WO2016074348A1 - Method for preparing hypophosphorous acid with ferrophosphorus - Google Patents
Method for preparing hypophosphorous acid with ferrophosphorus Download PDFInfo
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- WO2016074348A1 WO2016074348A1 PCT/CN2015/071520 CN2015071520W WO2016074348A1 WO 2016074348 A1 WO2016074348 A1 WO 2016074348A1 CN 2015071520 W CN2015071520 W CN 2015071520W WO 2016074348 A1 WO2016074348 A1 WO 2016074348A1
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- hypophosphorous acid
- phosphorus
- ferrophosphorus
- acid
- sulfuric acid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/165—Hypophosphorous acid; Salts thereof
Definitions
- the invention belongs to the field of chemical industry, and is a method for producing hypophosphorous acid by using an electro-furnace method to produce phosphorus iron (or similar substance) produced by yellow phosphorus as a raw material.
- hypophosphorous acid also known as hypophosphorous acid
- hypophosphorous acid is reductive and widely used in electroless plating, or in the production of nickel-hydrogen battery cathodes, food production, organic synthesis, medicine, and the like.
- the conventional preparation method of hypophosphorous acid generally adopts a two-step preparation method of preparing soluble hypophosphite and then acidifying by metathesis reaction to obtain hypophosphorous acid.
- yellow phosphorus is reacted with barium hydroxide to form a calcium hypophosphite solution, and then sulfuric acid is added to form barium sulfate precipitate, and the precipitate is filtered to obtain hypophosphorous acid.
- sulfuric acid is added to form barium sulfate precipitate, and the precipitate is filtered to obtain hypophosphorous acid.
- the reaction of yellow phosphorus with lime, caustic soda, sodium hypophosphite, ion-exchange membrane electrodialysis, ion exchange, electrolysis, etc. to produce hypophosphorous acid.
- Phosphorus iron is a kind of waste slag produced in the production of phosphorus chemical industry or a substance containing phosphorus and iron, such as yellow phosphorus, calcium phosphate fertilizer by-product phosphorus iron.
- Phosphorus iron generally has a metallic luster of silver-gray (or yellowish) solids, which is relatively hard and brittle and has a certain ferromagnetism. Through the chemical element analysis of ferrophosphorus, the results show that the largest content is iron, iron accounted for 55% to 75%, followed by phosphorus, and phosphorus accounts for 10% to 20%.
- ferrophosphorus contains a large amount of iron and phosphorus, its chemical properties are extremely stable. It does not oxidize slowly in the air like iron. It does not oxidize white smoke or even burn in the air like phosphorus. Phosphorus can be It persists in the air for a long time. It is indicated that there is no single state of phosphorus and iron in the ferrophosphorus. X-ray diffraction analysis of the ferrophosphorus showed that there were two forms of Fe 2 P and Fe 3 P in the ferrophosphorus.
- the conventional utilization of ferrophosphorus can be used as an alloying agent and deoxidizer for steelmaking.
- the chemical utilization is generally carried out by mixing soda ash with ferrophosphorus powder and then calcining at a high temperature, then leaching with water, and the filtrate is concentrated, crystallized and dried to obtain trisodium phosphate. The product, the filter residue is washed and dried to obtain iron oxide.
- hypophosphorous acid that is, the reaction of yellow phosphorus with lime milk and soda ash, to produce sodium hypophosphite, and then converted to hypophosphorous acid.
- the reaction of yellow phosphorus with alkali is a disproportionation reaction, which causes disproportionation of phosphine while producing hypophosphite, resulting in a decrease in yield and an increase in the difficulty of treating phosphine.
- the chemical nature of yellow phosphorus is active and easily reacts with air, which also increases the difficulty of production control.
- ferrophosphorus As a by-product of yellow phosphorus, ferrophosphorus is generally used as iron-containing waste, and its economic benefits are very low. There has been no better technology to increase the economic value of ferrophosphorus.
- the invention solves the defects of low utilization value of the original ferrophosphorus, less utilization channels, or long processing process, and the disadvantages of the production method of the hypophosphorous acid and the single material selection and the high processing cost, and proposes a new utilization mode of the phosphorus iron and A new method for the manufacture of hypophosphorous acid, which has the characteristics of low cost, full utilization of waste resources or by-products, and simple process.
- the technical solution adopted by the present invention is: a method for preparing hypophosphorous acid using phosphorus iron, comprising the following steps:
Abstract
Provided is a method for preparing hypophosphorous acid with ferrophosphorus, which comprises: pulverizing the ferrophosphorus, acid dipping with sulfuric acid, filtrating, extracting, removing the sulfuric acid, back extracting, and concentrating to obtain the hypophosphorous acid. The method uses the by-products or waste materials of phosphorus production in the chemical industry, and has the characteristics of a low cost, a simple process, and a good product quality.
Description
本发明属于化工领域，是一种用电炉法生产黄磷副产的磷铁（或类似物质）为原料生产次磷酸的方法。 The invention belongs to the field of chemical industry, and is a method for producing hypophosphorous acid by using an electro-furnace method to produce phosphorus iron (or similar substance) produced by yellow phosphorus as a raw material.
次磷酸又名次亚磷酸，具有还原性而广泛的应用于化学镀，或者用于镍氢电池阴极生产、食品生产、有机合成、医药等方面。
Hypophosphorous acid, also known as hypophosphorous acid, is reductive and widely used in electroless plating, or in the production of nickel-hydrogen battery cathodes, food production, organic synthesis, medicine, and the like.
次磷酸的常规制备方法，一般是采用先制备出可溶性次磷酸盐，再经复分解反应酸化后得到次磷酸的两步制备方法。如用黄磷与氢氧化钡反应，生成次磷酸钙溶液，再加硫酸生成硫酸钡沉淀，过滤沉淀后得到次磷酸。或以黄磷与石灰、烧碱反应先生成次磷酸钠，经离子膜电渗析法、离子交换法、电解法等制成次磷酸。
The conventional preparation method of hypophosphorous acid generally adopts a two-step preparation method of preparing soluble hypophosphite and then acidifying by metathesis reaction to obtain hypophosphorous acid. For example, yellow phosphorus is reacted with barium hydroxide to form a calcium hypophosphite solution, and then sulfuric acid is added to form barium sulfate precipitate, and the precipitate is filtered to obtain hypophosphorous acid. Or the reaction of yellow phosphorus with lime, caustic soda, sodium hypophosphite, ion-exchange membrane electrodialysis, ion exchange, electrolysis, etc. to produce hypophosphorous acid.
也有专利 CN201110063628
提出以葡萄糖和碱式磷酸盐为原料经过反应、分离、纯化等步骤生产次磷酸的方法。 There are also patents CN201110063628
A method for producing hypophosphorous acid by reacting, separating and purifying with glucose and basic phosphate as raw materials is proposed.
磷铁是一种磷化工生产中产生的废渣或者称为副产物的含有磷和铁的物质，如黄磷、钙镁磷肥副产的磷铁等。磷铁一般带有金属光泽的银灰色（或带黄色）固体，较坚硬且偏脆性，有一定的铁磁性。通过对磷铁进行化学元素分析，结果表明其含量最大的是铁元素，铁占
55% ～ 75% ，其次是磷元素，磷占 10% ～ 20% 。
Phosphorus iron is a kind of waste slag produced in the production of phosphorus chemical industry or a substance containing phosphorus and iron, such as yellow phosphorus, calcium phosphate fertilizer by-product phosphorus iron. Phosphorus iron generally has a metallic luster of silver-gray (or yellowish) solids, which is relatively hard and brittle and has a certain ferromagnetism. Through the chemical element analysis of ferrophosphorus, the results show that the largest content is iron, iron accounted for
55% to 75%, followed by phosphorus, and phosphorus accounts for 10% to 20%.
虽然磷铁中含有大量的铁和磷元素，但其化学性质异常稳定，不像铁那样在空气中会缓慢氧化，也不像磷那样在空气中会立即氧化冒白烟甚至燃烧，磷铁可以在空气中长期稳定存在。说明磷铁中不存在单质态的磷和铁。对磷铁进行
X 射线衍射分析，结果表明磷铁中存在的是 Fe2P 、 Fe3P 两种形态。Although ferrophosphorus contains a large amount of iron and phosphorus, its chemical properties are extremely stable. It does not oxidize slowly in the air like iron. It does not oxidize white smoke or even burn in the air like phosphorus. Phosphorus can be It persists in the air for a long time. It is indicated that there is no single state of phosphorus and iron in the ferrophosphorus. X-ray diffraction analysis of the ferrophosphorus showed that there were two forms of Fe 2 P and Fe 3 P in the ferrophosphorus.
磷铁的常规利用，可以作为炼钢的合金剂、脱氧剂，化学利用一般采用配入纯碱与磷铁粉混合后高温煅烧，然后用水浸取，滤液经浓缩、结晶、干燥制得磷酸三钠产品，滤渣经洗涤、烘干制得氧化铁。
The conventional utilization of ferrophosphorus can be used as an alloying agent and deoxidizer for steelmaking. The chemical utilization is generally carried out by mixing soda ash with ferrophosphorus powder and then calcining at a high temperature, then leaching with water, and the filtrate is concentrated, crystallized and dried to obtain trisodium phosphate. The product, the filter residue is washed and dried to obtain iron oxide.
次磷酸的常规生产方法，即用黄磷与石灰乳和纯碱反应，制得次磷酸钠，再转制为次磷酸。黄磷与碱的反应是歧化反应，在生成次磷酸根的同时，会歧化磷化氢，导致产率降低，同时增加处理磷化氢的难度。
而且，黄磷的化学性质活泼，易与空气反应，也增加了生产的控制难度。The conventional production method of hypophosphorous acid, that is, the reaction of yellow phosphorus with lime milk and soda ash, to produce sodium hypophosphite, and then converted to hypophosphorous acid. The reaction of yellow phosphorus with alkali is a disproportionation reaction, which causes disproportionation of phosphine while producing hypophosphite, resulting in a decrease in yield and an increase in the difficulty of treating phosphine.
Moreover, the chemical nature of yellow phosphorus is active and easily reacts with air, which also increases the difficulty of production control.
磷铁作为一种黄磷的副产物，一般是当作含铁的废料加以使用，经济效益很低。一直没有更好的技术提高磷铁的经济价值。As a by-product of yellow phosphorus, ferrophosphorus is generally used as iron-containing waste, and its economic benefits are very low. There has been no better technology to increase the economic value of ferrophosphorus.
本发明要解决原有磷铁的利用价值低、利用渠道少、或者加工流程冗长的缺点，以及次磷酸的生产方法及原料选择较单一、加工成本较高等缺点，提出全新的磷铁利用途径及次磷酸制造的新方法，该方法具有成本低、充分利用废弃资源或副产物、工艺简单的特点。
The invention solves the defects of low utilization value of the original ferrophosphorus, less utilization channels, or long processing process, and the disadvantages of the production method of the hypophosphorous acid and the single material selection and the high processing cost, and proposes a new utilization mode of the phosphorus iron and A new method for the manufacture of hypophosphorous acid, which has the characteristics of low cost, full utilization of waste resources or by-products, and simple process.
为了实现上述目地，本发明采取的技术方案为：一种用磷铁制备次磷酸的方法，包括以下步骤： In order to achieve the above object, the technical solution adopted by the present invention is: a method for preparing hypophosphorous acid using phosphorus iron, comprising the following steps:
- （1） 粉碎：用粉碎机械将块状磷铁破碎到足够细度。 (1) Crushing: The massive ferro-phosphorus is crushed to a sufficient fineness by a pulverizing machine.
- （2） 酸浸：控制适当的固液比、 硫酸 浓度、压力、反应温度等条件，使磷铁不断反应生成硫酸亚铁和次磷酸。 (2) Acid leaching: control the appropriate solid-liquid ratio, sulfuric acid concentration, pressure, reaction temperature and other conditions, so that phosphorus iron continuously reacts to form ferrous sulfate and hypophosphorous acid.
- （3） 过滤：过滤反应液，分离出未反应原料，得到含硫酸亚铁和次磷酸的滤液，未反应的磷铁返回继续使用。 (3) Filtration: The reaction solution was filtered, and unreacted raw materials were separated to obtain a filtrate containing ferrous sulfate and hypophosphorous acid, and unreacted ferrophosphorus was returned for continued use.
- （4） 萃取：次磷酸和硫酸亚铁的硫酸溶液用有机溶剂萃取，次磷酸及硫酸进入有机相，硫酸亚铁留在水相。 (4) Extraction: The sulfuric acid solution of hypophosphorous acid and ferrous sulfate is extracted with an organic solvent, hypophosphorous acid and sulfuric acid enter the organic phase, and ferrous sulfate remains in the aqueous phase.
- （5） 除硫酸：分离出有机相后，加入碳酸钙（或碳酸钡）反应，硫酸形成硫酸钙沉淀（或硫酸钡），分离沉淀。 (5) In addition to sulfuric acid: After separating the organic phase, calcium carbonate (or cesium carbonate) is added to react, and sulfuric acid forms a calcium sulfate precipitate (or barium sulfate), and the precipitate is separated.
- （6） 反萃：分离硫酸钙的有机相，用水反萃，分离出含次磷酸的溶液。 (6) Stripping: separating the organic phase of calcium sulfate, stripping with water, and separating the solution containing hypophosphorous acid.
- （7） 浓缩：将次磷酸溶液蒸发浓缩到需要的浓度。 (7) Concentration: The hypophosphorous acid solution is concentrated by evaporation to the desired concentration.
用鄂式破碎机大块磷铁粗碎，然后用圆盘粉碎机进一步破碎到 1 ～ 2mm 粒径，用球磨机再磨细至过
200 目，取上述磷铁原料 400g ，用 3000g40% 的 H 2 SO 4 在 100 ℃、搅拌速度为 500r/min 的条件下反应 12h
，反应结束后进行过滤，溶液过滤后为滤液 2200g ，滤液用 2000g 磷酸三丁酯萃取，得到有机相 2500g
，加入碳酸钙除掉硫酸，过滤去掉硫酸钙，滤液为次磷酸溶液。 Use a jaw crusher to grind large pieces of ferro-phosphorus, and then further crush it to a particle size of 1 to 2 mm with a disc crusher, and then grind it with a ball mill.
200 mesh, take 400g of the above-mentioned ferrophosphorus raw material, and react with 3000g of 40% H 2 SO 4 at 100 °C and stirring speed of 500r/min for 12h.
After the completion of the reaction, the mixture was filtered, and the solution was filtered to obtain 2200 g of a filtrate. The filtrate was extracted with 2000 g of tributyl phosphate to obtain an organic phase of 2500 g.
Add calcium carbonate to remove sulfuric acid, remove calcium sulfate by filtration, and the filtrate is a hypophosphorous acid solution.
用粉碎设备将大块磷铁粉碎到要求的细度，取粉状磷铁原料 500g ，用 2000g40% 的 H 2
SO 4 在 105 ℃、搅拌速度为 500r/min 的条件下反应 10h ，反应结束后进行过滤，溶液过滤后为滤液 1700g ，滤液用 1500g
正丁醇萃取，萃出相加热蒸发，分离出有机相，水相再加入适量的碳酸钙与硫酸刚好完全，反应生成硫酸钙以除掉硫酸，过滤，滤渣为硫酸钙，得滤液 2000g
即为次磷酸溶液，再浓缩到需要的浓度。 Grinding large pieces of ferrophosphorus to the required fineness with a pulverizing equipment, taking 500g of powdered ferrophosphorus raw material, using 2000g of 40% H 2
SO 4 was reacted at 105 ° C and stirring speed of 500 r / min for 10 h. After the reaction was completed, it was filtered. After filtration, the solution was filtered to obtain 1700 g of filtrate and 1500 g of filtrate.
After n-butanol extraction, the extraction phase is heated and evaporated, and the organic phase is separated. The aqueous phase is added with appropriate amount of calcium carbonate and sulfuric acid, and the reaction forms calcium sulfate to remove sulfuric acid, and the filter residue is calcium sulfate, and the filtrate is obtained.
This is a hypophosphorous acid solution and is concentrated to the desired concentration.
Claims (6)
- 一种用磷铁制备生产次磷酸的 方法。A method for producing hypophosphorous acid using phosphorus iron.
- 权利要求 1 的 一种用磷铁制备生产次磷酸的 方法 ， 其特征在于使用的磷化工废料为磷矿加工后形成的废料或副产物，包括黄磷生产所产生的磷铁、钙镁磷肥生产所产生的磷铁。 A method for producing hypophosphorous acid by using ferrophosphorus according to claim 1, The utility model is characterized in that the phosphorus chemical waste used is waste or by-product formed after the phosphate rock processing, and the ferro-phosphorus produced by the production of the phosphorus iron and the calcium magnesium phosphate fertilizer produced by the yellow phosphorus production.
- 权利要求 2 的 一种用磷铁制备生产次磷酸的 方法 ， 其特征在于这种含磷含铁的 磷化工废料 含有铁元素35%～85%，含有磷10%～30%。A method for producing hypophosphorous acid by using ferrophosphorus according to claim 2, characterized in that the phosphorus-containing phosphorus-containing chemical waste It contains 35% to 85% of iron and contains 10% to 30% of phosphorus.
- 权利要求1的 一种用磷铁制备生产次磷酸的 方法 ，其特征在于采用硫酸与磷铁反应。A method for producing hypophosphorous acid produced by using phosphorus iron according to claim 1, characterized in that sulfuric acid is reacted with ferrophosphorus.
- 权利要求4的一种用磷铁制备生产次磷酸的 方法 ，其特征在于采用硫酸与磷铁反应后生产含有次磷酸的溶液。Method for producing hypophosphorous acid by using ferrophosphorus according to claim 4 It is characterized in that a solution containing hypophosphorous acid is produced by reacting sulfuric acid with ferrophosphorus.
- 权利要求1的一种用磷铁制备生产次磷酸的 方法 ，其特征在于 包括以下步骤的一步或多步：A method of producing hypophosphorous acid produced by using ferrophosphorus according to claim 1, characterized by comprising one or more steps of the following steps:（1） 粉碎：用粉碎机械将块状磷铁破碎到足够细度。(1) Crushing: The massive ferro-phosphorus is crushed to a sufficient fineness by a pulverizing machine.（2） 酸浸：控制适当的固液比、 硫酸 浓度、压力、反应温度等条件，使磷铁不断反应生成硫酸亚铁和次磷酸。(2) Acid leaching: control of proper solid-liquid ratio, sulfuric acid Conditions such as concentration, pressure, and reaction temperature cause the ferrophosphorus to continuously react to form ferrous sulfate and hypophosphorous acid.（3） 过滤：过滤反应液，分离出未反应原料，得到含硫酸亚铁和次磷酸的滤液，未反应的磷铁返回作原料继续使用。(3) Filtration: The reaction solution was filtered, and the unreacted raw materials were separated to obtain a filtrate containing ferrous sulfate and hypophosphorous acid, and the unreacted ferrophosphorus was returned as a raw material for further use.（4） 萃取：次磷酸和硫酸亚铁的硫酸溶液用有机溶剂萃取，次磷酸及硫酸进入有机相，硫酸亚铁留在水相。(4) Extraction: The sulfuric acid solution of hypophosphorous acid and ferrous sulfate is extracted with an organic solvent, hypophosphorous acid and sulfuric acid enter the organic phase, and ferrous sulfate remains in the aqueous phase.（5） 除硫酸：分离出有机相后，加入碳酸钙（或碳酸钡）反应，硫酸形成硫酸钙沉淀（或硫酸钡），分离沉淀。(5) In addition to sulfuric acid: After separating the organic phase, calcium carbonate (or cesium carbonate) is added to react, and sulfuric acid forms a calcium sulfate precipitate (or barium sulfate), and the precipitate is separated.（6） 反萃：分离硫酸钙的有机相，用水反萃，分离出含次磷酸水溶液。(6) Stripping: separating the organic phase of calcium sulfate, stripping with water, and separating the aqueous solution containing hypophosphorous acid.浓缩：将次磷酸溶液蒸发浓缩到需要的浓度。Concentration: The hypophosphorous acid solution is concentrated by evaporation to the desired concentration.
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| CN201410646509.3 | 2014-11-15 | ||
| CN201410646509.3A CN104386659B (en) | 2014-11-15 | 2014-11-15 | A method of hypophosphorous acid is produced with phosphorous chemical industry waste material |
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| CN113061354A (en) * | 2021-02-25 | 2021-07-02 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Modified ferrophosphorus powder and preparation method and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1341779A (en) * | 2001-09-07 | 2002-03-27 | 南开大学 | Method for preparing hypophosphorous acid by using electrolytic method |
| CN101181983A (en) * | 2007-12-12 | 2008-05-21 | 湖北兴发化工集团股份有限公司 | Method for producing hypophosphorous acid |
| CN101481102A (en) * | 2008-01-11 | 2009-07-15 | 桑达-阿比克有限责任公司 | Method for obtaining sodium hypophosphite from phosphorus-containing slime |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1341779A (en) * | 2001-09-07 | 2002-03-27 | 南开大学 | Method for preparing hypophosphorous acid by using electrolytic method |
| CN101181983A (en) * | 2007-12-12 | 2008-05-21 | 湖北兴发化工集团股份有限公司 | Method for producing hypophosphorous acid |
| CN101481102A (en) * | 2008-01-11 | 2009-07-15 | 桑达-阿比克有限责任公司 | Method for obtaining sodium hypophosphite from phosphorus-containing slime |
Non-Patent Citations (1)
| Title |
|---|
| MAO, ANZHANG;: "Review on Preparation of Hypophosphorous Acid and Hypophosphite and Recovery of Byproduct", GUANGDONG CHEMICAL INDUSTRY, 31 December 2004 (2004-12-31), pages 1 - 3 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113061354A (en) * | 2021-02-25 | 2021-07-02 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Modified ferrophosphorus powder and preparation method and application thereof |
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