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TW202400812A - Preparation method for lumpy desulfurizing agent avoiding the problem that the content of sulfur in molten steel cannot be reduced effectively because the desulfurizing agent is sucked by a dust collecting apparatus - Google Patents

Preparation method for lumpy desulfurizing agent avoiding the problem that the content of sulfur in molten steel cannot be reduced effectively because the desulfurizing agent is sucked by a dust collecting apparatus Download PDF

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TW202400812A
TW202400812A TW111123879A TW111123879A TW202400812A TW 202400812 A TW202400812 A TW 202400812A TW 111123879 A TW111123879 A TW 111123879A TW 111123879 A TW111123879 A TW 111123879A TW 202400812 A TW202400812 A TW 202400812A
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desulfurizer
block
calcium oxide
preparation
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TWI814460B (en
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吳威德
羅紹峰
林啟明
張育恩
沈峻名
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國立中興大學
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  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

A preparation method for a lumpy desulfurizing agent includes the following steps: performing a hydration reaction on a first component containing calcium oxide with a particle size of 1.4mm or less with water to convert a portion of calcium oxide into calcium hydroxide to obtain a mixture containing calcium hydroxide and calcium oxide; and drying the mixture to remove the water to obtain a dry product; mixing the dry product with a second component containing aluminum dross, and performing pressurizing and molding. The lumpy desulfurizing agent prepared by using the preparation method of this invention retains its original form after storage and has good molding stability, which makes it easy to use and has good operability when being used in a steelmaking process. Meanwhile, the problem of poor desulfurization efficiency caused by a fact that the content of sulfur in molten steel can not be reduced effectively because the desulfurizing agent is sucked in by a dust collecting apparatus of a steelmaking device can be avoided when the desulfurizing agent is put into the steelmaking device.

Description

塊狀脫硫劑的製備方法Preparation method of block desulfurizer

本發明是有關於一種去除劑的製備方法,特別是指一種塊狀脫硫劑的製備方法。The present invention relates to a method for preparing a removal agent, in particular to a method for preparing a massive desulfurizer.

由於鋼鐵的用途日益廣泛,致使對鋼鐵性能的要求也日漸提高,而要使鋼鐵性能提升的關鍵技術之一是使鋼液的純淨度提升,尤其是降低該鋼液中的硫含量,因此,如何降低鋼液中的硫含量為廣泛被研究的議題。一般來說,降低鋼液中的硫含量的方法大多是利用脫硫劑來進行。As the uses of steel become more and more widespread, the requirements for the performance of steel are also increasing day by day. One of the key technologies to improve the performance of steel is to improve the purity of molten steel, especially to reduce the sulfur content in the molten steel. Therefore, How to reduce the sulfur content in molten steel is a widely studied topic. Generally speaking, most methods to reduce the sulfur content in molten steel are by using desulfurizers.

中國大陸專利公告第1074685號揭示一種能夠用於氣態物料或液態物料中脫除H 2S的脫硫劑,且該脫硫劑的製備方法包含將鐵源粉末、鈣源粉末及結構助劑混合,然後,依序進行加水攪拌、成型、乾燥、焙燒及冷卻等步驟。該鐵源粉末例如氧化鐵粉末、氫氧化鐵粉末,或硝酸鐵粉末等。該鈣源粉末例如氧化鈣、氫氧化鈣、碳酸氫鈣,或碳酸鈣等。該結構助劑例如氧化鋁、氧化矽、膨潤土、高嶺土,或皂土等。 Mainland China Patent Announcement No. 1074685 discloses a desulfurizer that can be used to remove H 2 S from gaseous or liquid materials, and the preparation method of the desulfurizer includes mixing iron source powder, calcium source powder and structural aids , and then perform steps such as adding water, stirring, shaping, drying, roasting and cooling in sequence. The iron source powder is, for example, iron oxide powder, iron hydroxide powder, or iron nitrate powder. The calcium source powder is, for example, calcium oxide, calcium hydroxide, calcium bicarbonate, or calcium carbonate. The structural aids include alumina, silica, bentonite, kaolin, or bentonite.

雖然該專利案的脫硫劑能夠成型,然而,一般而言,該脫硫劑生產後往往不一定能夠立即被銷售出去或使用,因此,該脫硫劑在儲放後是否會崩解或粉末化而有成型安定性的問題產生是生產者所需要思量的事項,而之所以需要思量,是因為當脫硫劑的成型安定性不佳,會導致用於煉鋼的過程中不便使用而有操作性不佳的問題產生,同時,因成型安定性不佳而容易崩解產生粉末化現象,致使當投入煉鋼設備中,易被該煉鋼設備的集塵裝置吸入,導致無法有效地降低鋼液中的硫含量,從而有脫硫效率不佳的問題產生。Although the desulfurizer in this patent can be molded, generally speaking, the desulfurizer may not be sold or used immediately after production. Therefore, whether the desulfurizer will disintegrate or become powder after storage The problem of molding stability caused by desulfurization is something that producers need to consider. The reason why they need to be considered is because when the desulfurizer has poor molding stability, it will cause inconvenience and problems in the steelmaking process. The problem of poor operability arises. At the same time, due to poor molding stability, it is easy to disintegrate and produce powder. As a result, when put into steelmaking equipment, it is easily sucked into the dust collection device of the steelmaking equipment, resulting in the inability to effectively reduce the dust. The sulfur content in the molten steel causes the problem of poor desulfurization efficiency.

因此,本發明的目的,即在提供一種塊狀脫硫劑的製備方法。Therefore, the object of the present invention is to provide a method for preparing a block desulfurizer.

於是,本發明塊狀脫硫劑的製備方法,包含:將包括粒徑為1.4mm以下的氧化鈣的第一組分與水進行水合反應,以使部分的氧化鈣轉變成氫氧化鈣,而獲得包含氫氧化鈣及氧化鈣的混合物;將該混合物進行乾燥處理,以去除水分,獲得乾燥物;將該乾燥物與包括鋁渣的第二組分混合,並進行加壓成型處理,其中,該鋁渣包括三氧化二鋁。Therefore, the preparation method of the block desulfurizer of the present invention includes: performing a hydration reaction between the first component including calcium oxide with a particle size of 1.4 mm or less and water, so that part of the calcium oxide is converted into calcium hydroxide, and Obtain a mixture containing calcium hydroxide and calcium oxide; dry the mixture to remove moisture to obtain a dry product; mix the dry product with a second component including aluminum slag, and perform a pressure forming process, wherein, The aluminum slag includes aluminum oxide.

本發明的功效在於:透過上述流程的設計,尤其是使氧化鈣轉變成氫氧化鈣的設計,由本發明的塊狀脫硫劑的製備方法所製得的塊狀脫硫劑在含有水氣環境中存放一段時間後,不易有因氧化鈣遇水氣而產生的膨脹現象,導致崩解而產生粉末化的問題產生,致使仍保有原有形態而具有不錯的成型安定性,以至於用於煉鋼的過程中,方便使用而具有不錯的操作性,且因在一段時間的存放後不會有因崩解而產生粉末化的現象,所以當投入煉鋼設備中時能夠避免被該煉鋼設備的集塵裝置吸入而無法有效地降低鋼液中的硫含量,致使脫硫效率不佳的問題產生。The effect of the present invention is: through the design of the above-mentioned process, especially the design of converting calcium oxide into calcium hydroxide, the block desulfurizer prepared by the preparation method of the block desulfurizer of the present invention can be used in an environment containing water vapor. After being stored in a medium for a period of time, calcium oxide will not easily expand due to the presence of water vapor, leading to disintegration and powdering. As a result, it still retains its original shape and has good molding stability, so that it can be used for refining. In the process of making steel, it is easy to use and has good operability, and because there will be no powdering due to disintegration after a period of storage, it can avoid being used by the steelmaking equipment when it is put into the steelmaking equipment. The dust collection device sucks in the dust and cannot effectively reduce the sulfur content in the molten steel, resulting in the problem of poor desulfurization efficiency.

本發明塊狀脫硫劑的製備方法包含將包括粒徑為1.4mm以下的氧化鈣的第一組分與水進行水合反應,以使部分的氧化鈣轉變成氫氧化鈣,而獲得包含氫氧化鈣及氧化鈣的混合物;將該混合物進行乾燥處理,以去除水分,獲得乾燥物;將該乾燥物與包括鋁渣的第二組分混合,並進行加壓成型處理,其中,該鋁渣包括三氧化二鋁。The preparation method of the block desulfurizer of the present invention includes performing a hydration reaction between the first component including calcium oxide with a particle size of 1.4 mm or less and water, so that part of the calcium oxide is converted into calcium hydroxide, so as to obtain a calcium oxide containing hydroxide. A mixture of calcium and calcium oxide; drying the mixture to remove moisture to obtain a dry product; mixing the dry product with a second component including aluminum slag, and performing a pressure forming process, wherein the aluminum slag includes Aluminum trioxide.

以下對本發明進行詳細說明。The present invention will be described in detail below.

透過該水合反應使部分氧化鈣轉變成氫氧化鈣的設計,由本發明塊狀脫硫劑的製備方法所製得的塊狀脫硫劑中存在適量的氧化鈣,因此,當該塊狀脫硫劑在含有水氣環境中存放一段時間後,不易有因氧化鈣遇水氣而大幅度地產生膨脹現象,導致崩解而產生粉末化的問題產生,致使仍保有原有形態而具有不錯的成型安定性。在本發明的一些實施態樣中,該水合反應的溫度範圍為25℃至150℃,且時間範圍為10分鐘至180分鐘。Part of the calcium oxide is converted into calcium hydroxide through the hydration reaction. There is an appropriate amount of calcium oxide in the block desulfurizer prepared by the method for preparing the block desulfurizer of the present invention. Therefore, when the block desulfurizer is After the agent is stored in an environment containing water vapor for a period of time, it is not easy for calcium oxide to expand significantly when exposed to water vapor, leading to disintegration and powdering. As a result, it still retains its original shape and has good molding. Stability. In some embodiments of the present invention, the temperature of the hydration reaction ranges from 25°C to 150°C, and the time ranges from 10 minutes to 180 minutes.

在本發明的一些實施態樣中,該第一組分還包括精煉渣,且該精煉渣包括氧化鈣。由於該精煉渣是透過回收方式取得且該精煉渣包括氧化鈣,因此,該精煉渣能夠用來取代天然的氧化鈣及減少該第一組分中來自天然的氧化鈣的用量,而採用如此的方式,有助於本發明塊狀脫硫劑的製備方法具有達到廢棄物再利用、淨零排放及低製造成本的優點。該精煉渣例如但不限於來自煉鋼廠的精煉渣。In some embodiments of the present invention, the first component further includes refining slag, and the refining slag includes calcium oxide. Since the refining slag is obtained through recycling and the refining slag includes calcium oxide, the refining slag can be used to replace natural calcium oxide and reduce the amount of natural calcium oxide in the first component. By using such This method helps the preparation method of the block desulfurizer of the present invention to achieve the advantages of waste reuse, net-zero emissions and low manufacturing cost. The refining slag is, for example, but not limited to, refining slag from a steel mill.

在本發明的一些實施態樣中,該氧化鈣、該水及該精煉渣的重量比例範圍為1:0.45至2:大於0且1.5以下。In some embodiments of the present invention, the weight ratio of the calcium oxide, the water and the refining slag ranges from 1:0.45 to 2: greater than 0 and less than 1.5.

透過該乾燥處理去除該混合物中的水分,使得該乾燥物的含水率低,致使能夠避免該乾燥物存在水分時,水分與該第二組分中的鋁渣反應產生具有刺激氣味的氨氣,而有嗅覺不適感的問題產生。The moisture in the mixture is removed through the drying process, so that the moisture content of the dried product is low, so that when there is moisture in the dried product, the moisture reacts with the aluminum slag in the second component to generate ammonia gas with a pungent smell, And there is the problem of olfactory discomfort.

由於在以往的脫硫劑中,是使用來自天然的三氧化二鋁,而存在有成本高且天然資源消耗的問題,因此,為降低以往脫硫劑的成本以及減少天然資源的使用,在本發明中,由於該鋁渣是透過回收方式取得且該鋁渣包含三氧化二鋁,因此,該鋁渣能夠用來取代天然的三氧化二鋁,而採用如此的方式,有助於達到廢棄物再利用以及淨零排放的目的。該鋁渣例如但不限於來自煉鋁廠的鋁渣。在本發明的一些實施態樣中,以該第二組分的總量為100wt%計,該鋁渣的用量的範圍為32wt%以上。在本發明的一些實施態樣中,在該塊狀脫硫劑中該氧化鈣的含量範圍為2wt%至18wt%,且該鋁渣的含量範圍為20wt%至30wt%。Since in the past desulfurizers, natural aluminum oxide is used, which has the problem of high cost and consumption of natural resources. Therefore, in order to reduce the cost of previous desulfurizers and reduce the use of natural resources, this paper In the invention, since the aluminum slag is obtained through recycling and the aluminum slag contains aluminum oxide, the aluminum slag can be used to replace natural aluminum oxide. In this way, it helps to reduce waste reuse and net zero emissions. The aluminum slag is, for example, but not limited to, aluminum slag from an aluminum smelter. In some embodiments of the present invention, based on the total amount of the second component being 100wt%, the amount of aluminum slag ranges from 32wt% or more. In some embodiments of the present invention, the calcium oxide content in the block desulfurizer ranges from 2wt% to 18wt%, and the aluminum slag content ranges from 20wt% to 30wt%.

在本發明的一些實施態樣中,該第二組分還包括黏著劑。該黏著劑的目的在於讓該第二組分中各成分能夠團聚在一起。該黏著劑例如但不限於水泥、氫氧化鈣或硬脂酸鋅等。在本發明的一些實施態樣中,該黏著劑選自於水泥、氫氧化鈣、硬脂酸鋅,或上述任意的組合。在本發明的一些實施態樣中,以該第二組分的總量為100wt%計,該黏著劑的用量的範圍為大於0wt%且31wt%以下。在本發明的一些實施態樣中,以該塊狀脫硫劑的總量為100wt%計,在該塊狀脫硫劑中該氧化鈣的含量範圍為2wt%至18wt%、該鋁渣的含量範圍為20wt%至30wt%,且該黏著劑的含量範圍為大於0wt%且20wt%以下。In some embodiments of the invention, the second component further includes an adhesive. The purpose of the adhesive is to allow the components of the second component to agglomerate together. The adhesive may be, but is not limited to, cement, calcium hydroxide or zinc stearate. In some embodiments of the present invention, the adhesive is selected from cement, calcium hydroxide, zinc stearate, or any combination of the above. In some embodiments of the present invention, based on the total amount of the second component being 100wt%, the amount of the adhesive ranges from greater than 0wt% to less than 31wt%. In some embodiments of the present invention, based on the total amount of the massive desulfurizer being 100wt%, the content of the calcium oxide in the massive desulfurizer ranges from 2wt% to 18wt%, and the content of the aluminum slag is The content range is 20wt% to 30wt%, and the content range of the adhesive is greater than 0wt% and less than 20wt%.

在本發明的一些實施態樣中,該第二組分還包括精煉渣。該精煉渣的目的在於減少氧化鈣的消耗量。該精煉渣例如但不限於來自煉鋼廠的精煉渣。在本發明的一些實施態樣中,以該第二組分的總量為100wt%計,該精煉渣的用量的範圍為大於0wt%且53wt%以下。在本發明的一些實施態樣中,以該塊狀脫硫劑的總量為100wt%計,在該塊狀脫硫劑中該氧化鈣的含量範圍為2wt%至18wt%、該鋁渣的含量範圍為20wt%至30wt%,且該精煉渣的含量範圍為大於30wt%且40wt%以下。In some embodiments of the present invention, the second component further includes refining slag. The purpose of this refining slag is to reduce calcium oxide consumption. The refining slag is, for example, but not limited to, refining slag from a steel mill. In some embodiments of the present invention, based on the total amount of the second component being 100wt%, the amount of the refining slag ranges from greater than 0wt% to less than 53wt%. In some embodiments of the present invention, based on the total amount of the massive desulfurizer being 100wt%, the content of the calcium oxide in the massive desulfurizer ranges from 2wt% to 18wt%, and the content of the aluminum slag is The content range is 20wt% to 30wt%, and the content range of the refining slag is greater than 30wt% and less than 40wt%.

在本發明的一些實施態樣中,該加壓成型處理的8kg/cm 2至15kg/cm 2,且時間範圍為2秒至90秒。 In some embodiments of the present invention, the pressure forming process ranges from 8 kg/cm 2 to 15 kg/cm 2 and the time ranges from 2 seconds to 90 seconds.

本發明將就以下實施例來作進一步說明,但應瞭解的是,該等實施例僅為例示說明之用,而不應被解釋為本發明實施之限制。The present invention will be further described with reference to the following examples, but it should be understood that these examples are only for illustration and should not be construed as limitations on the implementation of the present invention.

實施例1Example 1

步驟(a):將包括31.5克且粒徑為0.27mm以下的氧化鈣(廠牌:CHONEYE PURE CHEMICAL)及36克的精煉渣的第一組分與14.2克的水混合,其中,該氧化鈣、該水及該精煉渣的重量比例為1:0.45:1.15,而該精煉渣來自台灣煉鋼廠,且包含55.4wt%的氧化鈣(CaO)、4.8wt%的氧化鎂(MgO)、2.7wt%的三氧化二鋁、27.2wt%的二氧化矽、7.0wt%的二氟化鈣(CaF 2)、1.9wt%的一氧化鐵(FeO)、0.4wt%的一氧化錳(MnO),及0.6wt%的硫。然後,於25℃的條件下進行30分鐘的水合反應,獲得包含氫氧化鈣及氧化鈣的混合物。 Step (a): Mix the first component including 31.5 grams of calcium oxide with a particle size of less than 0.27mm (brand: CHONEYE PURE CHEMICAL) and 36 grams of refining slag with 14.2 grams of water, wherein the calcium oxide The weight ratio of the water and the refining slag is 1:0.45:1.15, and the refining slag comes from a Taiwan steelmaking plant and contains 55.4wt% calcium oxide (CaO), 4.8wt% magnesium oxide (MgO), 2.7 wt% aluminum oxide, 27.2wt% silica, 7.0wt% calcium fluoride (CaF 2 ), 1.9wt% iron monoxide (FeO), 0.4wt% manganese monoxide (MnO) , and 0.6wt% sulfur. Then, a hydration reaction was performed at 25° C. for 30 minutes to obtain a mixture containing calcium hydroxide and calcium oxide.

步驟(b):將該混合物置於溫度設定為110℃的烘箱中進行60分鐘的乾燥處理,以去除水分,獲得74.6克的乾燥物。Step (b): Place the mixture in an oven set at a temperature of 110° C. for 60 minutes to dry to remove moisture, and obtain 74.6 grams of dry matter.

步驟(c):將該乾燥物與包括10克的氫氧化鈣(作為黏著劑)及22.5克的鋁渣的第二組分導入一台成型設備(型號:PM-20)中進行混合,並以壓力為15kg/cm 2進行2秒的加壓成型處理,獲得長為4.5cm、寬為3.8cm且高為6cm的錠狀脫硫劑,其中,該鋁渣來自台灣煉鋁廠,且包含4.4wt%的氧化鎂(MgO)、73.6wt%的三氧化二鋁、5.2wt%的金屬鋁、0.3wt%的二氧化矽、0.2wt%的氧化鉀(K 2O),及16.3wt%的氮化鋁(AlN)。 Step (c): Introduce the dried product and the second component including 10 grams of calcium hydroxide (as a binder) and 22.5 grams of aluminum slag into a molding equipment (model: PM-20) for mixing, and Pressure forming treatment was carried out for 2 seconds at a pressure of 15kg/ cm2 to obtain an ingot-shaped desulfurizer with a length of 4.5cm, a width of 3.8cm and a height of 6cm. The aluminum slag came from a Taiwan aluminum smelting plant and contained 4.4wt% magnesium oxide (MgO), 73.6wt% aluminum oxide, 5.2wt% metallic aluminum, 0.3wt% silicon dioxide, 0.2wt% potassium oxide (K 2 O), and 16.3wt% of aluminum nitride (AlN).

實施例2至4Examples 2 to 4

實施例2至4的製備方法是與實施例1的製備方法大致相同,且主要不同在於:在實施例2中,無氫氧化鈣。在實施例3至4中,是將實施例1的氫氧化鈣依序置換為硬脂酸鋅(廠牌:CHONEYE PURE CHEMICAL)及水泥(廠牌:南星),且用量依序為10克及10克。The preparation methods of Examples 2 to 4 are substantially the same as those of Example 1, and the main difference is that in Example 2, there is no calcium hydroxide. In Examples 3 to 4, the calcium hydroxide in Example 1 was replaced with zinc stearate (brand: CHONEYE PURE CHEMICAL) and cement (brand: Nanxing) in sequence, and the dosages were 10 grams and 10 grams.

實施例5Example 5

步驟(a):將包括31.5克且粒徑為0.27mm以下的氧化鈣(廠牌:CHONEYE PURE CHEMICAL)及36克的精煉渣的第一組分與14.2克的水混合,其中,該氧化鈣、該水及該精煉渣的重量比例為1:0.45:1.15,而該精煉渣來自台灣煉鋼廠,且包含55.4wt%的氧化鈣(CaO)、4.8wt%的氧化鎂(MgO)、2.7wt%的三氧化二鋁、27.2wt%的二氧化矽、7.0wt%的二氟化鈣(CaF 2)、1.9wt%的一氧化鐵(FeO)、0.4wt%的一氧化錳(MnO),及0.6wt%的硫。然後,於25℃的條件下進行30分鐘的水合反應,獲得包含氫氧化鈣及氧化鈣的混合物。 Step (a): Mix the first component including 31.5 grams of calcium oxide with a particle size of less than 0.27mm (brand: CHONEYE PURE CHEMICAL) and 36 grams of refining slag with 14.2 grams of water, wherein the calcium oxide The weight ratio of the water and the refining slag is 1:0.45:1.15, and the refining slag comes from a Taiwan steelmaking plant and contains 55.4wt% calcium oxide (CaO), 4.8wt% magnesium oxide (MgO), 2.7 wt% aluminum oxide, 27.2wt% silica, 7.0wt% calcium fluoride (CaF 2 ), 1.9wt% iron monoxide (FeO), 0.4wt% manganese monoxide (MnO) , and 0.6wt% sulfur. Then, a hydration reaction was performed at 25° C. for 30 minutes to obtain a mixture containing calcium hydroxide and calcium oxide.

步驟(b):將該混合物置於溫度設定為110℃的烘箱中進行60分鐘的乾燥處理,獲得74.6克的乾燥物。Step (b): Place the mixture in an oven with a temperature set to 110°C for 60 minutes to dry, to obtain 74.6 grams of dried product.

步驟(c):將該乾燥物與包括10克的氫氧化鈣(作為黏著劑)及22.5克的鋁渣的第二組分導入一台成型設備(型號:PM-20)中進行混合,並以壓力為15kg/cm 2進行2秒的加壓成型處理,獲得長為4.5cm、寬為3.8cm且高為6cm的錠狀脫硫劑,其中,該鋁渣來自台灣煉鋁廠,且包含4.4wt%的氧化鎂(MgO)、73.6wt%的三氧化二鋁、5.2wt%的金屬鋁、0.3wt%的二氧化矽、0.2wt%的氧化鉀(K 2O),及16.3wt%的氮化鋁(AlN)。 Step (c): The dry material and the second component including 10 grams of calcium hydroxide (as a binder) and 22.5 grams of aluminum slag are introduced into a molding equipment (model: PM-20) for mixing, and Pressure forming treatment was carried out for 2 seconds at a pressure of 15kg/ cm2 to obtain an ingot-shaped desulfurizer with a length of 4.5cm, a width of 3.8cm and a height of 6cm. The aluminum slag came from a Taiwan aluminum smelting plant and contained 4.4wt% magnesium oxide (MgO), 73.6wt% aluminum oxide, 5.2wt% metallic aluminum, 0.3wt% silica, 0.2wt% potassium oxide (K 2 O), and 16.3wt% of aluminum nitride (AlN).

實施例6至13Examples 6 to 13

實施例6至13的製備方法是與實施例5的製備方法大致相同,且主要不同在於:改變該氧化鈣的粒徑或/及該水的用量比例,參閱表1及表2。The preparation methods of Examples 6 to 13 are substantially the same as those of Example 5, and the main difference lies in changing the particle size of the calcium oxide or/and the dosage ratio of the water. See Table 1 and Table 2.

實施例14Example 14

步驟(a):將31.5克且粒徑為1.4mm以下的氧化鈣及31.5克的水混合。然後,於25℃的條件下進行90分鐘的水合反應,獲得包含氫氧化鈣及氧化鈣的混合物。Step (a): Mix 31.5 grams of calcium oxide with a particle size of less than 1.4 mm and 31.5 grams of water. Then, a hydration reaction was performed at 25° C. for 90 minutes to obtain a mixture containing calcium hydroxide and calcium oxide.

步驟(b):將該混合物置於溫度設定為110℃的烘箱中進行60分鐘的乾燥處理,獲得40.5克的乾燥物。Step (b): Place the mixture in an oven with a temperature set to 110° C. for 60 minutes to dry, to obtain 40.5 grams of dried product.

步驟(c):將該乾燥物與包括10克的氫氧化鈣(作為黏著劑)、22.5克的鋁渣及36克的精煉渣的第二組分導入一台成型設備(型號:PM-20)中進行混合,並以壓力為15kg/cm 2進行2秒的加壓成型處理,獲得長為4.5cm、寬為3.8cm且高為6cm的錠狀脫硫劑,其中,該鋁渣來自台灣煉鋁廠,且包含4.4wt%的氧化鎂(MgO)、73.6wt%的三氧化二鋁、5.2wt%的金屬鋁、0.3wt%的二氧化矽、0.2wt%的氧化鉀(K 2O),及16.3wt%的氮化鋁(AlN),而該精煉渣來自台灣煉鋼廠,且包含55.4wt%的氧化鈣(CaO)、4.8wt%的氧化鎂(MgO)、2.7wt%的三氧化二鋁、27.2wt%的二氧化矽、7.0wt%的二氟化鈣(CaF 2)、1.9wt%的一氧化鐵(FeO)、0.4wt%的一氧化錳(MnO),及0.6wt%的硫。 Step (c): Introduce the dried product and the second component including 10 grams of calcium hydroxide (as a binder), 22.5 grams of aluminum slag and 36 grams of refining slag into a molding equipment (model: PM-20 ), and perform a pressure molding process at a pressure of 15kg/ cm2 for 2 seconds to obtain an ingot-shaped desulfurizer with a length of 4.5cm, a width of 3.8cm and a height of 6cm. The aluminum slag comes from Taiwan. Aluminum smelter, and contains 4.4wt% magnesium oxide (MgO), 73.6wt% aluminum oxide, 5.2wt% metallic aluminum, 0.3wt% silicon dioxide, 0.2wt% potassium oxide (K 2 O ), and 16.3wt% aluminum nitride (AlN), and the refining slag comes from a Taiwan steelmaking plant and contains 55.4wt% calcium oxide (CaO), 4.8wt% magnesium oxide (MgO), 2.7wt% Aluminum trioxide, 27.2wt% silica, 7.0wt% calcium fluoride (CaF 2 ), 1.9wt% iron monoxide (FeO), 0.4wt% manganese monoxide (MnO), and 0.6 wt% sulfur.

比較例1      錠狀脫硫劑Comparative Example 1 Tablet Desulfurizer

將31.5克且粒徑為0.27mm以下的氧化鈣、36克的精煉渣、10克的氫氧化鈣(作為黏著劑)及22.5克的鋁渣導入一台成型設備(型號:PM-20)中進行混合,並以壓力為15kg/cm 2進行2秒的加壓成型處理,獲得長為4.5cm、寬為3.8cm且高為6cm的錠狀脫硫劑。其中,該精煉渣來自台灣煉鋼廠,且包含55.4wt%的氧化鈣(CaO)、4.8wt%的氧化鎂(MgO)、2.7wt%的三氧化二鋁、27.2wt%的二氧化矽、7.0wt%的二氟化鈣(CaF 2)、1.9wt%的一氧化鐵(FeO)、0.4wt%的一氧化錳(MnO),及0.6wt%的硫,而該鋁渣來自台灣煉鋁廠,且包含4.4wt%的氧化鎂(MgO)、73.6wt%的三氧化二鋁、5.2wt%的金屬鋁、0.33wt%的二氧化矽、0.17wt%的氧化鉀(K 2O),及16.28wt%的氮化鋁(AlN)。 Introduce 31.5 grams of calcium oxide with a particle size of less than 0.27mm, 36 grams of refining slag, 10 grams of calcium hydroxide (as a binder) and 22.5 grams of aluminum slag into a molding equipment (model: PM-20) Mix and perform pressure molding treatment at a pressure of 15kg/ cm2 for 2 seconds to obtain a tablet-shaped desulfurizer with a length of 4.5cm, a width of 3.8cm and a height of 6cm. Among them, the refining slag comes from a Taiwan steelmaking plant and contains 55.4wt% calcium oxide (CaO), 4.8wt% magnesium oxide (MgO), 2.7wt% aluminum oxide, 27.2wt% silica, 7.0wt% calcium difluoride (CaF 2 ), 1.9wt% iron monoxide (FeO), 0.4wt% manganese monoxide (MnO), and 0.6wt% sulfur, and the aluminum slag comes from Taiwan aluminum smelting factory, and contains 4.4wt% magnesium oxide (MgO), 73.6wt% aluminum oxide, 5.2wt% metallic aluminum, 0.33wt% silicon dioxide, 0.17wt% potassium oxide (K 2 O), and 16.28wt% aluminum nitride (AlN).

比較例2至4Comparative Examples 2 to 4

比較例2至4的製備方法是與比較例1的製備方法大致相同,且主要不同在於:在比較例2中,無氫氧化鈣。在比較例3至4中,是將比較例1的氫氧化鈣依序置換為硬脂酸鋅及水泥,且用量依序為10克及10克。The preparation methods of Comparative Examples 2 to 4 are substantially the same as those of Comparative Example 1, and the main difference is that in Comparative Example 2, there is no calcium hydroxide. In Comparative Examples 3 to 4, the calcium hydroxide in Comparative Example 1 was replaced with zinc stearate and cement in sequence, and the dosages were 10 grams and 10 grams respectively.

比較例5至6Comparative Examples 5 to 6

比較例5至6的製備方法是與比較例1的製備方法大致相同,且主要不同在於:在比較例5至6中,該氫氧化鈣的用量依序為15克及20克。The preparation methods of Comparative Examples 5 to 6 are substantially the same as the preparation methods of Comparative Example 1, and the main difference is that in Comparative Examples 5 to 6, the amounts of calcium hydroxide used are 15 grams and 20 grams respectively.

比較例7至8Comparative Examples 7 to 8

比較例7至8的製備方法是與實施例5的製備方法大致相同,且主要不同在於:改變該氧化鈣的粒徑或/及該水的用量比例,參閱表3。The preparation methods of Comparative Examples 7 to 8 are approximately the same as those of Example 5, and the main difference lies in changing the particle size of the calcium oxide or/and the dosage ratio of the water, see Table 3.

評價項目Evaluation items

成型安定性:將實施例1至14的錠狀脫硫劑與比較例1至8的錠狀脫硫劑靜置在溫度為25℃且相對濕度為60%至99%的大氣環境下一段時間,並施予一外力,觀察是否有崩解或粉化的現象。Molding stability: Leave the tablet-shaped desulfurizers of Examples 1 to 14 and the tablet-shaped desulfurizers of Comparative Examples 1 to 8 for a period of time in an atmospheric environment with a temperature of 25°C and a relative humidity of 60% to 99%. , and apply an external force to observe whether there is disintegration or powdering.

表1   實施例 1 2 3 4 5 6 7 第一組分 氧化鈣 用量 31.5 31.5 31.5 31.5 31.5 31.5 31.5 粒徑(mm) 0.27以下 0.27以下 14.2 14.2 14.2 14.2 14.2 31.5 63 精煉渣 36 36 36 36 36 36 36 氧化鈣、水及精煉渣的重量比例 1:0.45:1.15 1:0.45:1.15 1:1:1.15 1:2:1.15 水合反應 溫度(℃) 25 25 25 25 25 25 25 時間(分鐘) 30 30 30 30 30 30 30 混合物 氫氧化鈣(克) 29.2 29.2 29.2 29.2 29.2 32.9 37.8 氧化鈣(克) 9.4 9.4 9.4 9.4 9.4 6.6 2.9 乾燥物 74.6 74.6 74.6 74.6 74.6 75.5 76.7 第二組分 鋁渣 22.5 22.5 22.5 22.5 22.5 22.5 22.5 精煉渣 0 0 0 0 0 0 0 氫氧化鈣 10 0 0 0 10 10 10 硬脂肪酸 0 0 10 0 0 0 0 水泥 0 0 0 10 0 0 0 碇狀脫硫劑(wt%) 精煉渣 33.6 37.1 33.6 33.6 33.6 33.3 33.0 鋁渣 21.0 23.2 21.0 21.0 21.0 20.8 20.6 黏著劑 9.3 0 9.3 9.3 9.3 9.3 9.2 氧化鈣 8.8 9.7 8.8 8.8 8.8 6.1 2.6 氫氧化鈣 27.3 30.0 27.3 27.3 27.3 30.5 34.6 成型安定性 靜置180天無崩解或粉化 靜置90天無崩解或粉化 Table 1 Example 1 2 3 4 5 6 7 first component calcium oxide Dosage 31.5 31.5 31.5 31.5 31.5 31.5 31.5 Particle size (mm) 0.27 or less 0.27 or less water 14.2 14.2 14.2 14.2 14.2 31.5 63 Refining slag 36 36 36 36 36 36 36 Weight ratio of calcium oxide, water and refining slag 1:0.45:1.15 1:0.45:1.15 1:1:1.15 1:2:1.15 hydration reaction Temperature(℃) 25 25 25 25 25 25 25 time (minutes) 30 30 30 30 30 30 30 mixture Calcium hydroxide (g) 29.2 29.2 29.2 29.2 29.2 32.9 37.8 Calcium oxide(g) 9.4 9.4 9.4 9.4 9.4 6.6 2.9 dry matter 74.6 74.6 74.6 74.6 74.6 75.5 76.7 second component Aluminum dross 22.5 22.5 22.5 22.5 22.5 22.5 22.5 Refining slag 0 0 0 0 0 0 0 calcium hydroxide 10 0 0 0 10 10 10 hard fatty acid 0 0 10 0 0 0 0 cement 0 0 0 10 0 0 0 Sticky desulfurizer (wt%) Refining slag 33.6 37.1 33.6 33.6 33.6 33.3 33.0 Aluminum dross 21.0 23.2 21.0 21.0 21.0 20.8 20.6 Adhesive 9.3 0 9.3 9.3 9.3 9.3 9.2 calcium oxide 8.8 9.7 8.8 8.8 8.8 6.1 2.6 calcium hydroxide 27.3 30.0 27.3 27.3 27.3 30.5 34.6 Forming stability No disintegration or powdering after 180 days of standing No disintegration or powdering after 90 days of resting

表2 單位:克 實施例 8 9 10 11 12 13 14 第一組分 氧化鈣 用量 31.5 31.5 31.5 31.5 31.5 31.5 31.5 粒徑(mm) 大於0.27且1.18以下 大於1.18且1.4以下 1.4以下 14.2 31.5 63 14.2 31.5 63 31.5 精煉渣 36 36 36 36 36 36 0 氧化鈣、水及精煉渣的重量比例 1:0.45:1.15 1:1:1.15 1:2:1.15 1:0.45:1.15 1:1:1.15 1:2:1.15 1:1:0 水合反應 溫度(℃) 25 25 25 25 25 25 25 時間 (分鐘) 30 30 30 30 30 30 30 混合物 氫氧化鈣(克) 21 32.9 37.8 16.9 32.9 37.8 37 氧化鈣(克) 15.6 6.6 2.9 18.7 6.6 2.9 3.5 乾燥物 72.6 75.5 76.7 71.6 75.5 76.7 40.5 第二組分 鋁渣 22.5 22.5 22.5 22.5 22.5 22.5 22.5 精煉渣 0 0 0 0 0 0 36 氫氧化鈣 10 10 10 10 10 10 10 硬脂肪酸 0 0 0 0 0 0 0 水泥 0 0 0 0 0 0 0 碇狀脫硫劑(wt%) 精煉渣 34.3 33.3 33.0 34.6 33.3 33.0 33.0 鋁渣 21.4 20.8 20.6 21.6 20.8 20.6 20.6 黏著劑 9.5 9.3 9.2 9.6 9.3 9.2 9.2 氧化鈣 14.9 6.1 2.6 18.0 6.1 2.6 3.2 氫氧化鈣 19.9 30.5 34.6 16.2 30.5 34.6 34.0 成型安定性 靜置7天無崩解或粉化 靜置90天無崩解或粉化 靜置5天無崩解或粉化 靜置90天無崩解或粉化 靜置180天無崩解或粉化 Table 2 Unit: Gram Example 8 9 10 11 12 13 14 first component calcium oxide Dosage 31.5 31.5 31.5 31.5 31.5 31.5 31.5 Particle size(mm) Greater than 0.27 and less than 1.18 Greater than 1.18 and less than 1.4 1.4 or less water 14.2 31.5 63 14.2 31.5 63 31.5 Refining slag 36 36 36 36 36 36 0 Weight ratio of calcium oxide, water and refining slag 1:0.45:1.15 1:1:1.15 1:2:1.15 1:0.45:1.15 1:1:1.15 1:2:1.15 1:1:0 hydration reaction Temperature(℃) 25 25 25 25 25 25 25 time (minutes) 30 30 30 30 30 30 30 mixture Calcium hydroxide (g) twenty one 32.9 37.8 16.9 32.9 37.8 37 Calcium oxide(g) 15.6 6.6 2.9 18.7 6.6 2.9 3.5 dry matter 72.6 75.5 76.7 71.6 75.5 76.7 40.5 second component Aluminum dross 22.5 22.5 22.5 22.5 22.5 22.5 22.5 Refining slag 0 0 0 0 0 0 36 calcium hydroxide 10 10 10 10 10 10 10 hard fatty acid 0 0 0 0 0 0 0 cement 0 0 0 0 0 0 0 Sticky desulfurizer (wt%) Refining slag 34.3 33.3 33.0 34.6 33.3 33.0 33.0 Aluminum dross 21.4 20.8 20.6 21.6 20.8 20.6 20.6 Adhesive 9.5 9.3 9.2 9.6 9.3 9.2 9.2 calcium oxide 14.9 6.1 2.6 18.0 6.1 2.6 3.2 calcium hydroxide 19.9 30.5 34.6 16.2 30.5 34.6 34.0 Forming stability No disintegration or powdering after 7 days of resting No disintegration or powdering after 90 days of resting No disintegration or powdering after 5 days of standing No disintegration or powdering after 90 days of resting No disintegration or powdering after 180 days of standing

表3 「--」:未進行 單位:克 比較例 1 2 3 4 5 6 7 8 氧化鈣 用量 31.5 31.5 31.5 31.5 31.5 31.5 31.5 31.5 粒徑(mm) 0.27以下 大於1.4 0 0 0 0 0 0 14.2 31.5 精煉渣 36 36 36 36 36 36 36 36 水合反應 溫度(℃) -- -- -- -- -- -- 25 25 時間(分鐘) -- -- -- -- -- -- 30 30 混合物 氫氧化鈣(克) -- -- -- -- -- -- 6.2 8.2 氧化鈣(克) -- -- -- -- -- -- 26.8 25.3 乾燥物 -- -- -- -- -- -- 69 69.5 鋁渣 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 精煉渣 0 0 0 0 0 0 0 0 氫氧化鈣 10 0 0 0 15 20 10 10 硬脂肪酸 0 0 10 0 0 0 0 0 水泥 0 0 0 10 0 0 0 0 碇狀脫硫劑(wt%) 精煉渣 36.0 40.0 36.0 36.0 34.3 32.7 35.5 35.3 鋁渣 22.5 25.0 22.5 22.5 21.4 20.5 22.2 22.1 黏著劑 10.0 0 10.0 10.0 14.3 18.2 9.9 9.8 氧化鈣 31.5 35.0 31.5 31.5 30.0 28.6 26.3 24.7 氫氧化鈣 0 0 0 0 0 0 6.1 8.1 成型安定性 靜置1天粉化 table 3 "--": Not in progress Unit: grams Comparative example 1 2 3 4 5 6 7 8 calcium oxide Dosage 31.5 31.5 31.5 31.5 31.5 31.5 31.5 31.5 Particle size (mm) 0.27 or less greater than 1.4 water 0 0 0 0 0 0 14.2 31.5 Refining slag 36 36 36 36 36 36 36 36 hydration reaction Temperature(℃) -- -- -- -- -- -- 25 25 time (minutes) -- -- -- -- -- -- 30 30 mixture Calcium hydroxide (g) -- -- -- -- -- -- 6.2 8.2 Calcium oxide(g) -- -- -- -- -- -- 26.8 25.3 dry matter -- -- -- -- -- -- 69 69.5 Aluminum dross 22.5 22.5 22.5 22.5 22.5 22.5 22.5 22.5 Refining slag 0 0 0 0 0 0 0 0 calcium hydroxide 10 0 0 0 15 20 10 10 hard fatty acid 0 0 10 0 0 0 0 0 cement 0 0 0 10 0 0 0 0 Sticky desulfurizer (wt%) Refining slag 36.0 40.0 36.0 36.0 34.3 32.7 35.5 35.3 Aluminum dross 22.5 25.0 22.5 22.5 21.4 20.5 22.2 22.1 Adhesive 10.0 0 10.0 10.0 14.3 18.2 9.9 9.8 calcium oxide 31.5 35.0 31.5 31.5 30.0 28.6 26.3 24.7 calcium hydroxide 0 0 0 0 0 0 6.1 8.1 Forming stability Let stand for 1 day to powder

綜上所述,透過上述流程的設計,尤其是使部分氧化鈣轉變成氫氧化鈣的設計,由本發明的塊狀脫硫劑的製備方法所製得的塊狀脫硫劑在含有水氣環境中存放一段時間後,不易有因氧化鈣遇水氣而產生的膨脹現象,導致崩解而產生粉末化的問題產生,致使仍保有原有形態而具有不錯的成型安定性,以至於用於煉鋼的過程中,方便使用而具有不錯的操作性,且因在一段時間的存放後不會有因崩解而產生粉末化的現象,所以當投入煉鋼設備中時能夠避免被該煉鋼設備的集塵裝置吸入而無法有效地降低鋼液中的硫含量,致使脫硫效率不佳的問題產生,故確實能達成本發明的目的。In summary, through the design of the above process, especially the design of converting part of the calcium oxide into calcium hydroxide, the block desulfurizer prepared by the method for preparing the block desulfurizer of the present invention can be used in an environment containing water vapor. After being stored in a medium for a period of time, calcium oxide will not easily expand due to the presence of water vapor, leading to disintegration and powdering. As a result, it still retains its original shape and has good molding stability, so that it can be used for refining. In the process of making steel, it is easy to use and has good operability, and because there will be no powdering due to disintegration after a period of storage, it can avoid being used by the steelmaking equipment when it is put into the steelmaking equipment. The dust collecting device sucks in the dust and cannot effectively reduce the sulfur content in the molten steel, resulting in the problem of poor desulfurization efficiency. Therefore, the purpose of the present invention can indeed be achieved.

惟以上所述者,僅為本發明的實施例而已,當不能以此限定本發明實施的範圍,凡是依本發明申請專利範圍及專利說明書內容所作的簡單的等效變化與修飾,皆仍屬本發明專利涵蓋的範圍內。However, the above are only examples of the present invention and should not be used to limit the scope of the present invention. All simple equivalent changes and modifications made based on the patent scope of the present invention and the content of the patent specification are still within the scope of the present invention. within the scope covered by the patent of this invention.

無。without.

Claims (11)

一種塊狀脫硫劑的製備方法,包含: 將包括粒徑為1.4mm以下的氧化鈣的第一組分與水進行水合反應,以使部分的氧化鈣轉變成氫氧化鈣,而獲得包含氫氧化鈣及氧化鈣的混合物; 將該混合物進行乾燥處理,以去除水分,獲得乾燥物; 將該乾燥物與包括鋁渣的第二組分混合,並進行加壓成型處理。 A method for preparing block desulfurizer, including: Perform a hydration reaction between the first component including calcium oxide with a particle size of 1.4 mm or less and water, so that part of the calcium oxide is converted into calcium hydroxide, and a mixture containing calcium hydroxide and calcium oxide is obtained; The mixture is dried to remove moisture and obtain a dry product; The dried product is mixed with a second component including aluminum slag, and subjected to pressure forming treatment. 如請求項1所述的塊狀脫硫劑的製備方法,其中,該第一組分還包括精煉渣,且該精煉渣包括氧化鈣。The preparation method of block desulfurizer according to claim 1, wherein the first component also includes refining slag, and the refining slag includes calcium oxide. 如請求項1所述的塊狀脫硫劑的製備方法,其中,該第二組分還包括黏著劑。The preparation method of block desulfurizer according to claim 1, wherein the second component further includes a binder. 如請求項3所述的塊狀脫硫劑的製備方法,其中,該黏著劑選自於水泥、氫氧化鈣、硬脂酸鋅,或上述任意的組合。The method for preparing a block desulfurizer according to claim 3, wherein the adhesive is selected from cement, calcium hydroxide, zinc stearate, or any combination of the above. 如請求項1所述的塊狀脫硫劑的製備方法,其中,該水合反應的溫度範圍為50℃至150℃,且時間範圍為10分鐘至180分鐘。The preparation method of block desulfurization agent as described in claim 1, wherein the temperature range of the hydration reaction is 50°C to 150°C, and the time range is 10 minutes to 180 minutes. 如請求項1所述的塊狀脫硫劑的製備方法,其中,該加壓成型處理的壓力範圍為8kg/cm 2至15kg/cm 2,且時間範圍為2秒至90秒。 The preparation method of block desulfurizer as described in claim 1, wherein the pressure range of the pressure forming process is 8kg/cm 2 to 15kg/cm 2 , and the time range is 2 seconds to 90 seconds. 如請求項2所述的塊狀脫硫劑的製備方法,其中,該氧化鈣、該水及該精煉渣的重量比例範圍為1:0.45至2:大於0且1.5以下。The preparation method of block desulfurizer as described in claim 2, wherein the weight ratio of the calcium oxide, the water and the refining slag ranges from 1:0.45 to 2: greater than 0 and less than 1.5. 如請求項1所述的塊狀脫硫劑的製備方法,其中,該第二組分還包括精煉渣。The preparation method of block desulfurizer as described in claim 1, wherein the second component also includes refining slag. 如請求項1所述的塊狀脫硫劑的製備方法,其中,以該塊狀脫硫劑的總量為100wt%計,該塊狀脫硫劑中的氧化鈣的含量範圍為2wt%至18wt%,及該鋁渣的含量範圍為20wt%至30wt%。The preparation method of block desulfurizer as described in claim 1, wherein, based on the total amount of the block desulfurizer being 100wt%, the content of calcium oxide in the block desulfurizer ranges from 2 wt% to 18wt%, and the content of the aluminum slag ranges from 20wt% to 30wt%. 如請求項3所述的塊狀脫硫劑的製備方法,其中,以該塊狀脫硫劑的總量為100wt%計,該塊狀脫硫劑中的該氧化鈣的含量範圍為2wt%至18wt%、該鋁渣的含量範圍為20wt%至30wt%,且該黏著劑的含量範圍為大於0wt%且20wt%以下。The preparation method of block desulfurizer as described in claim 3, wherein, based on the total amount of the block desulfurizer being 100wt%, the content range of the calcium oxide in the block desulfurizer is 2wt% to 18wt%, the content of the aluminum slag ranges from 20wt% to 30wt%, and the content of the adhesive ranges from greater than 0wt% to less than 20wt%. 如請求項8所述的塊狀脫硫劑的製備方法,其中,以該塊狀脫硫劑的總量為100wt%計,該塊狀脫硫劑中的該氧化鈣的含量範圍為2wt%至18wt%、該鋁渣的含量範圍為20wt%至30wt%,且該精煉渣的含量範圍為大於30wt%且40wt%以下。The preparation method of block desulfurizer as described in claim 8, wherein, based on the total amount of the block desulfurizer being 100 wt%, the content range of the calcium oxide in the block desulfurizer is 2 wt% to 18wt%, the content of the aluminum slag ranges from 20wt% to 30wt%, and the content of the refining slag ranges from greater than 30wt% to less than 40wt%.
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