TW201607893A - Process for producing ferrous sulphate - Google Patents
Process for producing ferrous sulphate Download PDFInfo
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Abstract
Description
本發明係關於製造包含硫酸亞鐵之產物之方法。 This invention relates to a process for making a product comprising ferrous sulfate.
眾所周知可經由熱處理水綠礬(硫酸亞鐵七水合物)以便減少水之含量且獲得具有自由流動特徵之乾燥產物來製造尤其呈單水合物形式之硫酸亞鐵。 It is known to produce ferrous sulfate, especially in the form of a monohydrate, by heat-treating water green hydrazine (ferrous sulphate heptahydrate) in order to reduce the water content and to obtain a dry product having free-flow characteristics.
舉例而言，WO 84/01942揭示使用乾燥及添加吸收材料之組合乾燥硫酸亞鐵七水合物之方法。具體而言，該方法要求在20℃至60℃間之溫度下乾燥以獲得自由流動乾燥粉末。 For example, WO 84/01942 discloses a method of drying ferrous sulfate heptahydrate using a combination of drying and addition of an absorbent material. Specifically, the method requires drying at a temperature between 20 ° C and 60 ° C to obtain a free flowing dry powder.
US 2,771,342亦闡述在低於其熔點之溫度下乾燥潮濕硫酸亞鐵七水合物，隨後添加細磨的碳酸鈣並充分混合，以獲得不會聚結之自由流動產物。 US 2,771,342 also teaches drying wet ferrous sulfate heptahydrate at temperatures below its melting point, followed by the addition of finely ground calcium carbonate and thorough mixing to obtain free flowing products that do not coalesce.
然而，該等方法及業內已知之其他方法之缺點在於為得到自由流動且表面上乾燥之產物，必須在某些溫度下乾燥硫酸亞鐵七水合物以幫助去除水。因此，此熱方法涉及高能量消耗，增加製造成本且可導致由此獲得之產物具有熱相關之穩定性問題。 However, such methods and other methods known in the art have the disadvantage that in order to obtain a free flowing and surface dried product, the ferrous sulfate heptahydrate must be dried at certain temperatures to aid in the removal of water. Therefore, this thermal method involves high energy consumption, increases manufacturing costs, and can result in heat-related stability problems for the products thus obtained.
鑒於上述內容，業內仍需要研發更廉價且更環保之方法，該等方法需要顯著更少的能量及設備來製造有用的硫酸亞鐵產物。 In view of the above, there is still a need in the industry to develop cheaper and more environmentally friendly methods that require significantly less energy and equipment to make useful ferrous sulfate products.
具體而言，業內期望容許製造自由流動硫酸亞鐵產物同時避免或減少一或多個上述問題之方法。 In particular, the industry desires methods that permit the manufacture of free flowing ferrous sulfate products while avoiding or reducing one or more of the above problems.
在第一態樣中，本發明提供製造包含硫酸亞鐵之產物之方法，該方法包含：(i)合併硫酸亞鐵單水合物、半水石膏及硫酸亞鐵七水合物以提供反應混合物；及然後(ii)混合反應混合物以獲得包含硫酸亞鐵之自由流動產物。 In a first aspect, the invention provides a method of making a product comprising ferrous sulfate, the method comprising: (i) combining ferrous sulfate monohydrate, hemihydrate gypsum, and ferrous sulfate heptahydrate to provide a reaction mixture; And then (ii) mixing the reaction mixture to obtain a free flowing product comprising ferrous sulfate.
本發明由此涉及簡單混合方法，其利用不同組份與存於水綠礬產物中之自由水反應之能力來製造自由流動硫酸亞鐵產物。所獲得產物相對乾燥，如可藉由產物之自由流動性質看出。 The invention thus relates to a simple mixing process that utilizes the ability of different components to react with the free water present in the aqueous green hydrazine product to produce a free flowing ferrous sulfate product. The product obtained is relatively dry, as can be seen by the free flowing nature of the product.
在本發明中，自由流動產物係滿足以下標準中之一者或兩者之產物：(a)當在室溫下將1000克產物填充至具有½英吋(1.27cm)頸部之漏斗中時，產物花費少於2分鐘及30秒之時間流出漏斗之頸部；(b)當在室溫下將1000克產物填充至具有1英吋(2.54cm)頸部之漏斗中時，產物花費少於40秒之時間流出漏斗之頸部。 In the present invention, the free-flowing product meets the product of one or both of the following criteria: (a) when 1000 g of product is filled into a funnel having a 1⁄2 inch (1.27 cm) neck at room temperature The product took less than 2 minutes and 30 seconds to flow out of the neck of the funnel; (b) when 1000 grams of product was filled into a funnel with a 1 inch (2.54 cm) neck at room temperature, the product cost less Flowed out of the neck of the funnel in 40 seconds.
較佳地，自由流動產物滿足標準(a)及(b)。 Preferably, the free flowing product meets criteria (a) and (b).
適宜地，在室溫或接近室溫下(例如在實質上室溫下)實施本發明方法。無需加熱。 Suitably, the process of the invention is carried out at or near room temperature (e.g., at substantially room temperature). No heating is required.
因此，與典型已知方法不同，本發明方法可改良包含硫酸亞鐵之產物之製造而無需熱乾燥。不使用外部提供之熱製備該等產物之方法顯然更經濟、環保且易於實施。 Thus, unlike typical known methods, the process of the present invention can improve the manufacture of products comprising ferrous sulfate without the need for thermal drying. The method of preparing such products without the use of externally supplied heat is clearly more economical, environmentally friendly and easy to implement.
如藉由本發明方法獲得之包含硫酸亞鐵之所得產物不褪色或展現顯著氧化。其即使在延長儲存後亦保留優良長期流動性質。 The resulting product comprising ferrous sulfate obtained by the process of the invention does not fade or exhibit significant oxidation. It retains excellent long-term flow properties even after prolonged storage.
另外，完全缺乏提供用於脫水之熱之需要亦使得產物較熱乾燥之硫酸亞鐵產物更穩定且更不易於再水化及結塊。 In addition, the complete lack of the need to provide heat for dehydration also makes the ferrous sulfate product which is more thermally dry than the product more stable and less prone to rehydration and agglomeration.
因此，所獲得硫酸亞鐵產物適於硫酸亞鐵之所有典型應用，具體而言作為鉻(VI)還原劑(例如在水泥製造中)或在農業中作為肥料。 然而，其亦具有其他益處，例如在長期穩定性方面。 Thus, the obtained ferrous sulfate product is suitable for all typical applications of ferrous sulfate, in particular as a chromium (VI) reducing agent (for example in the manufacture of cement) or as a fertilizer in agriculture. However, it also has other benefits, such as in terms of long-term stability.
在一個較佳實施例中，如所獲得之包含硫酸亞鐵之產物呈自由流動粉末形式。 In a preferred embodiment, the product comprising ferrous sulfate as obtained is in the form of a free flowing powder.
如上所述，可藉由穿過½英吋漏斗之流動時間及/或藉由穿過1英吋漏斗之流動時間評價產物之自由流動性質。在每一情形下，在室溫及室壓下實施測試。 As noted above, the free flow properties of the product can be evaluated by the flow time through a 1⁄2 inch funnel and/or by the flow time through a 1 inch funnel. In each case, the test was carried out at room temperature and room pressure.
在一個實施例中，滿足標準(a)。因此，當將1000克產物填充至具有½英吋(1.27cm)頸部之漏斗中時，產物花費少於2分鐘及30秒之時間流出漏斗之頸部。舉例而言，流動時間可為5秒至2分鐘及30秒，例如10秒至2分鐘及30秒，或20秒至2分鐘及30秒，或25秒至2分鐘及30秒，或30秒至2分鐘及30秒，或35秒至2分鐘及30秒，或40秒至2分鐘及30秒。 In one embodiment, criterion (a) is met. Thus, when 1000 grams of product was filled into a funnel having a 1⁄2 inch (1.27 cm) neck, the product took less than 2 minutes and 30 seconds to flow out of the neck of the funnel. For example, the flow time can be 5 seconds to 2 minutes and 30 seconds, such as 10 seconds to 2 minutes and 30 seconds, or 20 seconds to 2 minutes and 30 seconds, or 25 seconds to 2 minutes and 30 seconds, or 30 seconds. Up to 2 minutes and 30 seconds, or 35 seconds to 2 minutes and 30 seconds, or 40 seconds to 2 minutes and 30 seconds.
在一個該實施例中，當將1000克產物填充至具有½英吋(1.27cm)頸部之漏斗中時，產物花費少於2分鐘及20秒之時間流出漏斗之頸部。舉例而言，流動時間可為5秒至2分鐘及20秒，例如10秒至2分鐘及20秒，或20秒至2分鐘及20秒，或25秒至2分鐘及20秒，或30秒至2分鐘及20秒，或35秒至2分鐘及20秒，或40秒至2分鐘及20秒。 In one such embodiment, when 1000 grams of product was filled into a funnel having a 1⁄2 inch (1.27 cm) neck, the product took less than 2 minutes and 20 seconds to flow out of the neck of the funnel. For example, the flow time can be 5 seconds to 2 minutes and 20 seconds, such as 10 seconds to 2 minutes and 20 seconds, or 20 seconds to 2 minutes and 20 seconds, or 25 seconds to 2 minutes and 20 seconds, or 30 seconds. Up to 2 minutes and 20 seconds, or 35 seconds to 2 minutes and 20 seconds, or 40 seconds to 2 minutes and 20 seconds.
在一個實施例中，滿足標準(b)。因此，當將1000克產物填充至具有1英吋(2.54cm)頸部之漏斗中時，產物花費少於40秒之時間流出漏斗之頸部。舉例而言，流動時間可為1秒至40秒，例如2秒至40秒，或5秒至40秒，或8秒至40秒，或10秒至40秒，或15秒至40秒，或20秒至40秒。 In one embodiment, criterion (b) is met. Thus, when 1000 grams of product was filled into a funnel with a 1 inch (2.54 cm) neck, the product took less than 40 seconds to flow out of the neck of the funnel. For example, the flow time can be from 1 second to 40 seconds, such as from 2 seconds to 40 seconds, or from 5 seconds to 40 seconds, or from 8 seconds to 40 seconds, or from 10 seconds to 40 seconds, or from 15 seconds to 40 seconds, or 20 seconds to 40 seconds.
在一個該實施例中，當將1000克產物填充至具有1英吋(2.54cm)頸部之漏斗中時，產物花費少於35秒之時間流出漏斗之頸部。舉例而言，流動時間可為1秒至35秒，例如2秒至35秒，或5秒至35秒，或8秒至35秒，或10秒至35秒，或15秒至35秒，或20秒至35秒。 In one such embodiment, when 1000 grams of product was filled into a funnel having a 1 inch (2.54 cm) neck, the product took less than 35 seconds to exit the neck of the funnel. For example, the flow time can be from 1 second to 35 seconds, such as from 2 seconds to 35 seconds, or from 5 seconds to 35 seconds, or from 8 seconds to 35 seconds, or from 10 seconds to 35 seconds, or from 15 seconds to 35 seconds, or 20 seconds to 35 seconds.
在一個實施例中，滿足如上所述之兩個標準(a)及(b)。 In one embodiment, the two criteria (a) and (b) as described above are met.
如上所述，產物之自由流動性質指示藉由本發明方法獲得之產物相對乾燥。 As noted above, the free-flowing nature of the product indicates that the product obtained by the process of the invention is relatively dry.
本發明並非限於如所獲得之自由流動產物中之任何具體水含量。然而，在一個實施例中，包含硫酸亞鐵之產物中之自由水含量基於該產物之總重量為5w/w%或更低，例如4.5w/w%或更低；更佳4w/w%或更低，例如3.5w/w%或更低；甚至更佳3w/w%或更低。其基於產物之總重量可為(例如)0至5w/w%，或0.05w/w%至4.5w/w%，或0.05w/w%至4w/w%，或0.1w/w%至3.5w/w%，或0.1w/w%至3w/w%。 The invention is not limited to any particular water content as in the free flowing products obtained. However, in one embodiment, the free water content in the product comprising ferrous sulfate is 5 w/w% or less based on the total weight of the product, such as 4.5 w/w% or less; more preferably 4 w/w% Or lower, such as 3.5 w/w% or lower; even more preferably 3 w/w% or lower. It may be, for example, from 0 to 5 w/w%, or from 0.05 w/w% to 4.5 w/w%, or from 0.05 w/w% to 4 w/w%, or from 0.1 w/w% to the total weight of the product. 3.5 w/w%, or 0.1 w/w% to 3 w/w%.
在本發明之所有實施例中，倘若提及自由水含量，則可藉由卡爾費雪程序(Karl Fischer procedure)測定此值。該程序應為僅測定自由水含量而不測定任何結晶水之任何含量之程序。 In all embodiments of the invention, if a free water content is mentioned, this value can be determined by the Karl Fischer procedure. The procedure should be a procedure that only measures free water content without determining any content of any crystallized water.
在此一經修改卡爾費雪程序中，所實施量測僅測定自由水含量，而不測定任何晶體水分，此乃因在室溫下使用丙醇(無水丙-1-醇)實施初始萃取以去除樣品之自由水分。然後，使用標準卡爾費雪容量滴定程序滴定此丙醇樣品之等份樣品，以獲得自由水含量之值。 In the modified Karl Fischer program, the measurement was performed to determine only the free water content without determining any crystal moisture, as the initial extraction was carried out using propanol (anhydrous propan-1-ol) at room temperature to remove Free moisture of the sample. An aliquot of this propanol sample was then titrated using a standard Karl Fischer volumetric titration procedure to obtain a free water content value.
具體而言，可使用如附錄A中所闡述之卡爾費雪程序。在此經修改卡爾費雪程序中，所實施量測僅測定自由水含量而不測定任何晶體水分。 Specifically, the Karl Fischer program as set forth in Appendix A can be used. In the modified Karl Fischer program, the measurements were performed to determine only the free water content without determining any crystal moisture.
在一個實施例中，製造包含硫酸亞鐵之產物之方法包含：(i)合併60w/w%至85w/w%硫酸亞鐵七水合物、2w/w%至15w/w%半水石膏及5w/w%至35w/w%硫酸亞鐵單水合物以提供反應混合物，其中所述量係基於用於形成反應混合物之反應物之總重量；及(ii)混合該反應混合物以獲得包含硫酸亞鐵之產物。由此獲得之包含硫酸亞鐵之產物中之自由水之含量可為5w/w%或更少，例如0.01w/w%至5 w/w%。 In one embodiment, a method of making a product comprising ferrous sulfate comprises: (i) combining 60 w/w% to 85 w/w% ferrous sulfate heptahydrate, 2 w/w% to 15 w/w% hemihydrate gypsum, and 5w/w% to 35w/w% ferrous sulfate monohydrate to provide a reaction mixture, wherein the amount is based on the total weight of the reactants used to form the reaction mixture; and (ii) mixing the reaction mixture to obtain sulfuric acid The product of ferrous iron. The content of free water in the product containing ferrous sulfate thus obtained may be 5 w/w% or less, for example, 0.01 w/w% to 5 w/w%.
在一個實施例中，將包含硫酸亞鐵之產物與一或多種農業上可接受之載劑、農業上可接受之稀釋劑及/或肥料材料進一步混合，以形成肥料產物。 In one embodiment, the product comprising ferrous sulfate is further mixed with one or more agriculturally acceptable carriers, agriculturally acceptable diluents and/or fertilizer materials to form a fertilizer product.
在一個實施例中，將包含硫酸亞鐵之產物與一或多種水泥添加劑、水泥成份及/或水泥黏合劑進一步混合，以形成水泥混合物。 In one embodiment, the product comprising ferrous sulfate is further mixed with one or more cement additives, cement components, and/or cement binders to form a cementitious mixture.
在第二態樣中，本發明進一步提供如可藉由實施第一態樣之方法獲得之包含硫酸亞鐵之產物。 In a second aspect, the invention further provides a product comprising ferrous sulfate as obtained by carrying out the method of the first aspect.
如可藉由實施本文所闡述之方法獲得之包含硫酸亞鐵之產物適宜地具有低自由水含量。較佳地，硫酸亞鐵產物實質上乾燥。舉例而言，其可具有5w/w%或更少、例如0.01w/w%至5w/w%之自由水含量。 The product comprising ferrous sulfate obtained by carrying out the process as set forth herein suitably has a low free water content. Preferably, the ferrous sulfate product is substantially dry. For example, it may have a free water content of 5 w/w% or less, such as from 0.01 w/w% to 5 w/w%.
包含硫酸亞鐵之產物係自由流動產物。舉例而言，在某些實施例中，包含硫酸亞鐵之產物係自由流動粉末。 The product comprising ferrous sulfate is a free flowing product. For example, in certain embodiments, the product comprising ferrous sulfate is a free flowing powder.
在一個實施例中，如可藉由實施第一態樣之方法獲得之包含硫酸亞鐵之產物係與一或多種農業上可接受之載劑、農業上可接受之稀釋劑及/或肥料材料之混合物。因此，產物可為肥料。 In one embodiment, the product comprising ferrous sulfate obtained by carrying out the method of the first aspect is associated with one or more agriculturally acceptable carriers, agriculturally acceptable diluents and/or fertilizer materials. a mixture. Therefore, the product can be a fertilizer.
在一個實施例中，如可藉由實施第一態樣之方法獲得之包含硫酸亞鐵之產物係與一或多種水泥添加劑、水泥成份及/或水泥黏合劑之混合物。因此，產物可為水泥混合物。 In one embodiment, a mixture of a product comprising ferrous sulfate and one or more cement additives, cement components and/or cement binders obtainable by the method of carrying out the first aspect. Thus, the product can be a cement mixture.
舉例而言，水泥可為水硬性水泥，例如波特蘭水泥(Portland cement)。波特蘭水泥(亦稱為普通波特蘭水泥或OPC)可定義為滿足ASTM C150之要求或歐洲標準EN197.1之要求之具膠結性材料。然而，可使用其他水泥。 For example, the cement can be a hydraulic cement such as Portland cement. Portland cement (also known as ordinary Portland cement or OPC) can be defined as a cementitious material that meets the requirements of ASTM C150 or European Standard EN 197.1. However, other cements can be used.
在一個實施例中，將水泥混合物與水進一步混合，以便形成硬化水泥產物。 In one embodiment, the cement mixture is further mixed with water to form a hardened cement product.
在一個該實施例中，將水泥混合物與骨材(例如礫石及/或砂)及水混合，以便形成混凝土或砂漿產物。在一個實施例中，將水泥混合物與骨材(例如礫石及/或砂)混合，然後將其與水混合。 In one such embodiment, the cement mixture is mixed with aggregates (e.g., gravel and/or sand) and water to form a concrete or mortar product. In one embodiment, the cement mixture is mixed with an aggregate such as gravel and/or sand and then mixed with water.
在第三態樣中，本發明提供混合硫酸亞鐵單水合物、半水石膏及硫酸亞鐵七水合物之步驟之用途，其用於獲得包含硫酸亞鐵之自由流動產物，而無需熱乾燥。 In a third aspect, the invention provides the use of a step of mixing ferrous sulfate monohydrate, hemihydrate gypsum and ferrous sulfate heptahydrate for obtaining a free flowing product comprising ferrous sulfate without thermal drying .
在第四態樣中，本發明進一步提供第二態樣之產物之用途，其用作鉻(VI)還原劑。 In a fourth aspect, the invention further provides the use of a second aspect of the product for use as a chromium (VI) reducing agent.
在一個實施例中，可使用包含硫酸亞鐵之產物降低水泥、尤其波特蘭水泥中之Cr(VI)含量。 In one embodiment, the product comprising ferrous sulfate can be used to reduce the Cr(VI) content of the cement, particularly Portland cement.
在第五態樣中，本發明提供第二態樣之產物之用途，其用作水泥(例如波特蘭水泥)之添加劑。 In a fifth aspect, the invention provides the use of a second aspect of the product for use as an additive to cement (e.g., Portland cement).
本發明進一步提供包含第二態樣之產物之水泥混合物。本發明亦提供包含第二態樣之產物之硬化水泥產物。本發明亦提供包含第二態樣之產物之混凝土或砂漿產物。 The invention further provides a cementitious mixture comprising the product of the second aspect. The invention also provides a hardened cement product comprising the product of the second aspect. The invention also provides a concrete or mortar product comprising the product of the second aspect.
本發明亦提供包含第二態樣之產物之肥料。 The invention also provides a fertilizer comprising the product of the second aspect.
本發明亦提供製造肥料之方法，其中該方法包含：(i)藉由實施第一態樣之方法製造包含硫酸亞鐵之產物，及(ii)將包含硫酸亞鐵之產物與一或多種農業上可接受之載劑、農業上可接受之稀釋劑及/或肥料材料混合。 The invention also provides a method of making a fertilizer, wherein the method comprises: (i) producing a product comprising ferrous sulfate by performing the first aspect, and (ii) producing a product comprising ferrous sulfate with one or more agricultural products A mixture of acceptable carriers, agriculturally acceptable diluents and/or fertilizer materials.
本發明亦提供製造水泥混合物之方法，其中該方法包含：(i)藉由實施第一態樣之方法製造包含硫酸亞鐵之產物，及(ii)將包含硫酸亞鐵之產物與一或多種水泥添加劑、水泥成份及/或水泥黏合劑混合。 The invention also provides a method of making a cementitious mixture, wherein the method comprises: (i) producing a product comprising ferrous sulfate by performing the first aspect, and (ii) producing one or more products comprising ferrous sulfate Mixing cement additives, cement components and/or cement binders.
本發明亦提供製造硬化水泥產物之方法，其中該方法包含：(i)藉由實施之方法第一態樣製造包含硫酸亞鐵之產物，(ii)將包含硫酸 亞鐵之產物與一或多種水泥添加劑、水泥成份及/或水泥黏合劑混合，以形成水泥混合物，及(iii)將水泥混合物與水混合。 The invention also provides a method of making a hardened cement product, wherein the method comprises: (i) producing a product comprising ferrous sulfate by a first aspect of the method of implementation, (ii) comprising sulfuric acid The ferrous product is mixed with one or more cement additives, cement components and/or cement binder to form a cement mixture, and (iii) the cement mixture is mixed with water.
本發明亦提供製造混凝土或砂漿產物之方法，其中該方法包含：(i)藉由實施第一態樣之方法製造包含硫酸亞鐵之產物，(ii)將包含硫酸亞鐵之產物與一或多種水泥添加劑、水泥成份及/或水泥黏合劑混合，以形成水泥混合物，及(iii)將水泥混合物與骨材(例如礫石及/或砂)及水混合。在一個實施例中，將水泥混合物與骨材混合，然後將其與水混合。 The invention also provides a method of making a concrete or mortar product, wherein the method comprises: (i) producing a product comprising ferrous sulfate by performing the first aspect, (ii) producing a product comprising ferrous sulfate with one or A plurality of cement additives, cement components and/or cement binders are mixed to form a cement mixture, and (iii) the cement mixture is mixed with the aggregates (such as gravel and/or sand) and water. In one embodiment, the cement mixture is mixed with the aggregate and then mixed with water.
在本發明中，當提及「在室溫下」或「實質上在室溫下」時，舉例而言此可為15℃至25℃，例如16℃至25℃且尤其18℃至25℃；例如18℃至24℃或19℃至24℃或19℃至23℃或20℃至22℃，例如在約21℃下。 In the present invention, when referring to "at room temperature" or "substantially at room temperature", for example, this may be 15 ° C to 25 ° C, such as 16 ° C to 25 ° C and especially 18 ° C to 25 ° C. For example, 18 ° C to 24 ° C or 19 ° C to 24 ° C or 19 ° C to 23 ° C or 20 ° C to 22 ° C, for example at about 21 ° C.
在本發明中，當提及「在室壓下」或「在大氣壓下」時，舉例而言此可為95kPa至105kPa，例如98kPa至104kPa，例如99kPa至103kPa或100kPa至102kPa，例如在約101kPa下。 In the present invention, when referring to "under chamber pressure" or "at atmospheric pressure", for example, this may be from 95 kPa to 105 kPa, such as from 98 kPa to 104 kPa, such as from 99 kPa to 103 kPa or from 100 kPa to 102 kPa, for example at about 101 kPa. under.
圖1係顯示使用具有EDAX x射線微量分析附件之JEOL T330A掃描電子顯微鏡在實例1之硫酸亞鐵產物中檢測到之元素之光譜。 Figure 1 is a graph showing the spectra of the elements detected in the ferrous sulfate product of Example 1 using a JEOL T330A scanning electron microscope with an EDAX x-ray microanalytical attachment.
圖2係使用具有EDAX x射線微量分析附件之JEOL T330A掃描電子顯微鏡獲得之實例1之硫酸亞鐵產物之SEM影像。 Figure 2 is an SEM image of the ferrous sulfate product of Example 1 obtained using a JEOL T330A scanning electron microscope with an EDAX x-ray microanalytical accessory.
圖3係如在實例1之硫酸亞鐵產物中檢測到之元素Fe、S、Ca及Ti之一組x射線圖。 Figure 3 is a set of x-ray images of the elements Fe, S, Ca and Ti as detected in the ferrous sulfate product of Example 1.
圖4係顯示使用具有EDAX x射線微量分析附件之JEOL T330A掃描電子顯微鏡在實例1之硫酸亞鐵產物中檢測到之元素之光譜，如使用高於圖1之放大倍數掃描所檢測。 Figure 4 is a graph showing the spectra of the elements detected in the ferrous sulfate product of Example 1 using a JEOL T330A scanning electron microscope with an EDAX x-ray microanalytical attachment, as detected using a magnification scan higher than that of Figure 1.
圖5係來自高於圖2之放大倍數掃描之實例1硫酸亞鐵產物之SEM 影像，其係使用具有EDAX x射線微量分析附件之JEOL T330A掃描電子顯微鏡獲得。 Figure 5 is an SEM image of a ferrous sulfate product from Example 1 above the magnification scan of Figure 2, obtained using a JEOL T330A scanning electron microscope with an EDAX x-ray microanalytical accessory.
圖6係如來自高於圖3之放大倍數掃描之在實例1硫酸亞鐵產物中檢測到之元素Fe、S、Ca及Ti之一組x射線圖。 Figure 6 is a set of x-ray images of the elements Fe, S, Ca and Ti detected in the ferrous sulfate product of Example 1 as from a magnification scan of Figure 3.
本發明係關於製備包含硫酸亞鐵之產物之方法。該方法通常可闡述為涉及合併以下反應物：a)硫酸亞鐵七水合物、b)硫酸亞鐵單水合物及c)半水石膏；及然後混合該等反應物。 This invention relates to a process for preparing a product comprising ferrous sulfate. The method is generally described as involving the incorporation of the following reactants: a) ferrous sulfate heptahydrate, b) ferrous sulfate monohydrate, and c) hemihydrate gypsum; and then mixing the reactants.
在一個實施例中，可藉由將硫酸亞鐵單水合物及半水石膏添加至硫酸亞鐵七水合物中合併反應物，並混合該等反應物。然而，最後可以任一順序合併反應物。可視情況立即將其全部合併。 In one embodiment, the reactants may be combined by adding ferrous sulfate monohydrate and hemihydrate gypsum to the ferrous sulfate heptahydrate and mixing the reactants. However, the reactants can be combined in either order. Combine them all as soon as possible.
可以任一適宜方式合併反應物，此端視混合所用技術及每一反應物之濃度而定。可使用業內已知之技術(例如前置式裝載斗或固體混合器)將所有三種上文所提及之反應物混合在一起。本發明並非限於混合所使用之設備或技術，其可為手動的或自動化的。 The reactants may be combined in any suitable manner depending on the technique employed for mixing and the concentration of each reactant. All three of the above mentioned reactants can be mixed together using techniques known in the art, such as a front loading bucket or a solid mixer. The invention is not limited to the equipment or technology used for mixing, it can be manual or automated.
將各成份混合達足以容許該等成份反應並形成硫酸亞鐵產物之時間段。 The ingredients are mixed for a period of time sufficient to allow the components to react and form a ferrous sulfate product.
可容許反應物在合併步驟期間、在混合步驟期間反應且視情況可容許在混合後反應一段時間。一般而言，可容許反應物反應足量的時間以形成硫酸亞鐵產物。 The reactants may be allowed to react during the combining step, during the mixing step, and optionally allowed to react for a period of time after mixing. In general, the reactants can be allowed to react for a sufficient amount of time to form a ferrous sulfate product.
在某些實施例中，將各成份混合1分鐘或更長之時段，例如2分鐘或更長或5分鐘或更長。混合可視情況達最多90分鐘之時間段，例如最多60分鐘或最多30分鐘、例如最多25分鐘。混合可達2分鐘至90分鐘之時間段，例如5分鐘至60分鐘且尤其5分鐘至30分鐘，例如10分鐘至20分鐘或15分鐘至25分鐘。 In certain embodiments, the ingredients are mixed for a period of 1 minute or longer, such as 2 minutes or longer or 5 minutes or longer. The mixing can be as long as a period of up to 90 minutes, for example up to 60 minutes or up to 30 minutes, for example up to 25 minutes. Mixing can be for a period of from 2 minutes to 90 minutes, such as from 5 minutes to 60 minutes and especially from 5 minutes to 30 minutes, such as from 10 minutes to 20 minutes or from 15 minutes to 25 minutes.
視情況，可使反應物在混合後反應一段時間，例如1分鐘或更長 之時段，例如2分鐘或更長或5分鐘或更長，例如1分鐘至30分鐘，或2分鐘至25分鐘或5分鐘至20分鐘。 Optionally, the reactants may be reacted for a period of time after mixing, for example 1 minute or longer The period of time is, for example, 2 minutes or longer or 5 minutes or longer, such as 1 minute to 30 minutes, or 2 minutes to 25 minutes or 5 minutes to 20 minutes.
當產物滿足以下標準中之一者或二者(較佳地二者)時將反應視為完全的：(a)當在室溫下將1000克產物填充至具有½英吋(1.27cm)頸部之漏斗中時，產物花費少於2分鐘及30秒之時間流出漏斗之頸部；(b)當在室溫下將1000克產物填充至具有1英吋(2.54cm)頸部之漏斗中時，產物花費少於40秒之時間漏斗之頸部。 The reaction is considered complete when the product meets one or both of the following criteria (preferably both): (a) when 1000 grams of product is filled to have a 1⁄2 inch (1.27 cm) neck at room temperature In the funnel of the section, the product takes less than 2 minutes and 30 seconds to flow out of the neck of the funnel; (b) when 1000 grams of product is filled into a funnel with a neck of 1 inch (2.54 cm) at room temperature At the time, the product took less than 40 seconds to the neck of the funnel.
在該方法之所有上述步驟中，皆未施加外部熱。因此，適宜實質上在室溫下實施該方法。較佳地在大氣壓下實施該方法。 In all of the above steps of the method, no external heat was applied. Therefore, it is suitable to carry out the process substantially at room temperature. The process is preferably carried out at atmospheric pressure.
在完成反應後，可儲存產物。可將其散裝儲存或可將其儲存在個別袋或其他容器中，如業內已知。舉例而言，可將產物儲存在密封袋或其他容器中。 After the reaction is completed, the product can be stored. They may be stored in bulk or may be stored in individual bags or other containers as is known in the art. For example, the product can be stored in a sealed bag or other container.
已驚奇地發現，藉由使用所揭示之方法，可形成包含硫酸亞鐵之穩定產物。此產物之灰塵少於習用硫酸亞鐵單水合物產物。該產物係細粉末。該產物具有改良之自由流動特徵。該產物亦具有低自由水含量，但事實係並未涉及熱乾燥。 Surprisingly, it has been found that by using the disclosed method, a stable product comprising ferrous sulfate can be formed. This product has less dust than the conventional ferrous sulfate monohydrate product. This product is a fine powder. This product has improved free flow characteristics. The product also has a low free water content, but the fact is not related to thermal drying.
因此，當與工業內已知之其他硫酸亞鐵產物相比時，所製造之包含硫酸亞鐵之產物可更容易儲存、處置及分配。 Thus, the products comprising ferrous sulfate produced can be more easily stored, handled and dispensed when compared to other ferrous sulfate products known in the industry.
如本文所用，「自由流動」、「自由流動形式」或「自由流動特徵」意指不存在明顯黏著。如上文所論述，藉由流動時間測試量測流動性質，該測試係由量測標準量的粉末樣品自指定漏斗完全倒空之時長組成。適於測試粉末流動之漏斗具有帶有指定出口孔尺寸之漏嘴開口或頸部且係垂直地安裝且在出口中與水平相齊平。可利用1000克產物樣品填充此一漏斗，且然後量測該樣品穿過頸部之流動時間。在室溫及室壓下實施量測。 As used herein, "free flow", "free flow form" or "free flow characteristics" means that there is no significant adhesion. As discussed above, the flow properties were measured by a flow time test consisting of measuring the length of time during which a standard amount of powder sample was completely emptied from the designated funnel. A funnel suitable for testing powder flow has a nozzle opening or neck with a designated outlet orifice size and is mounted vertically and flush with the level in the outlet. This funnel can be filled with 1000 grams of product sample and then the flow time of the sample through the neck is measured. The measurement was carried out at room temperature and room pressure.
如藉由本發明方法製得之硫酸亞鐵產物實質上係乾燥的，且因此該產物可具有低於5w/w%之自由水含量。在較佳實施例中，包含硫酸亞鐵之產物中之自由水含量基於該產物之總重量低於4.5w/w%，更佳低於4w/w%，例如低於3.5w/w%且甚至更佳低於3w/w%。其可為(例如)0至5w/w%，或0.5w/w%至4w/w%，或1w/w%至3w/w%。包含硫酸亞鐵之產物中之自由水含量基於該產物之總重量可為0.1w/w%至5w/w%，或0.1w/w%至4w/w%，或0.1w/w%至3w/w%。 The ferrous sulfate product as produced by the process of the invention is substantially dry, and thus the product may have a free water content of less than 5 w/w%. In a preferred embodiment, the free water content of the product comprising ferrous sulfate is less than 4.5 w/w%, more preferably less than 4 w/w%, such as less than 3.5 w/w%, based on the total weight of the product. Even better than 3w/w%. It may be, for example, 0 to 5 w/w%, or 0.5 w/w% to 4 w/w%, or 1 w/w% to 3 w/w%. The free water content in the product comprising ferrous sulfate may range from 0.1 w/w% to 5 w/w%, or from 0.1 w/w% to 4 w/w%, or from 0.1 w/w% to 3 w, based on the total weight of the product. /w%.
本發明中可使用硫酸亞鐵單水合物之任一來源。舉例而言，本文所闡述方法中所使用之硫酸亞鐵單水合物化合物可為藉由習用乾燥硫酸亞鐵七水合物獲得之化合物。 Any source of ferrous sulfate monohydrate can be used in the present invention. For example, the ferrous sulfate monohydrate compound used in the methods described herein can be a compound obtained by conventionally drying ferrous sulfate heptahydrate.
該方法中所使用之硫酸亞鐵單水合物較佳地以實質上乾燥之形式提供。因此，硫酸亞鐵單水合物產物經提供較佳地具有低自由水含量，例如基於此反應物之總重量低於4w/w%自由水，或低於3.5w/w%；較佳地低於3w/w%，例如低於2.5w/w%，或低於2w/w%自由水。其可具有(例如)0.01w/w%至3w/w%或0.01w/w%至2w/w%之自由水含量，在一個實施例中，其具有低於1.5w/w%或甚至低於1w/w%之自由水。其可具有(例如)如下自由水含量：0.1w/w%至3w/w%或0.1w/w%至2.5w/w%；較佳地0.1w/w%至2w/w%；最佳0.1w/w%至1.5w/w%或0.1w/w%至1w/w%。基於硫酸亞鐵單水合物之總重量，硫酸亞鐵單水合物反應物可具有如下自由水含量：0.3w/w%至3w/w%，或0.3w/w%至2.5w/w%；較佳地0.3w/w%至2w/w%；最佳0.3w/w%至1.5w/w%或0.3w/w%至1w/w%。在一個實施例中，基於此反應物之總重量，自由水含量為約0.5w/w%至約1w/w%。 The ferrous sulfate monohydrate used in the process is preferably provided in a substantially dry form. Accordingly, the ferrous sulfate monohydrate product is preferably provided to have a low free water content, for example less than 4 w/w% free water, or less than 3.5 w/w% based on the total weight of the reactant; preferably low At 3 w/w%, for example less than 2.5 w/w%, or less than 2 w/w% free water. It may have a free water content of, for example, 0.01 w/w% to 3 w/w% or 0.01 w/w% to 2 w/w%, in one embodiment it has less than 1.5 w/w% or even low Free water at 1w/w%. It may have, for example, a free water content of from 0.1 w/w% to 3 w/w% or from 0.1 w/w% to 2.5 w/w%; preferably from 0.1 w/w% to 2 w/w%; 0.1 w/w% to 1.5 w/w% or 0.1 w/w% to 1 w/w%. The ferrous sulfate monohydrate reactant may have a free water content of from 0.3 w/w% to 3 w/w%, or from 0.3 w/w% to 2.5 w/w%, based on the total weight of the ferrous sulfate monohydrate; It is preferably from 0.3 w/w% to 2 w/w%; optimally from 0.3 w/w% to 1.5 w/w% or from 0.3 w/w% to 1 w/w%. In one embodiment, the free water content is from about 0.5 w/w% to about 1 w/w% based on the total weight of the reactants.
在一個實施例中，基於用於形成反應混合物之反應物之總重 量，硫酸亞鐵單水合物化合物可以5w/w%至35w/w%範圍內之量使用。舉例而言，在某些實施例中，硫酸亞鐵單水合物化合物係以10w/w%至30w/w%、例如15w/w%至25w/w%、或18w/w%至22w/w%範圍內之量使用。基於用於形成反應混合物之反應物之總重量，硫酸亞鐵單水合物可以5w/w%至30w/w%、或5w/w%至28w/w%、或5w/w%至23w/w%、或5w/w%至22w/w%之含量使用。在較佳實施例中，硫酸亞鐵單水合物之濃度為10w/w%至35w/w%，例如15w/w%至35w/w%，或15w/w%至30w/w%，或18w/w%至30w/w%，或18w/w%至25w/w%。 In one embodiment, based on the total weight of the reactants used to form the reaction mixture The amount of ferrous sulfate monohydrate compound can be used in an amount ranging from 5 w/w% to 35 w/w%. For example, in certain embodiments, the ferrous sulfate monohydrate compound is from 10 w/w% to 30 w/w%, such as from 15 w/w% to 25 w/w%, or from 18 w/w% to 22 w/w. The amount in the range of % is used. The ferrous sulfate monohydrate may be from 5 w/w% to 30 w/w%, or from 5 w/w% to 28 w/w%, or from 5 w/w% to 23 w/w, based on the total weight of the reactants used to form the reaction mixture. %, or 5w/w% to 22w/w% is used. In a preferred embodiment, the concentration of ferrous sulfate monohydrate is from 10 w/w% to 35 w/w%, such as from 15 w/w% to 35 w/w%, or from 15 w/w% to 30 w/w%, or 18 w. /w% to 30w/w%, or 18w/w% to 25w/w%.
在本發明中可使用半水石膏之任一來源。半水石膏亦稱為硫酸鈣半水合物或燒石膏，或可稱作CaSO4．nH2O，其中n在0.5至0.8之範圍內。 Any source of hemihydrate gypsum can be used in the present invention. Hemihydrate gypsum is also known as calcium sulphate hemihydrate or calcined gypsum, or may be referred to as CaSO 4 . nH 2 O, wherein n is in the range of 0.5 to 0.8.
舉例而言，半水石膏可為紅色半水石膏或白色半水石膏或其組合。本發明中所使用之半水石膏可為天然的或可為合成的。可使用α-半水合物及/或β-半水合物。 For example, the hemihydrate gypsum can be red hemihydrate gypsum or white hemihydrate gypsum or a combination thereof. The hemihydrate gypsum used in the present invention may be natural or may be synthetic. A-hemihydrate and/or β-hemihydrate can be used.
在一個實施例中，基於用於形成反應混合物之反應物之總重量，半水石膏化合物可以2w/w%至15w/w%範圍內之量使用。舉例而言，在某些實施例中，半水石膏化合物係以2w/w%至14w/w%、例如2w/w%至13w/w%或2w/w%至12w/w%範圍內之量使用。在一個實施例中，半水石膏係以3w/w%至15w/w%、例如3w/w%至14w/w%、或3w/w%至13w/w%、或3w/w%至12w/w%之量使用。在某些實施例中，半水石膏化合物係以4w/w%至14w/w%、例如4w/w%至12w/w%、或4w/w%至10w/w%範圍內之量使用。舉例而言，基於用於形成反應混合物之反應物之總重量，半水石膏化合物可以2w/w%至10w/w%或2w/w%至8w/w%、或3w/w%至10w/w%或3w/w%至7w/w%、例如4w/w%至8w/w%或4w/w%至6 w/w%之量使用。 In one embodiment, the hemihydrate gypsum compound can be used in an amount ranging from 2 w/w% to 15 w/w%, based on the total weight of the reactants used to form the reaction mixture. For example, in certain embodiments, the hemihydrate gypsum compound is in the range of 2 w/w% to 14 w/w%, such as 2 w/w% to 13 w/w% or 2 w/w% to 12 w/w%. The amount is used. In one embodiment, the hemihydrate gypsum is from 3 w/w% to 15 w/w%, such as from 3 w/w% to 14 w/w%, or from 3 w/w% to 13 w/w%, or from 3 w/w% to 12 w. /w% amount is used. In certain embodiments, the hemihydrate gypsum compound is used in an amount ranging from 4 w/w% to 14 w/w%, such as from 4 w/w% to 12 w/w%, or from 4 w/w% to 10 w/w%. For example, the hemihydrate gypsum compound may range from 2 w/w% to 10 w/w% or 2 w/w% to 8 w/w%, or 3 w/w% to 10 w/ based on the total weight of the reactants used to form the reaction mixture. W% or 3w/w% to 7w/w%, for example 4w/w% to 8w/w% or 4w/w% to 6 The amount of w/w% is used.
硫酸亞鐵七水合物具有化學式FeSO4‧7H2O。在本文所闡述之方法中可使用硫酸亞鐵七水合物化合物之任一來源。舉例而言，所使用之硫酸亞鐵七水合物化合物可為鋼及鈦工業之副產物。 Ferrous sulfate heptahydrate has the chemical formula FeSO 4 ‧7H 2 O. Any source of the ferrous sulfate heptahydrate compound can be used in the methods described herein. For example, the ferrous sulfate heptahydrate compound used can be a by-product of the steel and titanium industries.
人們對硫酸亞鐵七水合物副產物之使用有極大興趣，此乃因成本較低且其可大量製造。然而，該等副產物之已察覺到的問題在於其含有大量濕度，亦即其具有高殘餘自由水含量。然而，已驚奇地發現該等產物適用於本發明方法中，該方法允許獲得自由流動且具有低自由水含量之終端產物而無需使用熱乾燥。因此，濕硫酸亞鐵七水合物較佳作為本發明方法中之反應物用於獲得硫酸亞鐵產物。 There has been great interest in the use of ferrous sulfate heptahydrate by-products due to the lower cost and its high mass production. However, a perceived problem with such by-products is that they contain a large amount of humidity, i.e., they have a high residual free water content. However, it has been surprisingly found that these products are suitable for use in the process of the invention which allows to obtain a free flowing and end product having a low free water content without the use of thermal drying. Thus, wet ferrous sulfate heptahydrate is preferred as the reactant in the process of the invention for obtaining a ferrous sulfate product.
在一個實施例中，該方法中所使用之硫酸亞鐵七水合物實質上係濕的或潮濕的，亦即，其具有不可忽略的自由水含量。在一個實施例中，硫酸亞鐵七水合物之自由水含量基於此反應物之總重量為6w/w%或更多，例如6.5w/w%或更多，或7w/w%或更多或8w/w%或更多。在較佳實施例中，硫酸亞鐵七水合物之自由水含量為最多15w/w%，較佳地最多14w/w%，例如最多13%，或最多12%；更佳地，水含量為最多11%；最佳地，水含量為最多10w/w%。基於硫酸亞鐵七水合物之總重量，其可為6w/w%至15w/w%，例如7w/w%至15w/w%或8w/w%至15w/w%。舉例而言，在某些實施例中，硫酸亞鐵七水合物中之自由水含量基於此反應物之總重量為6w/w%至13w/w%，或6w/w%至12w/w%或6w/w%至11w/w%；較佳地7w/w%至12w/w%或7w/w%至11w/w%，例如8w/w%至10w/w%。 In one embodiment, the ferrous sulfate heptahydrate used in the process is substantially wet or moist, that is, it has a non-negligible free water content. In one embodiment, the free water content of the ferrous sulfate heptahydrate is 6 w/w% or more based on the total weight of the reactants, such as 6.5 w/w% or more, or 7 w/w% or more. Or 8w/w% or more. In a preferred embodiment, the free water content of the ferrous sulfate heptahydrate is at most 15 w/w%, preferably at most 14 w/w%, such as at most 13%, or at most 12%; more preferably, the water content is Up to 11%; optimally, the water content is up to 10 w/w%. It may range from 6 w/w% to 15 w/w%, such as from 7 w/w% to 15 w/w% or from 8 w/w% to 15 w/w%, based on the total weight of the ferrous sulfate heptahydrate. For example, in certain embodiments, the free water content of the ferrous sulfate heptahydrate is from 6 w/w% to 13 w/w%, or from 6 w/w% to 12 w/w%, based on the total weight of the reactants. Or 6w/w% to 11w/w%; preferably 7w/w% to 12w/w% or 7w/w% to 11w/w%, for example 8w/w% to 10w/w%.
在一些實施例中，用作反應物之硫酸亞鐵七水合物之鐵含量在18wt%至20wt%、例如18wt%至19wt%之範圍內。 In some embodiments, the iron content of the ferrous sulfate heptahydrate used as the reactant is in the range of 18 wt% to 20 wt%, such as 18 wt% to 19 wt%.
在一個實施例中，基於用於形成反應混合物之反應物之總重量，硫酸亞鐵七水合物係以60w/w%至85w/w%範圍內之量使用。在 一個較佳實施例中，硫酸亞鐵七水合物係以60w/w%至80w/w%、例如65w/w%至80w/w%、例如70w/w%至78w/w%範圍內之量使用。硫酸亞鐵七水合物在反應物混合物中之濃度可為65w/w%至85w/w%，或70w/w%至80w/w%，例如72w/w%至78w/w%。在一個實施例中，基於用於形成反應混合物之反應物之總重量，硫酸亞鐵七水合物之濃度為68w/w%至78w/w%，或70w/w%至78w/w%，或73w/w%至77w/w%。 In one embodiment, the ferrous sulfate heptahydrate is used in an amount ranging from 60 w/w% to 85 w/w%, based on the total weight of the reactants used to form the reaction mixture. in In a preferred embodiment, the ferrous sulfate heptahydrate is present in an amount ranging from 60 w/w% to 80 w/w%, such as from 65 w/w% to 80 w/w%, such as from 70 w/w% to 78 w/w%. use. The concentration of ferrous sulfate heptahydrate in the reactant mixture can range from 65 w/w% to 85 w/w%, or from 70 w/w% to 80 w/w%, such as from 72 w/w% to 78 w/w%. In one embodiment, the concentration of ferrous sulfate heptahydrate is from 68 w/w% to 78 w/w%, or from 70 w/w% to 78 w/w%, based on the total weight of the reactants used to form the reaction mixture, or 73w/w% to 77w/w%.
在較佳實施例中，本發明方法包含：(i)合併60w/w%至85w/w%(例如60%至80%)硫酸亞鐵七水合物、2w/w%至15w/w%(例如2%至10%)半水石膏及5w/w%至35w/w%(例如10%至30%)硫酸亞鐵單水合物以提供反應混合物，其中所述量係基於用於形成反應混合物之反應物之總重量；及(ii)混合反應混合物以獲得包含硫酸亞鐵之產物。 In a preferred embodiment, the method of the invention comprises: (i) combining 60 w/w% to 85 w/w% (eg 60% to 80%) ferrous sulfate heptahydrate, 2 w/w% to 15 w/w% ( For example 2% to 10%) hemihydrate gypsum and 5w/w% to 35w/w% (eg 10% to 30%) ferrous sulfate monohydrate to provide a reaction mixture, wherein the amount is based on the formation of the reaction mixture The total weight of the reactants; and (ii) mixing the reaction mixture to obtain a product comprising ferrous sulfate.
在較佳實施例中，本發明方法包含：(i)合併70w/w%至80w/w%(例如72%至78%)硫酸亞鐵七水合物、2w/w%至8w/w%(例如3%至7%)半水石膏及15w/w%至25w/w%(例如17%至23%)硫酸亞鐵單水合物以提供反應混合物，其中所述量係基於用於形成反應混合物之反應物之總重量；及(ii)混合反應混合物以獲得包含硫酸亞鐵之產物。 In a preferred embodiment, the method of the invention comprises: (i) combining 70 w/w% to 80 w/w% (eg, 72% to 78%) ferrous sulfate heptahydrate, 2 w/w% to 8 w/w% ( For example 3% to 7%) hemihydrate gypsum and 15 w/w% to 25 w/w% (eg 17% to 23%) ferrous sulfate monohydrate to provide a reaction mixture, wherein the amount is based on the reaction mixture used to form The total weight of the reactants; and (ii) mixing the reaction mixture to obtain a product comprising ferrous sulfate.
在一個較佳實施例中，製造包含硫酸亞鐵之產物之方法包含：(i)合併75w/w%硫酸亞鐵七水合物、5w/w%半水石膏及20w/w%硫酸亞鐵單水合物以提供反應混合物，其中所述量係基於用於形成反應混合物之反應物之總重量；及(ii)混合反應混合物以獲得包含硫酸亞鐵之產物。 In a preferred embodiment, a method of making a product comprising ferrous sulfate comprises: (i) combining 75 w/w% ferrous sulfate heptahydrate, 5 w/w% hemihydrate gypsum, and 20 w/w% ferrous sulfate Hydrate to provide a reaction mixture, wherein the amount is based on the total weight of the reactants used to form the reaction mixture; and (ii) mixing the reaction mixture to obtain a product comprising ferrous sulfate.
在一個實施例中，硫酸亞鐵單水合物、半水石膏及硫酸亞鐵七水合物係用於形成反應混合物之僅有的反應物。因此，硫酸亞鐵單水 合物之量加上半水石膏之量加上硫酸亞鐵七水合物之量等於100%(以重量計)。 In one embodiment, ferrous sulfate monohydrate, hemihydrate gypsum, and ferrous sulfate heptahydrate are used to form the only reactants of the reaction mixture. Therefore, ferrous sulfate monohydrate The amount of the compound plus the amount of hemihydrate gypsum plus the amount of ferrous sulfate heptahydrate is equal to 100% by weight.
在另一實施例中，可存在其他反應物及/或可存在低含量之雜質。較佳地，基於用於形成反應混合物之反應物之總重量，不為硫酸亞鐵單水合物、半水石膏及硫酸亞鐵七水合物之任何反應物/雜質之量為5% wt/wt或更少，例如4%或更少，或3%或更少，或2%或更少，或1%或更少。舉例而言，不為硫酸亞鐵單水合物、半水石膏及硫酸亞鐵七水合物之任何反應物/雜質之量可為0至3wt/wt%，例如0.01wt/wt%至2%，或0.05wt/wt%至1%，或0.05wt/wt%至0.5%，或0.1wt/wt%至0.3%。 In another embodiment, other reactants may be present and/or low levels of impurities may be present. Preferably, the amount of any reactant/impurity other than ferrous sulfate monohydrate, hemihydrate gypsum and ferrous sulfate heptahydrate is 5% wt/wt based on the total weight of the reactants used to form the reaction mixture. Or less, such as 4% or less, or 3% or less, or 2% or less, or 1% or less. For example, the amount of any reactant/impurity that is not ferrous sulfate monohydrate, hemihydrate gypsum, and ferrous sulfate heptahydrate may be from 0 to 3 wt/wt%, such as from 0.01 wt/wt% to 2%, Or 0.05 wt/wt% to 1%, or 0.05 wt/wt% to 0.5%, or 0.1 wt/wt% to 0.3%.
藉由該方法獲得之包含硫酸亞鐵之產物實質上係自由流動產物且其視情況具有低自由水含量。較佳地，自由流動硫酸亞鐵產物實質上係乾燥的。在較佳實施例中，包含硫酸亞鐵之自由流動產物中之自由水含量低於5w/w%，更佳低於4.5w/w%且甚至更佳低於4w/w%且甚至更佳低於3.5w/w%或低於3w/w%。其可為(例如)0至5w/w%，或0.5w/w%至4w/w%，或1w/w%至3w/w%。包含硫酸亞鐵之自由流動產物中之自由水含量基於自由流動產物之總重量可為0.1w/w%至5w/w%，或0.1w/w%至4w/w%，或0.1w/w%至3w/w%。 The product comprising ferrous sulfate obtained by this process is essentially a free flowing product and optionally has a low free water content. Preferably, the free flowing ferrous sulfate product is substantially dry. In a preferred embodiment, the free water content of the free flowing product comprising ferrous sulfate is less than 5 w/w%, more preferably less than 4.5 w/w% and even more preferably less than 4 w/w% and even better. Less than 3.5 w/w% or less than 3 w/w%. It may be, for example, 0 to 5 w/w%, or 0.5 w/w% to 4 w/w%, or 1 w/w% to 3 w/w%. The free water content in the free flowing product comprising ferrous sulfate may range from 0.1 w/w% to 5 w/w%, or from 0.1 w/w% to 4 w/w%, or 0.1 w/w, based on the total weight of the free flowing product. % to 3w/w%.
在一個實施例中，實質上在室溫下實施步驟(i)且實質上在室溫下實施步驟(ii)。在一個實施例中，實質上在室溫下實施整個方法。 In one embodiment, step (i) is carried out substantially at room temperature and step (ii) is carried out substantially at room temperature. In one embodiment, the entire process is carried out substantially at room temperature.
因此，在一個實施例中，在不施加任何外部熱之情況下實施步驟(i)且在不施加任何外部熱之情況下實施步驟(ii)。在一個實施例中，在不施加任何外部熱之情況下實施整個方法。 Thus, in one embodiment, step (i) is carried out without applying any external heat and step (ii) is carried out without applying any external heat. In one embodiment, the entire method is carried out without applying any external heat.
本發明之一個優點在於當將硫酸亞鐵七水合物(水綠礬)與硫酸亞鐵單水合物及半水石膏合併時，該等組份利用或吸收存於水綠礬起始材料中之自由水，藉此產生實質上乾燥的產物。如上文所解釋，亦驚 奇地發現此產物具有優良自由流動特徵。此外，該產物易於處置、分配及儲存。 An advantage of the present invention is that when ferrous sulfate heptahydrate (water green hydrazine) is combined with ferrous sulfate monohydrate and hemihydrate gypsum, the components are utilized or absorbed in the starting material of the water green sorghum. Free water, thereby producing a substantially dry product. As explained above, it is also shocking It is surprisingly found that this product has excellent free-flow characteristics. In addition, the product is easy to handle, dispense and store.
儘管不欲受限於任何具體理論，但相信半水石膏與存於自由水綠礬中之自由水反應，從而降低水含量且引起產物之自由流動性質。 另外，相信(例如)在半水石膏轉化為石膏時可在硫酸亞鐵七水合物之粒子上形成塗層，且此塗層可用於減少摩擦且因此使得粒子更具自由流動性且更易於處置。 While not wishing to be bound by any particular theory, it is believed that the hemihydrate gypsum reacts with the free water present in the free water green mash, thereby reducing the water content and causing the free flowing nature of the product. In addition, it is believed that, for example, a coating can be formed on the particles of ferrous sulfate heptahydrate when hemihydrate gypsum is converted to gypsum, and this coating can be used to reduce friction and thus make the particles more free-flowing and easier to handle .
另外，可在不施加任何外部熱用於乾燥/脫水之情況下獲得產物之事實亦使得該產物相對於彼等製造藉由熱方法者更加穩定。該產物較先前技術產物亦更不易於再水化及結塊。 In addition, the fact that the product can be obtained without applying any external heat for drying/dehydration also makes the product more stable with respect to their manufacture by thermal methods. This product is also less susceptible to rehydration and agglomeration than prior art products.
此產物之灰塵亦少於習用硫酸亞鐵單水合物產物。 The dust of this product is also less than the conventional ferrous sulfate monohydrate product.
本發明之另一優點在於硫酸亞鐵產物可用於各種工業中，例如彼等需要某一鐵形式者。舉例而言，硫酸亞鐵混合物可用作還原劑，例如其可用於降低尤其水泥工業中之產物之Cr(VI)含量。因此，其可用作水泥混合物中之添加劑。舉例而言，其可添加至波特蘭水泥混合物中以減少Cr(VI)。另外，硫酸亞鐵產物可用於陶瓷製造中。硫酸亞鐵產物亦可用作農業行業中、例如肥料中之鐵來源。 Another advantage of the present invention is that the ferrous sulfate product can be used in a variety of industries, such as those in which a certain iron form is desired. For example, a ferrous sulfate mixture can be used as a reducing agent, for example, it can be used to reduce the Cr(VI) content of products particularly in the cement industry. Therefore, it can be used as an additive in a cement mixture. For example, it can be added to a Portland cement mixture to reduce Cr(VI). In addition, the ferrous sulfate product can be used in ceramic manufacturing. The ferrous sulfate product can also be used as a source of iron in agricultural industries, such as fertilizers.
本發明之另一優點在於該方法不使用外部施加之熱製造硫酸亞鐵產物。而是化學乾燥該產物。因此，需要非常基礎的設備來製造該產物。基本上，唯一需要的是標準混合機器。此產生較廉價方法，該方法需要顯著更少的能量且更為環保。 Another advantage of the present invention is that the method does not use externally applied heat to produce a ferrous sulfate product. Instead, the product is chemically dried. Therefore, very basic equipment is needed to make the product. Basically, the only thing that is needed is a standard mixing machine. This results in a less expensive method that requires significantly less energy and is more environmentally friendly.
現將在以下實例中以非限制性方式進一步闡述本發明。 The invention will now be further elucidated in a non-limiting manner in the following examples.
使用表1中所闡述之反應物製備自由流動硫酸亞鐵混合物。 A free flowing ferrous sulfate mixture was prepared using the reactants set forth in Table 1.
硫酸亞鐵七水合物為自二氧化鈦工廠(Tioxide Europe’s Huelva工廠)獲得之化合物。將此化合物添加至混合器中。 Ferrous sulfate heptahydrate is a compound obtained from a titanium dioxide plant (Tioxide Europe's Huelva plant). This compound was added to the mixer.
然後，將硫酸亞鐵單水合物及半水石膏添加至混合器中。此實例中所使用之硫酸亞鐵單水合物亦係自二氧化鈦工廠(Tioxide Europe’s Huelva工廠)獲得。半水石膏係自Fibran SpA,Italy獲得。 Then, ferrous sulfate monohydrate and hemihydrate gypsum are added to the mixer. The ferrous sulfate monohydrate used in this example was also obtained from a titanium dioxide plant (Tioxide Europe's Huelva plant). Semi-aqueous gypsum is available from Fibran SpA, Italy.
將反應混合物在室溫下攪拌約15分鐘以達成均質混合物。 The reaction mixture was stirred at room temperature for about 15 minutes to achieve a homogeneous mixture.
藉由流動時間方法測定在潮濕硫酸亞鐵七水合物、硫酸亞鐵單水合物與半水石膏之間之反應之結束。藉由在已開始反應後在不同時間取產物之樣品觀察最終產物之自由流動能力之演化。量測樣品在室溫下穿過漏斗之流動時間。當滿足以下標準中之一者或二者時認為反應結束：(a)當在室溫下將1000克產物填充至具有½英吋(1.27cm)頸部之漏斗中時，產物花費少於2分鐘及30秒之時間流出漏斗之頸部；(b)當在室溫下將1000克產物填充至具有1英吋(2.54cm)頸部之漏斗中時，產物花費少於40秒之時間流出漏斗之頸部。 The end of the reaction between the moist ferrous sulfate heptahydrate, the ferrous sulfate monohydrate and the hemihydrate gypsum was determined by a flow time method. The evolution of the free-flowing ability of the final product was observed by taking samples of the product at different times after the reaction had begun. The flow time of the sample through the funnel at room temperature was measured. The reaction was considered to be complete when one or both of the following criteria were met: (a) When 1000 g of product was filled into a funnel with a 1⁄2 inch (1.27 cm) neck at room temperature, the product cost less than 2 Minutes and 30 seconds out of the neck of the funnel; (b) When 1000 g of product is filled into a funnel with a 1 inch (2.54 cm) neck at room temperature, the product takes less than 40 seconds to flow out The neck of the funnel.
當滿足兩個條件時，反應結束且產物準備好進行儲存。 When both conditions are met, the reaction is complete and the product is ready for storage.
所製造之硫酸亞鐵產物實質上係乾燥的，如在實例2中所測定。其係自由流動的，如在實例3中所測定。 The ferrous sulfate product produced was substantially dry as determined in Example 2. It is free flowing as determined in Example 3.
使用經修改卡爾費雪程序測定實例1中所用試劑及如實例1中所製造之硫酸亞鐵產物中之自由水含量。 The free water content of the reagents used in Example 1 and the ferrous sulfate product produced as in Example 1 was determined using a modified Karl Fischer program.
標準卡爾費雪程序(Angew.Chem.1935,48(26)：394-396)滴定自 由水及晶體水分。在本發明中，僅自由水含量係相關的。因此，自標準卡爾費雪程序修改所用卡爾費雪程序以確保所實施量測僅測定自由水含量，而不測定任何晶體水分。此可藉由在室溫下使用丙醇實施初始萃取以去除樣品之自由水分來達成。然後，使用標準卡爾費雪容量滴定程序滴定此丙醇樣品之等份樣品，以獲得自由水含量之值。 Standard Karl Fischer program (Angew. Chem. 1935, 48(26): 394-396) titrated from Moisture from water and crystals. In the present invention, only the free water content is relevant. Therefore, the Karl Fischer program used was modified from the standard Karl Fischer program to ensure that the measurements performed were only measured for free water content without determining any crystal moisture. This can be achieved by performing an initial extraction using propanol at room temperature to remove free moisture from the sample. An aliquot of this propanol sample was then titrated using a standard Karl Fischer volumetric titration procedure to obtain a free water content value.
經修改卡爾費雪程序闡述於下文附錄A中。 The modified Carl Fisher procedure is described in Appendix A below.
利用此經修改卡爾費雪程序量測實例1中所使用之硫酸亞鐵七水合物及硫酸亞鐵單水合物化合物之自由水含量。亦以此方式測定所製造之硫酸亞鐵產物之自由水含量。 The free water content of the ferrous sulfate heptahydrate and ferrous sulfate monohydrate compounds used in Example 1 was measured using this modified Karl Fischer program. The free water content of the produced ferrous sulfate product was also determined in this manner.
結果概述於表2中。 The results are summarized in Table 2.
藉由量測在實例1中製造之硫酸亞鐵產物之流動時間證實自由流動能力。 The free flow ability was confirmed by measuring the flow time of the ferrous sulfate product produced in Example 1.
篩濾(在4mm下；5網目)2kg在實例1中製造之硫酸亞鐵產物樣品以消除粗糙材料。 Sifting (at 4 mm; 5 mesh) 2 kg of the ferrous sulfate product sample produced in Example 1 to eliminate the rough material.
利用1千克每一經篩濾材料填充兩個具有漏嘴開口(頸部)之漏斗(一者具有½英吋頸部且一者具有1英吋頸部)。然後，量測使產物流動穿過兩個頸部將漏斗完全倒空所花費之時間。 Two funnels with a spout opening (neck) were filled with 1 kg of each screened material (one with a 1⁄2 inch neck and one with a 1 inch neck). Then, measure the time it takes for the product to flow through the two necks to completely empty the funnel.
½英吋漏斗中之流動時間少於2分鐘及30秒且在1英吋漏斗中少於 40秒。 The flow time in the 1⁄2 inch funnel is less than 2 minutes and 30 seconds and less than 1 inch in the funnel 40 seconds.
在Huntsman Pigment Innovation Centre處使用具有EDAX x射線微量分析附件之JEOL T330A掃描電子顯微鏡分析實例1之硫酸亞鐵產物。 The ferrous sulfate product of Example 1 was analyzed at the Huntsman Pigment Innovation Centre using a JEOL T330A scanning electron microscope with an EDAX x-ray microanalytical accessory.
圖1係顯示所檢測到元素之光譜 Figure 1 shows the spectrum of the detected elements
圖2係產物之SEM影像 Figure 2 is an SEM image of the product
圖3係元素Fe、S、Ca及Ti之一組x射線圖 Figure 3 is a group of elemental Fe, S, Ca and Ti x-ray diagram
所檢測到的主要元素係鐵、硫、碳、氧及鈣。一些鈦、錳、鋁及鎂亦以較低濃度存在。粒子似乎主要由鐵、硫及鈣組成。 The main elements detected were iron, sulfur, carbon, oxygen and calcium. Some titanium, manganese, aluminum and magnesium are also present in lower concentrations. The particles appear to consist mainly of iron, sulfur and calcium.
鈣似乎作為黏著至較大晶體之表面之較小粒子存在。因此，在較高放大倍數下獲得影像及元素掃描以觀察此是否可更清晰地測定。 Calcium appears to be present as smaller particles that adhere to the surface of larger crystals. Therefore, image and element scans are obtained at higher magnification to see if this can be determined more clearly.
圖4係顯示自較高放大倍數掃描檢測到之元素之光譜 Figure 4 shows the spectrum of the elements detected from the higher magnification scan.
圖5係來自較高放大倍數掃描之產物之SEM影像 Figure 5 is an SEM image of a product from a higher magnification scan.
圖6係來自較高放大倍數掃描之元素Fe、S、Ca及Ti之一組x射線圖 Figure 6 is a set of x-ray images of elements Fe, S, Ca, and Ti from a higher magnification scan.
較高放大倍數下之光譜使得更加明確鈣係存於較大晶體之表面上之粒子中。元素x射線圖上之圓圈區顯示具有高鈣含量但似乎沒有任何鐵之粒子且該等粒子與顯微圖上似乎黏著至表面之粒子一致。重疊影像顯示該等粒子分佈於大多數晶體表面上方。 The higher magnification spectrum makes it clearer that calcium is present in the particles on the surface of larger crystals. The circled area on the elemental x-ray image shows particles with a high calcium content but does not appear to have any iron and which are consistent with the particles on the micrograph that appear to adhere to the surface. Overlapping images show that the particles are distributed over most of the crystal surface.
因此，硫酸亞鐵七水合物之粒子似乎具有硫酸鈣塗層。此塗層可用於減少摩擦且因此使得粒子更具流動性且更易於處置。 Therefore, the particles of ferrous sulfate heptahydrate appear to have a calcium sulfate coating. This coating can be used to reduce friction and thus make the particles more fluid and easier to handle.
實施實驗以便測定三種不同波特蘭水泥樣品中六價鉻減少之百分比。 Experiments were conducted to determine the percentage reduction in hexavalent chromium in three different Portland cement samples.
針對三個不同添加率(0.1w/w%；0.2w/w%；0.3w/w%)實施測試，其中在製造期間未添加還原劑。 The test was carried out for three different addition rates (0.1 w/w%; 0.2 w/w%; 0.3 w/w%), wherein no reducing agent was added during the manufacture.
將1克自水泥磨機獲得之不含任何還原劑之每一水泥之樣品與實例1之硫酸亞鐵產物混合，且利用以下程序進行分析。 One gram of each cement sample obtained from the cement mill without any reducing agent was mixed with the ferrous sulfate product of Example 1 and analyzed using the following procedure.
利用10ml蒸餾水萃取每一樣品並離心(3500rpm達3分鐘)。分離水並收集。利用新鮮水將此程序重複三次。 Each sample was extracted with 10 ml of distilled water and centrifuged (3500 rpm for 3 minutes). Separate the water and collect. This procedure was repeated three times with fresh water.
在50ml燒瓶中收集萃取水且添加10v/v%HCl至pH最高為2±0.5。 The extracted water was collected in a 50 ml flask and 10 v/v% HCl was added to a pH of up to 2 ± 0.5.
然後，利用在540nm下(UV-VIS儀器)標準比色測定與1,5 DPC(1,5-二苯基卡肼)之紫色複合物來分析10ml此溶液樣品。 Then, 10 ml of this solution sample was analyzed by a standard colorimetric assay at 540 nm (UV-VIS instrument) with a purple complex of 1,5 DPC (1,5-diphenylcarbazide).
針對三個添加率且針對三種不同水泥樣品重複該程序。 This procedure was repeated for three addition rates and for three different cement samples.
減少之百分比報告於表3中。 The percentage reduction is reported in Table 3.
儀器：自動滴定器 Instrument: automatic titrator
分析範圍：0.0001-100% Analysis range: 0.0001-100%
在室溫及室壓下實施 Implemented at room temperature and room pressure
使用此程序測定含有結晶水之產物之自由水含量。此程序使用卡爾費雪(KF)滴定來測定水之量。將樣品溶解於甲醇中。 This procedure was used to determine the free water content of the product containing crystal water. This procedure uses Karl Fischer (KF) titration to determine the amount of water. The sample was dissolved in methanol.
ROH+SO2+R’N[R’NH]SO3R (反應1) ROH+SO 2 +R'N [R'NH]SO 3 R (Reaction 1)
其中R’N=鹼，ROH=醇，通常甲醇 Wherein R'N = base, ROH = alcohol, usually methanol
在室溫下利用二氧化硫及碘之無水溶液在與氫離子反應之緩衝液存在下定量滴定樣品內之水。 The water in the sample is quantitatively titrated in the presence of a buffer solution reacted with hydrogen ions using a solution of sulfur dioxide and iodine in water at room temperature.
[R’NH]SO3R+H2O+I2+2R’N→2[R’NH]I+[R’NH]SO4R (反應2) [R'NH]SO 3 R+H 2 O+I 2 +2R'N→2[R'NH]I+[R'NH]SO 4 R (Reaction 2)
利用施加至雙銷鉑電極之電流電測法測定終點。 The endpoint was determined by current electrometry applied to a double pin platinum electrode.
反應2中烷基亞硫酸鹽氧化為烷基硫酸鹽所消耗之水應僅來自樣品。由於水及碘(I2)係以1：1化學計量比消耗，故藉由量測在完成反應後剩餘的I2的濃度來計算初始樣品中水之量。體積法量測I2。 The water consumed in the oxidation of the alkyl sulfite to the alkyl sulfate in Reaction 2 should be from the sample only. Since water and iodine (I 2 ) are consumed in a 1:1 stoichiometric ratio, the amount of water in the initial sample is calculated by measuring the concentration of I 2 remaining after completion of the reaction. Volumetric measurement of I 2 .
‧Hydranal®-複合物5=用於體積單組份卡爾費雪滴定之試劑(不含甲醇)，滴定度：1ml至5mg水，如自Sigma Aldrich獲得。此試劑含有碘、二氧化硫及咪唑及2-甲基咪唑之混合物，其係溶解於二乙二醇單乙基醚(DEGEE)中(參見註解A) ‧Hydranal®-complex 5 = reagent for volume single-component Karl Fischer titration (without methanol), titer: 1 ml to 5 mg water, as obtained from Sigma Aldrich. This reagent contains iodine, sulfur dioxide, and a mixture of imidazole and 2-methylimidazole, which is dissolved in diethylene glycol monoethyl ether (DEGEE) (see Note A).
‧Hydranal®-無水甲醇=用於體積單組份卡爾費雪滴定之試劑(工作介質)，如自Sigma Aldrich獲得。此試劑係水0.01%之甲醇。(參見註解A) ‧ Hydranal® - anhydrous methanol = reagent for bulk single-component Karl Fischer titration (working medium), as obtained from Sigma Aldrich. This reagent is water 0.01% methanol. (See Note A)
‧無水丙-1-醇 ‧ Anhydrous propan-1-ol
去礦物質之水 Mineral water
Metrohm USA公司體積卡爾費雪滴定器：「Karl-Fischer 890 Titrando」 Metrohm USA Volume Karl Fischer Titrator: "Karl-Fischer 890 Titrando"
雙鉑絲電極 Double platinum wire electrode
天平0.1mG Balance 0.1mG
注射器100μl Syringe 100μl
離心管 Centrifuge tube
離心機 Centrifuge
微量吸量管1ml Micro pipette 1ml
標準化： standardization:
‧開啟KF Titrando。 ‧Open KF Titrando.
‧選擇軟體上之KF滴定方法。 ‧ Select the KF titration method on the software.
‧輸入樣品ID資訊。 ‧ Enter sample ID information.
‧使用幫浦利用新鮮無水甲醇沖洗滴定池，在池中留下約25-30ml。按下軟體上之START按鈕以開始調整過程。在調整池中之甲醇後，螢幕上出現調整OK。 • Use a pump to rinse the titration cell with fresh anhydrous methanol, leaving approximately 25-30 ml in the pool. Press the START button on the software to start the adjustment process. After adjusting the methanol in the pool, the adjustment OK appears on the screen.
‧稱含有50μl去礦物質水之100μl注射器之皮重，並將此添加至滴定池中。重新稱重注射器且算出添加至滴定池之水。錄入所添加水之重量並按下START。 ‧ The tare weight of a 100 μl syringe containing 50 μl of demineralized water was weighed and added to the titration cell. The syringe is reweighed and the water added to the titration cell is calculated. Enter the weight of the added water and press START.
‧在完成滴定後，將展現水%結果。 ‧ After the titration is completed, the water % result will be displayed.
‧一式三份實施滴定測定。 • Perform titration assays in triplicate.
用於KF烘箱方法之Apura® 1%固體標準品(參見註解B) Apra® 1% solid standard for KF oven method (see Note B)
‧開啟KF Titrando。 ‧Open KF Titrando.
‧選擇軟體上之KF測定方法。 ‧ Select the KF measurement method on the software.
‧將約10g樣品置於離心管中。 ‧ Place approximately 10 g of sample in a centrifuge tube.
‧將25ml丙-1-醇添加至離心管並使用玻璃攪拌器充分混合。 • Add 25 ml of propan-1-ol to the centrifuge tube and mix well using a glass stirrer.
‧將管置於離心機中並以7500rpm將樣品分離1分鐘。 • Place the tube in a centrifuge and separate the sample for 1 minute at 7500 rpm.
‧輸入樣品ID資訊並錄入樣品之重量。重量=所取重量/所添加丙-1-醇之體積×滴定至滴定池中之體積。 ‧ Enter the sample ID information and enter the weight of the sample. Weight = weight taken / volume of added propan-1-ol × volume titrated into the titration cell.
‧使用幫浦利用新鮮無水甲醇沖洗滴定池，池中留下約25-30ml。按下軟體上之START按鈕以開始調整過程。在調整池中之甲醇後，螢幕上出現調整OK。 ‧Use the pump to rinse the titration cell with fresh anhydrous methanol, leaving about 25-30ml in the pool. Press the START button on the software to start the adjustment process. After adjusting the methanol in the pool, the adjustment OK appears on the screen.
‧當已停止離心時，去除離心管並將1ml上清液吸取至滴定池中並按下OK。(參見註解C) ‧ When centrifugation has been stopped, remove the centrifuge tube and pipe 1 ml of the supernatant into the titration cell and press OK. (See Note C)
‧在完成滴定後，將展現水%結果。 ‧ After the titration is completed, the water % result will be displayed.
‧編輯樣品資訊且添加正確重量並重新計算水%。 • Edit the sample information and add the correct weight and recalculate the water %.
‧一式兩份實施滴定(參見註解D)。 • Perform titration in duplicate (see Note D).
‧無需計算，此乃因可自PC直接閱讀結果。 ‧ No calculation is required, because the results can be read directly from the PC.
記錄結果：2位小數 Record result: 2 decimal places
報告結果：2位小數 Report result: 2 decimal places
單位：% Unit: %
‧一個操作者實施8個重複 ‧One operator implements 8 repetitions
A-Hydranal®溶液之儲放壽命為打開後3年。 The storage life of A-Hydranal® solution is 3 years after opening.
B-參見TiO2之水含量，藉由卡爾費雪方法SPMM測得 B - see the water content of TiO 2 as measured by the Karl Fischer method SPMM
C-確保將樣品添加至滴定池中而不接觸滴定池之表面及溶液。 C-Ensure that the sample is added to the titration cell without contacting the surface and solution of the titration cell.
D-在完成滴定後，儀器/軟體自動開始調整過程準備好用於下一樣品。 D- After the titration is completed, the instrument/software automatically begins the adjustment process and is ready for the next sample.
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| JPS59501825A (en) * | 1982-11-17 | 1984-11-01 | アクテイ−ゼルスカベツト アアルボルグ ポ−トランド−セメント−フアブリク | How to improve powder properties |
| FR2566383B1 (en) * | 1984-06-20 | 1988-12-16 | Sarval | PROCESS FOR THE TREATMENT OF FERROUS SULPHATE HEPTAHYDRATE, TO SUPPRESS ITS TENDENCY TO AGGLOMERATE AND MAKE IT AFFECTIVE TO FLOW FREELY |
| US5268159A (en) * | 1990-01-30 | 1993-12-07 | Bayer Aktiengesellschaft | Process for the production of storable, free-flowing hydrated ferrous sulfate |
| EP2452921A1 (en) * | 2010-11-16 | 2012-05-16 | Tioxide Europe, S.L. | Process for producing a modified grade of iron sulphate heptahydrate |
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