WO2011150636A1 - Method for preparing disodium stannous citrate - Google Patents
Method for preparing disodium stannous citrate Download PDFInfo
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- WO2011150636A1 WO2011150636A1 PCT/CN2010/079426 CN2010079426W WO2011150636A1 WO 2011150636 A1 WO2011150636 A1 WO 2011150636A1 CN 2010079426 W CN2010079426 W CN 2010079426W WO 2011150636 A1 WO2011150636 A1 WO 2011150636A1
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- citrate
- stannous
- aqueous solution
- disodium
- trisodium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
Definitions
- the invention relates to a method for preparing a food additive, in particular to a method for preparing disodium citrate disodium. So? Sakamoto
- Sodium citrate disodium is also known as lemon stannous acid disodium citrate sodium stannous citrate, 8301 color protecting agent, molecular formula C 6 SiiN, molecular weight 370.79, the structural formula is as follows:
- Disodium citrate disodium is a s-colored powdery solid, highly soluble in water, easy to absorb moisture, and easily oxidized. The melting point is (decomposed), and 260 l begins to turn yellow and turns brown.
- the oral LI1 ⁇ 2 of mice is 27Wfflg/i3 ⁇ 4, which is negative for the sudden and septic test and is a microtoxic chemical. This product has strong reducibility, smear anti-oxidation copper in preservative additives: preservatives and color protectants.
- disodium citrate is suitable for mushrooms, apples, lemons, chestnuts, ginkgo, green plums, light citrus, walnuts, Aloes, ridges, lychees, carrots, beetroots, juices and other canned fruits and vegetables, so it is a kind of food additive.
- disodium citrate disodium can exert anti-oxidation, anti-corrosion and color protection functions is to maintain the color and phoenix flavor of food based on its ability to gradually consume residual oxygen in cans, and Sn 2 ⁇ is converted into Sn 4 ⁇ .
- disodium citrate disodium salt from stannous chloride has two major disadvantages: one is high sodium chloride content; the second is that it is easy to obtain a large amount of solid substance dissolved in water, and the obtained product is difficult to meet the standard requirements.
- the second edition of the Food Additives Manual edited by Ling Guanting is made up of citric acid, stannous chloride and sodium hydroxide to form dibasic citrate precipitate, and then reacted with sodium oxide and citric acid.
- Lime sample an aqueous solution of stannous acid disodium, which is concentrated in a vacuum and filtered to remove insoluble matter.
- the applicant provides a preparation method for preparing stannous citrate disodium salt in an alcohol medium by using the invention patent No. ZL200610 2438S, 1 to convert the stannous chloride with sodium oxide. It is a gas oxidized stannous oxide, which reacts with citric acid to form di-stannous citrate. In the ethanol medium, bis- 3E tin and citric acid should be converted into stannous citrate and then reacted with sodium hydroxide ethanol solution. , stannous citrate is converted to disodium citrate disodium. The use of sodium hydroxide to convert vaporized stannous to hydrogen hydroxide.
- the object of the present invention is to overcome the above-mentioned deficiencies and to provide a process for preparing a lemon sulfonium disodium salt which is produced by a chemical process.
- the invention uses trisodium citrate and stannous gasification as raw materials, including 1 ⁇ 2 lower steps: dissolving sodium citrate and stannous chloride respectively in water;
- di-stannous citrate is added to a trisodium citrate aqueous solution having a weight concentration of 2:0 to 40%, and the reaction is stirred until completely agitated.
- the molar ratio of di-tin citrate to trisodium citrate is 1: 0.9S- i.15r
- step A in order to prevent the oxidation of stannous and accelerate the dissolution process: it is preferable to dissolve the stannous in the hot water and add a small amount of metal tin powder.
- the system temperature is preferably 10 ⁇ 55 ⁇ , more preferably close to room temperature 20-35 C 3 ⁇ 4
- step B when the trisodium citrate solution is added, the trisodium citrate aqueous solution is reacted with the vaporized stannous aqueous solution, and the system H value is preferably 1-5, more preferably 2 to 4, and the system temperature is preferably 10- 55X, more preferably 20-35 ⁇ 0 near room temperature.
- step B the trisodium citrate aqueous solution and the vaporized stannous aqueous solution are stirred and reacted for ⁇ . ⁇ ⁇ hours, and the molar ratio of trisodium citrate to sodium hydrogencarbonate is 1:0, 95, 1 ⁇ .
- the sodium carbonate-free aqueous solution was added to the mixture, and the reaction was stirred for 0.1 hour, and the filtration and pure water washing were carried out.
- step C and step D The chemical reactions that occur in step C and step D are:
- the above clarified lemon trisodium sulphate solution is added to the stannous chloride filtrate at room temperature, and the reaction system has a pH value of 2 to 4 by using a salt curtain and/or an aqueous sodium chlorate solution to prepare di-n-butyl citrate. Suspended matter.
- Tin content (% by weight): >31.6 ;
- Arsenic in terms of As, % by weight: ⁇ 0.00005;
- Heavy metals in terms of Pb, % by weight: ⁇ 0.0002.
- Chlorine (calculated as C-, % by weight): ⁇ 0,005.
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Abstract
Disclosure is a method for preparing disodium stannous citrate, comprising the following steps: selecting trisodium citrate and stannous chloride as starting materials and respectively dissolving trisodium citrate and stannous chloride in water; adding the aqueous solution of trisodium citrate to the aqueous solution of stannous chloride to obtain the solid product of distannous citrate; adding distannous citrate to the aqueous solution of trisodium citrate, stirring and reacting until dissolve entirely; then adding the aqueous solution of sodium bicarbonate to obtain the solution of disodium stannous citrate; and concentrating, drying and grinding to obtain the solid powder of disodium stannous citrate. The method omits the step of preparing stannous hydroxide and prevents bivalent tin from being in the alkaline solution environment by controlling the pH value of the reaction system below 5.0 before precipitating stannous citrate, thereby avoiding the problem on the antioxidant treatment in the process of preparing disodium stannous citrate and improving the quality of the product of disodium stannous citrate.
Description
说 明 书 柠檬酸亚锡二钠的制备方法 技术领域 Description: Preparation method of stannous citrate disodium
本发明涉及一种食品添加剂的制备方法， 具体是柠檬酸亚锡二钠的制 备方法。 索？殳本 The invention relates to a method for preparing a food additive, in particular to a method for preparing disodium citrate disodium. So? Sakamoto
柠檬酸亚锡二钠又名柠檬纖亚锡酸二钠 柠檬酸亚锡钠、 8301护色剂, 分子式 C6 SiiN ， 分子量 370.79， 结构式如下： Sodium citrate disodium is also known as lemon stannous acid disodium citrate sodium stannous citrate, 8301 color protecting agent, molecular formula C 6 SiiN, molecular weight 370.79, the structural formula is as follows:
H?C—— COONa H ? C - COONa
HO― Ί C— -COOSnOH HO― Ί C— -COOSnOH
H2C i COONa 柠檬酸亚锡二钠为 s色粉状固体， 极易溶于水， 易吸湿灌觯， 椽易氧 化。熔点为 (分解) ， 260 l开始变黄， 变成棕色。 小鼠口服的 LI½ 为 27Wfflg/i¾, 致突、 致崎试验为阴性， 属微毒性化学品。 本品有强 还原性， 在會品添加剂中诈 ¾抗氧化铜:、防腐剂和护色剂。根据 2003- 05-28 修订的 《食; 添加剂使用卫生标准》（GB276:0- 1996), 柠檬酸亚锡二钠适用 于蘑菇、 苹果、 柠檬、 板栗、 银杏、 青梅、 輕合 柑橘、 核桃、 芦夢、 脊 豆、 荔枝、 胡萝卜、 甜菜根、 果汁等果蔬罐头食品， 因此是一 '种应用广 g的 食品添加剂。 柠檬酸亚锡二钠之所以能发挥抗氧化、 防腐和护色作用， 保 持食品的色质与凤味的原理是基于其能逐渐消耗罐头中残余氧气， Sn2÷被 化成 Sn4÷。 由于其毒性低， 能安全有效地替代含硫护色剂， 而且护色效果 拧檬酸亚锡二钠作为食品添加剂在觀夕卜就已得到广泛使用。 但至今国 外专利或公幵的资料均无柠檬酸亚锡二钠的制备方法介绍。 中国食品添加
剂产业网 ( www.feic.cn ) 在稳定和凝固剂一栏 43简单介绍了柠檬酸亚锡二 钠制备方法， 是由氣化亚锡、 柠檬酸与氢氧化钠反应制得。 但从氯化亚锡 为原料制备柠樣酸亜锡二钠有二大缺点， 一是氯化钠含量高； 其次是容易 获得大量 溶于水的固体物质， 所得产物难以达到标准的要求。 H 2 C i COONa Disodium citrate disodium is a s-colored powdery solid, highly soluble in water, easy to absorb moisture, and easily oxidized. The melting point is (decomposed), and 260 l begins to turn yellow and turns brown. The oral LI1⁄2 of mice is 27Wfflg/i3⁄4, which is negative for the sudden and septic test and is a microtoxic chemical. This product has strong reducibility, smear anti-oxidation copper in preservative additives: preservatives and color protectants. According to the 2003- 05-28 revised "Food; Hygienic Standards for the Use of Additives" (GB276:0-1996), disodium citrate is suitable for mushrooms, apples, lemons, chestnuts, ginkgo, green plums, light citrus, walnuts, Aloes, ridges, lychees, carrots, beetroots, juices and other canned fruits and vegetables, so it is a kind of food additive. The reason why disodium citrate disodium can exert anti-oxidation, anti-corrosion and color protection functions is to maintain the color and phoenix flavor of food based on its ability to gradually consume residual oxygen in cans, and Sn 2 ÷ is converted into Sn 4 ÷ . Because of its low toxicity, it can safely and effectively replace the sulfur-containing color-protecting agent, and the color-protecting effect of stannous disodium citrate as a food additive has been widely used in the past. However, the data of foreign patents or public funds have not been introduced in the preparation method of disodium citrate disodium. Chinese food addition Agent Industry Network (www.feic.cn) coagulant and a stabilizing bar 43 simply introduces stannous citrate, disodium preparation method, the reaction is produced by the gasification, stannous citrate and sodium hydroxide was prepared. However, the preparation of disodium citrate disodium salt from stannous chloride has two major disadvantages: one is high sodium chloride content; the second is that it is easy to obtain a large amount of solid substance dissolved in water, and the obtained product is difficult to meet the standard requirements.
凌关庭主编的 《食品添加剂手册》 第二版提到的制法为先由柠檬酸、 氯化亚锡和氢氧化钠生成柠檬酸二亚锡沉淀， 再加氛氧化钠和柠檬酸反应 后， 得柠樣：酸亚锡二钠水溶液， 经真空浓縮、 滤去不溶物后真 S千燥而成。 此法虽然可以解决产物中氯离子高的问题， 但由于柠檬酸亚锡二钠很难结 晶， 柠檬酸:亚锡二钠溶液的浓缩一定要到完全千燥才能拿出块状園体， ϋ 粉碎后才能得到无定形粉末， 产物在千燥过程中粘壁很严重， 产品取出较 困难.， 而且大量水分的蒸发能耗极大。 《食品添加剂手册》提及的方法由于 经历浓缩过程， 由于氧化的原因， 水不溶物通常也难以达到中国企标的要 - 。 The second edition of the Food Additives Manual edited by Ling Guanting is made up of citric acid, stannous chloride and sodium hydroxide to form dibasic citrate precipitate, and then reacted with sodium oxide and citric acid. Lime sample: an aqueous solution of stannous acid disodium, which is concentrated in a vacuum and filtered to remove insoluble matter. Although this method can solve the problem of high chloride ion in the product, since the disodium citrate disodium is difficult to crystallize, the concentration of the citric acid: stannous disodium solution must be completely dry to take out the block-shaped garden, ϋ After pulverization, an amorphous powder can be obtained. The product sticks to the wall during the drying process, the product is difficult to remove, and the evaporation of a large amount of water is extremely energy-intensive. The method mentioned in the “Food Additives Handbook” is difficult to meet the requirements of Chinese enterprises due to the process of concentration and water insolubles due to oxidation.
为了克服上述缺陷， 申请人在专利号为 ZL200610 2438S、1的发明专利 中提供了一种在醇介质中制备柠様酸亚锡二钠钓制备方法， 先用無氧化钠 将氯化亚锡转化为氣氧化亚锡， 与柠檬酸反应生成柠檬酸二亚锡， 在乙醇 介质中， 拧檬酸二 3E锡与柠檩酸 应遂步转化成柠檬酸亚锡， 再与氢氧化 钠乙醇溶液反应， 狞檬酸亚锡转化成柠檬酸亚锡二钠。 用氢氧化钠将氣化 亚锡转化为氢氧化.亚锡 ^下问题： 一是反应歩骤多， 清洗氣氧化亚锡的 废水量较大； 二是碱性介质使氯化亚锡或者氢氧化亚锡极其容易被氧化为 囲价锡， 抗氧化处理使生产操作存在一定的难度。 In order to overcome the above drawbacks, the applicant provides a preparation method for preparing stannous citrate disodium salt in an alcohol medium by using the invention patent No. ZL200610 2438S, 1 to convert the stannous chloride with sodium oxide. It is a gas oxidized stannous oxide, which reacts with citric acid to form di-stannous citrate. In the ethanol medium, bis- 3E tin and citric acid should be converted into stannous citrate and then reacted with sodium hydroxide ethanol solution. , stannous citrate is converted to disodium citrate disodium. The use of sodium hydroxide to convert vaporized stannous to hydrogen hydroxide. Stannous ^ problems: First, the reaction is much more, the amount of waste water for the cleaning gas stannous oxide is larger; the second is the alkaline medium to make stannous chloride or hydrogen Stannous oxide is extremely easy to be oxidized to bismuth tin, and the anti-oxidation treatment makes the production operation difficult.
发明内容 Summary of the invention
本发明的目的在于克服上述缺陷, 提供一种 ®化生产歩骤的柠檬漦亚 锡二钠的制备方法。
本发明以拧檬酸三钠和氣化亚锡为原料， 包括 ½下歩骤： 、 将柠檬酸 Ξί钠和氯化亚锡分别溶于水； SUMMARY OF THE INVENTION The object of the present invention is to overcome the above-mentioned deficiencies and to provide a process for preparing a lemon sulfonium disodium salt which is produced by a chemical process. The invention uses trisodium citrate and stannous gasification as raw materials, including 1⁄2 lower steps: dissolving sodium citrate and stannous chloride respectively in water;
β, 按柠檬酸三钠与氯化亚锡摩尔比 1： 1,95~2.15的比例将柠檬酸三 钠水溶液加入到氯化亚锡水溶液中， 搅拌反应 小时， 过滤 f 热的 纯水洗涤， 得柠檬黢二亚锡固体产物； beta], stannous chloride with sodium citrate according to the molar ratio of 1: 1.95 ~ 2.15 trisodium citrate solution was added to an aqueous solution of stannous chloride, the reaction was stirred for hours, filtered and washed with hot water f, Obtaining a solid product of lemon and dithizone;
将上述的柠檬酸二亚锡加入到重量浓度为 2:0〜40%的柠檬酸三钠水 溶液中， 搅拌反应至完全磨解， 柠檬酸二亚锡与柠檬酸三钠按摩尔比为 1 ： 0.9S- i.15r The above-mentioned di-stannous citrate is added to a trisodium citrate aqueous solution having a weight concentration of 2:0 to 40%, and the reaction is stirred until completely agitated. The molar ratio of di-tin citrate to trisodium citrate is 1: 0.9S- i.15r
D、 在上述反应体系中按柠檬酸二亚锡与碳酸氣鈉摩尔比 1 ： 0,95-115的比顿加入重量浓度为 4〜10%的碳酸観钠水溶液 f 得.； 1色透^ 柠檬酸亚锡二钠的溶液， 经浓缩， 干燥， 粉碎， 得到柠檬酸亚锡二钠固# 粉末 D, in the above reaction system, according to the molar ratio of distann citrate to sodium carbonate sodium 1: 0, 95-115 by the addition of 4~10% by weight of sodium bismuth carbonate aqueous solution f ; a solution of disodium citrate disodium, concentrated, dried, and pulverized to obtain a stannous citrate disodium solid # powder
歩骤 A中， 为防止亚锡的氧化和加速溶解过程:， 在氣化亚锡最好溶解 在 热水中，并加入少量的金属锡粉。加入柠檬酸三钠溶液进行反 应时， 体系温度优选是 10〜55υ， 更优选接近室温的 20-35 C ¾ In step A, in order to prevent the oxidation of stannous and accelerate the dissolution process: it is preferable to dissolve the stannous in the hot water and add a small amount of metal tin powder. When trisodium citrate solution was added to the reaction, the system temperature is preferably 10~55υ, more preferably close to room temperature 20-35 C ¾
步骤 B中.， 加入柠檬酸三钠溶液便柠檬酸三钠水溶液与氣化亚锡水溶 液迸行反应时， 体系 H 值优通 1-5, 更优选是 2〜4， 体系温度优选是 10-55X， 更优选搂近室温的 20-35^0。 In step B, when the trisodium citrate solution is added, the trisodium citrate aqueous solution is reacted with the vaporized stannous aqueous solution, and the system H value is preferably 1-5, more preferably 2 to 4, and the system temperature is preferably 10- 55X, more preferably 20-35^0 near room temperature.
在步骤 B 中， 所述柠檬酸三钠水溶液与氣化亚锡水溶液搅拌反应 Ο.δ Ο小时后， 可:以按柠檬酸三钠与碳酸氢钠摩尔比 1： 0,95 、1δ 例援拌加入碳酸無钠的水溶液， 在 搅拌反应 0.^1 ,0小时， 再进 行所述的过滤和纯水洗涤。 以便迸一歩陈化柠檬酸二亚锡沉淀， 方便过滤 和洗條清除残留的氣化钠， 再迸行所述过滤和洗涤。 In the step B, the trisodium citrate aqueous solution and the vaporized stannous aqueous solution are stirred and reacted for Ο. δ Ο hours, and the molar ratio of trisodium citrate to sodium hydrogencarbonate is 1:0, 95, 1δ. The sodium carbonate-free aqueous solution was added to the mixture, and the reaction was stirred for 0.1 hour, and the filtration and pure water washing were carried out. In order to precipitate the precipitated bis-stann citrate, it is convenient to filter and wash the strip to remove residual sodium vapor, and then carry out the filtration and washing.
歩骤 Β， 柠檬酸三钠水溶液加入到餐化亚锡溶液中发生了 ¾TF化学反
COONa r— COOSnOH 歩 Β Β Β Β Β Β Β Β Β Β Β 柠檬酸 柠檬酸 柠檬酸 柠檬酸 柠檬酸 柠檬酸 柠檬酸 柠檬酸 柠檬酸 柠檬酸 柠檬酸 COONa r — COOSnOH
-COONa + aSnCij HO— H—— COOSnOH + 3 aCl + HC1 -COONa + aSnCij HO— H—— COOSnOH + 3 aCl + HC1
-COONa L—cOOH -COONa L-cOOH
加入碳酸氬钠水溶液后发生的化学反应为 - The chemical reaction that occurs after the addition of aqueous sodium argon carbonate solution is -
HC1 * NaHG03 ^ KaCI + C02 + ¾0 歩骤 C和步骤 D发生的化学反应为： HC1 * NaHG0 3 ^ KaCI + C0 2 + 3⁄40 The chemical reactions that occur in step C and step D are:
COONa —— COOSROH J—— COONa COONa COONa - COOSROH J - COONa COONa
— CQQNa + HO eOOSnOH —— COONa — COO L ~ eOQH COONa ——■ GOONa aHC¾ * HO- — COOSnQH —COONa 本发明省去了制备氢氧化亚锡的过程， 柠檬酸二亚锡沉淀之前反应体 系的 pH值控制在 5<0以下， 避兔二翁锡处于碱性的溶液环境， 从而避开了 制备过程的抗氧化处理的问题， 进一歩简化了生产步骤、 降低了能耗和操 作难度， 并降低水不溶物含量， 提高了柠檬酸亚锡:二 Λ产品的品质。 — CQQNa + HO eOOSnOH —— COONa — COO L ~ eOQH COONa ——■ GOONa aHC3⁄4 * HO- — COOSnQH —COONa The present invention eliminates the process of preparing stannous hydroxide, the pH of the reaction system before the precipitation of dibasic citrate The value is controlled below 5<0, and the rabbit is in an alkaline solution environment, thus avoiding the problem of anti-oxidation treatment in the preparation process, which further simplifies the production steps, reduces energy consumption and operation difficulty, and reduces The water insoluble content increases the quality of the stannous citrate: diterpene product.
具体实施方式 detailed description
实施倒 Implement
将 294克柠檬酸三钠搅拌下溶于 600mL纯水， 过滤后备用《称取 4S1 克氣化亚锡溶于 10QC5mL 80Ό的热水， 加入 0.5克金属锡粉 保温搅拌反 应半小时， 热过滤。 于室温插摔下将上述澄清的柠檬黢三钠溶液加入氯化 亚锡滤液中， 用盐簾和 /或氯氧化钠水溶液调节反应体系的 ρΗ值为 2〜4， 制得柠檬酸二亚锡悬浮物。 加入 δ4克碳酸氢钠溶于 1700mL纯水的溶液, 继续搅拌反应 0,5小时 冷却至室温后过滤、纯水满漆除去氣化钠后，尽量 将水脱千， 制得柠檬観二亚锡中间体。再与: 294宪柠檬酸三钠溶于 600mL
纯水的潜液反应， 至画体全部溶解后， 得无色澄清透明溶液。 加入 84克碳 酸氣钠溶于 1700mL纯水的溶液， 加完后， 旋转蒸发至柠檬酸亚锡二钠完 全干燥， 得块状固体， 固体经粉碎得白色粉末产物, 经分析检验结果如下: Dissolve 294 g of trisodium citrate in 600 mL of pure water with stirring, and filter for use. Weigh 4S1 g of stannous gas dissolved in 10QC5mL of 80 Ό hot water, add 0.5 g of metal tin powder, stir and react for half an hour, and heat filter. The above clarified lemon trisodium sulphate solution is added to the stannous chloride filtrate at room temperature, and the reaction system has a pH value of 2 to 4 by using a salt curtain and/or an aqueous sodium chlorate solution to prepare di-n-butyl citrate. Suspended matter. Add δ4g of sodium bicarbonate dissolved in 1700mL of pure water, continue to stir the reaction for 0, 5 hours to cool to room temperature, filter, pure water full paint to remove sodium vaporized, try to remove water, try to make lemon bismuth Intermediate. And with: 294 constitution of trisodium citrate dissolved in 600mL The latent liquid reaction of pure water, after the entire body of the painting is dissolved, gives a clear and transparent solution without color. A solution of 84 g of sodium carbonate in 1700 mL of pure water was added. After the addition, the mixture was rotary evaporated to disodium citrate and completely dried to obtain a solid. The solid was pulverized to obtain a white powder product. The analysis results were as follows:
外观： 白色粉末状固体； Appearance: white powdery solid;
锡含量 （重量％): >31.6; Tin content (% by weight): >31.6 ;
水不溶物（重量％) 0.001 ; Water insoluble matter (% by weight) 0.001 ;
砷 （以 As计， 重量％): ^0.00005； Arsenic (in terms of As, % by weight): ^0.00005;
重金属 （以 Pb计， 重量％): ^0.0002. Heavy metals (in terms of Pb, % by weight) : ^0.0002.
氯 (以 C―计， 重量％ )： ^0,005.
Chlorine (calculated as C-, % by weight): ^0,005.
Claims
1. 柠檬酸亚锡二钠的制备方法， 其特征在于， 包括以下歩骤： A method for preparing disodium citrate disodium, which comprises the following steps:
A. 以柠檬酸三钠和氯化亚锡为原料，将柠檬酸三钠和氣化亚锡分别溶 "Ϊ 水; A. using trisodium citrate and stannous chloride as raw materials, respectively dissolving trisodium citrate and vaporized stannous in water;
Β. 桉柠檬酸三钠与氣化亚锡摩尔比 1： 1 , 9^2.15的比例将柠檬酸三钠 水溶液加入到氣化亚锡水溶液中， 搅拌反应 0,5 ,0小时， 过滤， 纯水洗涤: 得柠檬酸二亚锡固体产物; Β. 摩尔 摩尔 citrate trisodium and vaporized stannous molar ratio of 1: 1 , 9 ^ 2.15 ratio of trisodium citrate aqueous solution added to the vaporized stannous aqueous solution, stirring reaction 0,5,0 hours, filtered, pure Water washing: obtaining a solid product of stannous citrate;
C.将上述的柠檬酸二亚锡加入到重量浓度为 20^ 0%的柠檬酸三钠水 液中， 搅摔反应至完全溶解, 柠檬酸二亚锡与柠檬酸三钠按摩尔比为 1 : 0.95-1.15； C. The above-mentioned di-stannous citrate is added to a trisodium citrate aqueous solution having a weight concentration of 20% to 0%, and the reaction is stirred until completely dissolved. The ratio of di-tin citrate to trisodium citrate is 1 : 0.95-1.15;
D. 在上述反应体系中按拧檬酸二 IE锡与碳酸氢钠摩尔比 1： 0.9^11^ 的比例加入重量浓度为 4〜10%的碳酸 ¾钠水溶液，得无色透明柠檬酸亚锡::： 钠的溶液， 经浓缩， 千燥， 粉碎， 得到柠檬酸亚锡二钠固体粉末。 D. In the above reaction system, a molar ratio of di-tin-tin and sodium hydrogencarbonate in a ratio of 1:0.9^11^ is added to a 4~10% aqueous sodium carbonate solution to obtain a colorless transparent stannous citrate. ::: A solution of sodium, concentrated, dried, and pulverized to obtain a solid powder of stannous citrate disodium.
2. 根据权利要求 1所述柠檬酸亚锡二钠的劇备方法， 其特征在于， 步骤 B中 柠檬酸三钠水溶液与氯化亚锡水溶液反应体系 pH值为 1~5 2. The method for preparing disodium citrate disodium according to claim 1, wherein the reaction system of the aqueous solution of trisodium citrate and the aqueous solution of stannous chloride in step B has a pH of 1 to 5
3. 根据权利要求 2所述柠檬酸亚锡二钠的制备方法， 其特征在于， 所述 柠檬酸三钠水溶液与氯化亚锡水溶液反应体系 pH值为 2~4。 The method for preparing disodium citrate according to claim 2, wherein the reaction system of the aqueous solution of trisodium citrate and the aqueous solution of stannous chloride is at a pH of 2 to 4.
4. 根据权利要求 1所述柠檬酸亚锡二钠的制备方法 其特征在于 在歩 骤 B中， 拧檬酸三钠水溶液与氣化亚锡水溶液搅拌反应 小时后， 按 柠檬酸三钠与碳酸氣钠摩尔比 1 ： 0，95〜1 ,15 的比例搅摔加入碳酸氣钠的水 溶液， 再迸行所述的过滤和纯水洗涤。 4. The method for preparing disodium citrate according to claim 1, wherein in the step B, the trisodium citrate aqueous solution and the vaporized stannous aqueous solution are stirred and reacted for a small period of time, followed by trisodium citrate and carbonic acid. The ratio of gas to sodium molar ratio of 1: 0, 95 to 1, 15 was added to the aqueous solution of sodium carbonate, and the filtration and pure water washing were carried out.
5. 根据权利要求 4所述柠檬酸亚锡二钠的制备方法， 其特征在于， 加入 碳酸氮钠的水溶液的反应温度为 60〜100Γ。 The method for producing disodium citrate according to claim 4, wherein the reaction temperature of the aqueous solution of sodium carbonate is 60 to 100 Torr.
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| US8603442B2 (en) | 2009-08-03 | 2013-12-10 | Mcneil-Ppc, Inc. | Tooth sensitivity treatment compositions |
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| CN101823954B (en) * | 2010-06-03 | 2012-11-21 | 西陇化工股份有限公司 | Method for preparing disodium stannous citrate |
| CN104447286A (en) * | 2014-11-07 | 2015-03-25 | 李玉成 | Soluble selenium/calcium citrate and preparation method thereof |
| CN111019531B (en) * | 2019-11-12 | 2021-12-10 | 黄希 | Inorganic sol type cultural relic reinforcing composite material imitating natural silica-alumina gel and use method thereof |
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| US3213120A (en) * | 1963-02-11 | 1965-10-19 | Pfizer & Co C | Tin salts of citric acid and method of preparation |
| CN100556885C (en) * | 2006-12-25 | 2009-11-04 | 西陇化工股份有限公司 | The preparation method of distannous citrate |
| CN101823954A (en) * | 2010-06-03 | 2010-09-08 | 西陇化工股份有限公司 | Method for preparing disodium stannous citrate |
| CN101844979A (en) * | 2010-06-03 | 2010-09-29 | 西陇化工股份有限公司 | Preparation method of disodium stannous citrate crystal |
| CN101862013A (en) * | 2010-06-03 | 2010-10-20 | 西陇化工股份有限公司 | Method for preparing disodium stannous citrate equivalent composition |
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| US3213120A (en) * | 1963-02-11 | 1965-10-19 | Pfizer & Co C | Tin salts of citric acid and method of preparation |
| CN100556885C (en) * | 2006-12-25 | 2009-11-04 | 西陇化工股份有限公司 | The preparation method of distannous citrate |
| CN101823954A (en) * | 2010-06-03 | 2010-09-08 | 西陇化工股份有限公司 | Method for preparing disodium stannous citrate |
| CN101844979A (en) * | 2010-06-03 | 2010-09-29 | 西陇化工股份有限公司 | Preparation method of disodium stannous citrate crystal |
| CN101862013A (en) * | 2010-06-03 | 2010-10-20 | 西陇化工股份有限公司 | Method for preparing disodium stannous citrate equivalent composition |
Cited By (1)
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| US8603442B2 (en) | 2009-08-03 | 2013-12-10 | Mcneil-Ppc, Inc. | Tooth sensitivity treatment compositions |
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