorbent sulfur capacity airspeed Comparative table 2 Table one 2
Figure imgf000009_0001
Experiment 3 In a two-tower series experiment, the amount of desulfurizing agent in each reactor was 50 g, the space velocity was OOh- 1 , the raw material gas was industrial synthesis gas, the H 2 S content was 5000 ppm, the reaction temperature was 20 ° C, and the pressure was Normal pressure. The desulfurization tail gas H 2 S is controlled below 1.0 ppm. When the content of the outlet gas H 2 S exceeds 1.0 ppm, it is considered that the desulfurizing agent has been penetrated, and the experiment is finished, and the sulfur capacity of the reactor is measured by a conventional method. The desulfurizing agent of the present invention adopts the desulfurizing agent prepared in Example 5. The sulfur capacity data of the double tower experiment are shown in Table 3 and Table 1.
Figure imgf000009_0002
Experiment 4 The experiment examined the removal of H 2 S in a liquid material with different H 2 S content under the conditions of 20 ° C, normal pressure and space velocity of lh- 1 . The desulfurizing agent of the present invention uses an example. 5 Desulfurizing agent prepared. The experimental test results are shown in Table 1-4. Table 1 Sample ΛΠ H 2 S (ppoi) H 2 S ^ 1 (ppm) Thiocyclohexane 25.3 <1 23.1 Liquid paraffin 30.2 <1 20.8 Aviation kerosene 133.5 <1 21.5 Aviation gasoline 216.4 <1 22.6 Hydrocoking Gasoline 531.5 <1 23.5 Hydrocoking gasoline> 2000 <1 25.6 The space velocity of Experiment 5 was 51 ^. Other conditions are the same as those of Experiment 4. The experimental results are shown in Table 5.
Figure imgf000010_0001
实验 4、 5中所用样品是将精制后的原料， 通入一定量的 ¾S标准 气，经检测标定后，再按实验要求配制而成的。其中 ¾S含量为 531.5ppm 的加氢焦化汽油是取自炼油厂的实际产品。 工业应用性 本发明涉及一种可在气态物料和液态物料中脱除 H2S气体的脱硫剂 及其制备方法，其有效活性组份为 C¾Fe205。它由主要成份为氧化铁和 /或氢氧化铁和 /或硝酸铁粉末与氧化钙和 /或氢氧化钙和 /或碳酸氢钙和 / 或碳酸钙粉末在高温下焙烧制成，该脱硫剂可广泛用于 煤气、合成气、 氨气、 氢气等各种含硫化氢气体中脱硫。 也可以在煤油、 汽油、环已垸 等液态物流中使用。 经工业实验证实， 其一次饱和硫容大于 20%， 具 有适用温度、 压力范围广， 效率高， 反应速度快， 脱硫精度高的特点。 在本发明中， 脱硫剂具有特定的 Ca2Fe205结构， 其 X射线衍射图 表明， 这种结构是以特定 Ca:Fe和焙烧温度为基础的， 不同的 Ca:Fe需 要不同的焙烧温度，而且含有杂质的原料不能或基本不能焙烧出特定的 Ca2Fe205结构。 与 CN1067828A所公开的技术相比， 本发明脱硫剂有如下不同： Ca:Fe有特定的比例； 在原料中没有其它杂质， 原料中不含铁； 混合物 料焙烧前要经搅拌、 捏合、 干燥步骤； 焙烧是在氧化气氛中进行的； 脱 硫的使用温度低； 硫容大； 在脱硫剂未被穿透之前都具有高的脱硫精 度； 只需一步即可完全脱除 H2S; 既可在气态物料中使用， 也可在液态 物料中使用。
Figure imgf000010_0001
The samples used in experiments 4 and 5 were made by refining the raw materials, passing a certain amount of ¾S standard gas, and testing and calibrating, and then preparing them according to the experimental requirements. The hydrocoking gasoline with a ¾S content of 531.5 ppm is an actual product taken from a refinery. INDUSTRIAL APPLICABILITY The present invention relates to a desulfurizing agent capable of removing H 2 S gas in a gaseous material and a liquid material, and a preparation method thereof. The effective active component is C ¾ Fe 2 0 5 . It is mainly made by roasting iron oxide and / or iron hydroxide and / or iron nitrate powder with calcium oxide and / or calcium hydroxide and / or calcium bicarbonate and / or calcium carbonate powder at high temperature. The desulfurizing agent It can be widely used for desulfurization in various hydrogen sulfide-containing gases such as coal gas, synthesis gas, ammonia gas, hydrogen gas, etc. It can also be used in liquid streams such as kerosene, gasoline, and cyclohexane. It has been confirmed by industrial experiments that its primary saturated sulfur capacity is greater than 20%, and has the characteristics of wide applicable temperature and pressure range, high efficiency, fast reaction speed, and high desulfurization accuracy. In the present invention, the desulfurizing agent has a specific Ca 2 Fe 2 0 5 structure, and its X-ray diffraction pattern shows that this structure is based on a specific Ca: Fe and roasting temperature, and different Ca: Fe requires different roasting. Temperature, and the raw materials containing impurities cannot or basically cannot calcine a specific Ca 2 Fe 2 0 5 structure. Compared with the technology disclosed in CN1067828A, the desulfurizing agent of the present invention has the following differences: Ca: Fe has a specific ratio; there are no other impurities in the raw material, and the raw material does not contain iron; the mixture is subjected to stirring, kneading and drying steps before firing ; Roasting is carried out in an oxidizing atmosphere; the temperature of desulfurization is low; the sulfur capacity is large; the desulfurization accuracy is high before the desulfurization agent is not penetrated; H 2 S can be completely removed in one step; Used in gaseous materials, but also in liquid materials.

Claims

权利要求 Rights request
1. 一种可在气态或液态物料中脱除 H2S的脱硫剂， 1. A desulfurizing agent capable of removing H 2 S in gaseous or liquid materials,
其特征在于: 该脱硫剂的有效活性组份为 Ca2Fe205。 It is characterized in that the effective active component of the desulfurizing agent is Ca 2 Fe 2 0 5 .
2. 如权利要求 1的脱硫剂，  2. The desulfurizing agent according to claim 1,
其特征在于: 有效活性组分 Ca2Fe205的量大于脱硫剂总重量的 40°/。。It is characterized in that the amount of the effective active component Ca 2 Fe 2 0 5 is greater than 40 ° / of the total weight of the desulfurizing agent. .
3. 如权利要求 2的脱硫剂， 3. The desulfurizing agent according to claim 2,
其特征在于: 有效活性组分 Ca2Fe205的量占脱硫剂总重量的 70%~90%。 It is characterized in that the amount of effective active component Ca 2 Fe 2 0 5 accounts for 70% to 90% of the total weight of the desulfurizing agent.
4. 如权利要求 2或 3的脱硫剂， 4. The desulfurizing agent according to claim 2 or 3,
其特征在于: 含有小于脱硫剂总重量 20%的水。 It is characterized by containing less than 20% of the total weight of the desulfurizer.
5. 如权利要求 2的脱硫剂， 5. The desulfurizing agent according to claim 2,
其特征在于: 含有小于脱硫剂总重量 40%的氧化钙、氢氧化钙和皂土类 的结构助剂。 It is characterized in that it contains less than 40% of the total weight of the desulfurizer by calcium oxide, calcium hydroxide and bentonite.
6. 如权利要求 2的脱硫剂， 6. The desulfurizing agent according to claim 2,
其特征在于: 该脱硫剂的比表面积为 1.8〜3 m2/g。 It is characterized in that the specific surface area of the desulfurizing agent is 1.8 to 3 m 2 / g.
7. 如权利要求 2的脱硫剂，  7. The desulfurizing agent according to claim 2,
其特征在于: 该脱硫剂的孔隙率为 50%~~65%。 It is characterized by: The porosity of the desulfurizing agent is 50% ~~ 65%.
8. 如权利要求 2的脱硫剂，  8. The desulfurizing agent according to claim 2,
其特征在于: 该脱硫剂的表观密度为: 1.0~1.5g/cm3。 It is characterized in that the apparent density of the desulfurizing agent is: 1.0 to 1.5 g / cm 3 .
9. 一种权利要求 1至 8中任何一项脱硫剂的制备方法， 其特征在于： 包括如下步骤：  9. A method for preparing a desulfurizing agent according to any one of claims 1 to 8, characterized in that it comprises the following steps:
a. 将主要成份为氧化铁和 /或氢氧化铁和 /或硝酸铁的粉末与氧化 b.钙和 /或氢氧化钙和 Z或碳酸氢钙和 /或碳酸钙的粉末混合， 其中 c 铁与钙的摩尔比为 1:1至 1:5;  a. Mix the powder whose main ingredient is iron oxide and / or iron hydroxide and / or iron nitrate with oxide b. Calcium and / or calcium hydroxide and Z or calcium bicarbonate and / or calcium carbonate powder, where c iron The molar ratio to calcium is 1: 1 to 1: 5;
d.将混合料加水搅拌， 成型， 干燥；  d. Mix the material with water, stir, shape, and dry;
e. 在 700°C~1100°C温度下的氧化性气氛中焙烧 0.5至 24小时；  e. Baking in an oxidizing atmosphere at 700 ° C ~ 1100 ° C for 0.5 to 24 hours;
9 9
替换页（细则第 26条） f. 待冷却后均匀喷洒少量水制得脱硫剂成品。 Replacement page (Article 26) f. After cooling, spray a small amount of water evenly to make the finished product of desulfurizer.
10. 如权利要求 9的方法，  10. The method of claim 9,
其特征在于: 所述的焙烧温度在 850°C〜950°C之间， 焙烧时间为 2至 3 小时。  It is characterized in that the roasting temperature is between 850 ° C and 950 ° C, and the roasting time is 2 to 3 hours.
11. 如权利要求 9的方法， 11. The method of claim 9,
其特征在于: 所述的焙烧温度在 950°C~1050°C之间， 焙烧时间为 0.5至It is characterized in that the roasting temperature is between 950 ° C ~ 1050 ° C, and the roasting time is 0.5 to
1.5小时。 1.5 hours.
12. 如权利要求 9的方法， 12. The method of claim 9,
其特征在于： 所述的干燥温度为 100°C〜200。 ( ， 干燥时间为 1至 4小时。 It is characterized in that the drying temperature is 100 ° C ~ 200. (, Drying time is 1 to 4 hours.
13. 如权利要求 9的方法， 13. The method of claim 9,
其特征在于: 步骤 a中的配料为 Fe203和 CaO， 铁与钙的摩尔比为 1:1至 1:2。 It is characterized in that the ingredients in step a are Fe 2 0 3 and CaO, and the molar ratio of iron to calcium is 1: 1 to 1: 2.
14. 如权利要求 13的方法，  14. The method of claim 13,
其特征在于: 所述摩尔比为 2:3。 It is characterized in that the molar ratio is 2: 3.
15. 如权利要求 9的方法， 15. The method of claim 9,
其特征在于: 步骤 a中的配料为 Fe203和 Ca(HC03)2， 铁与钙的摩尔比为 1:1至 1:2。 It is characterized in that the ingredients in step a are Fe 2 0 3 and Ca (HC0 3 ) 2 , and the molar ratio of iron to calcium is 1: 1 to 1: 2.
16. 如权利要求 15的方法，  16. The method of claim 15,
其特征在于: 所述摩尔比为 2:3。 It is characterized in that the molar ratio is 2: 3.
17. 如权利要求 9所述的方法， 17. The method of claim 9,
其特征在于: 步骤 a中的配料为 Fe203和 Ca(OH)2， 铁与钙的摩尔比为 1:1 至 1:2。 It is characterized in that the ingredients in step a are Fe 2 0 3 and Ca (OH) 2 , and the molar ratio of iron to calcium is 1: 1 to 1: 2.
18. 如权利要求 17的方法，  18. The method of claim 17,
其特征在于: 所述摩尔比为 2:3。 It is characterized in that the molar ratio is 2: 3.
19. 如权利要求 9的方法， 19. The method of claim 9,
其特征在于: 步骤 a中的配料为 Fe(OH)3和 CaO， 铁与钙的摩尔比为 1:1 至 1:2。 It is characterized in that the ingredients in step a are Fe (OH) 3 and CaO, and the molar ratio of iron to calcium is 1: 1 to 1: 2.
20. 如权利要求 19的方法， 其特征在于: 所述摩尔比为 2:3。 20. The method of claim 19, It is characterized in that the molar ratio is 2: 3.
21. 如权利要求 9的方法，  21. The method of claim 9,
其特征在于: 在步骤 a中加入小于脱硫剂总重量 5〜30%的高岭土和 /或作 为结构助剂。 It is characterized in that, in step a, kaolin and / or as a structural assistant are added in an amount of 5 to 30% of the total weight of the desulfurizing agent.
22. 如权利要求 9的方法，  22. The method of claim 9,
其特征在于: 在步骤 a中加入少量碳粉或淀粉作为造孔剂。 It is characterized by adding a small amount of carbon powder or starch as a pore-forming agent in step a.
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CN113813946A (en) * 2021-10-26 2021-12-21 中冶赛迪上海工程技术有限公司 Desulfurizer doped with oxygen-containing functional group and preparation and application thereof
CN113813946B (en) * 2021-10-26 2023-10-24 中冶赛迪上海工程技术有限公司 Desulfurizing agent doped with oxygen-containing functional groups, and preparation and application thereof
CN114307617A (en) * 2022-02-25 2022-04-12 太原理工大学 Copper oxide composite desulfurizer and preparation method and application thereof
CN114345117A (en) * 2022-02-25 2022-04-15 太原理工大学 Ferric oxide composite desulfurizer and preparation method and application thereof
CN114345117B (en) * 2022-02-25 2023-03-14 太原理工大学 Ferric oxide composite desulfurizer and preparation method and application thereof
CN115814580A (en) * 2022-10-26 2023-03-21 北京予知环保科技有限公司 Carbide slag modified desulfurizer composition, desulfurizer, preparation method and application thereof
CN115814580B (en) * 2022-10-26 2023-09-12 北京予知环保科技有限公司 Desulfurizing agent, preparation method and application thereof
CN116422355A (en) * 2023-04-11 2023-07-14 山东泰北环保设备股份有限公司 Desulfurizing agent, preparation method and application thereof in flue gas desulfurization
CN117563413A (en) * 2024-01-15 2024-02-20 福建朝旭新能源科技有限公司 Desulfurizing agent for removing hydrogen sulfide in flue gas and preparation method thereof
CN117563413B (en) * 2024-01-15 2024-03-22 福建朝旭新能源科技有限公司 Desulfurizing agent for removing hydrogen sulfide in flue gas and preparation method thereof

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