WO2009026773A1 - Process for producing formic acid by acidifying sodium formate with acidifying agent - Google Patents

Process for producing formic acid by acidifying sodium formate with acidifying agent Download PDF

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WO2009026773A1
WO2009026773A1 PCT/CN2007/071086 CN2007071086W WO2009026773A1 WO 2009026773 A1 WO2009026773 A1 WO 2009026773A1 CN 2007071086 W CN2007071086 W CN 2007071086W WO 2009026773 A1 WO2009026773 A1 WO 2009026773A1
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formic acid
acidifying
sodium formate
formate
inhibitor
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PCT/CN2007/071086
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French (fr)
Chinese (zh)
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Yun Luo
Zhengxiang Cao
Min Deng
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Yibin Tianyuan Group Company Limited
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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
    • C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids

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  • the present invention relates to a process for producing formic acid, and more particularly to a process for preparing formic acid by acidifying sodium formate with an acidifying assistant.
  • formic acid is prepared from sodium formate, and acidification can be carried out by acidification with an acidification aid such as sulfuric acid, phosphoric acid, perphosphoric acid or polyphosphoric acid or phosphorus pentoxide.
  • an acidification aid such as sulfuric acid, phosphoric acid, perphosphoric acid or polyphosphoric acid or phosphorus pentoxide.
  • 10200857.3 discloses various acidification auxiliaries for the acidification of sodium formate to prepare formic acid. These methods have been tested and proven to be effective. However, since acidification is an exothermic reaction, formic acid is easily decomposed under local overheating to produce carbon monoxide and water; if the decomposition temperature is greater than 100 ° C, formic acid is oxidized to form carbon dioxide and water, and the resulting water causes the concentration of formic acid to be low. , can not get more than 95% of high concentration of formic acid; further produce sodium carbonate, not only will greatly reduce the concentration of formic acid, but also bring more problems of by-products, degradation of formic acid quality and serious three wastes.
  • Chinese Patent No. 200610200857.3 discloses a method for preparing 95% high concentration formic acid by acidifying sodium formate to produce 95% high concentration of formic acid by using a reducing multicomponent polymeric phosphoric acid mixture as an acidifying agent, the principle is The high adsorption property of the mixed phosphoric acid mixture absorbs the moisture in the reaction system, thereby increasing the concentration of formic acid.
  • the disadvantage of the process is that the amount of the polymerization phosphoric acid mixture is increased, and a certain amount of formic acid may be adsorbed, although it is capable of adsorbing 95% high concentration of formic acid is obtained, but in the actual production process, this concentration is far from being reached.
  • the subsequent treatment process is more complicated than the conventional technology.
  • the object of the present invention is to provide a method for preparing a high concentration of formic acid by overcoming the above deficiencies of the prior art.
  • the method can control the reaction temperature, limit the occurrence of side reactions, and is easy to operate.
  • reaction temperature needs to be controlled below 80 ° C during the acidification of sodium formate, if the reaction can be The large amount of heat can be uniformly taken away, and the present invention is based on the following considerations: adding one or more inhibitors to control the temperature of the reaction:
  • the inhibitor does not react with any substance in the reaction system
  • the inhibitor has a boiling point below 80 ° C;
  • the inhibitor is non-toxic and has no effect on product quality.
  • the technical scheme of the present invention is to add an inhibitor during the reaction of acidifying a sodium formate to prepare formic acid, which is an anthracene hydrocarbon, a hydrocarbon, a hydrocarbon having a boiling point of less than 80 ° C. Or at least one of formic acid esters.
  • the inhibitor is preferably added in an amount of not less than 5% by weight of sodium formate. It has been found through repeated experiments that the amount of addition is less than 5%, the formic acid is easily decomposed, and the reaction is not easily controlled; At 10%, not only the inhibitor evaporating time is prolonged, but also the loss of the inhibitor is easily caused. Therefore, the best solution is that the inhibitor is added in an amount of 5-10% by weight of sodium formate.
  • the terpene hydrocarbons include pentamidine, hydrazine or solvent oil having a boiling point of less than 80 ° C;
  • the cyclic hydrocarbon includes cyclohexene, cyclopentamidine or cyclopropene
  • the ether includes isopropyl ether, diethyl ether or propyl ether;
  • the formic acid ester includes isopropyl formate, propyl formate or isobutyl formate.
  • the present invention selects an inhibitor in the acidification reaction system which does not react with any substance in the reaction system and is non-toxic and has a boiling point of less than 80 ° C, once the reaction system is overheated, these low boiling point inhibitors are The heat is volatilized, taking away a large amount of heat released by the acidification reaction, thereby effectively controlling the temperature of the reaction system, avoiding the decomposition of formic acid caused by excessive local temperature, avoiding the occurrence of side reactions such as hydrolysis and oxidation, and making the yield of formic acid More than 98%, a high concentration of formic acid with a formic acid content of more than 98%; in addition, because of the choice of this inhibitor, the acidification reaction can be carried out under normal temperature and pressure, without adding any auxiliary equipment, the operation is very convenient; Toxic inhibitors have a significant effect on ensuring the quality of the product, optimizing the operating environment, and controlling pollution. In addition, the volatilized inhibitor can be condensed and returned to the reactor for use, which save
  • Example 1 In the reactor, anhydrous sodium formate was added, and a 6% boiling point of 40-60 ° C of pentamidine was added, and 98% of sulfuric acid was metered in. The heat of reaction was determined by the gasification zone of pentamidine. The reactor was cooled down by cooling water at 10-20 ° C, condensed and returned to the reactor. When the measured 98% sulfuric acid drop acceleration is controlled for 1-2 hours, the reaction is continued for 20-30 minutes after the addition, until there is no reflux, the solvent is distilled off at 80 ° C, and the later vacuum is distilled to the formic acid to be distilled off.
  • the pentamidine and a small amount of formic acid are used in the next batch of sodium formate acidification reaction, and the solvent recovery rate is greater than 96%.
  • the solvent-removed reaction material is distilled off formic acid at an absolute pressure of 0.03-0.04 MPa, and the formic acid content is greater than 94%, and the yield is greater than 98%.
  • Example 2 In the reactor, add anhydrous sodium formate, add sodium methoxide to feed 6% of cyclopentanyl, metered in 100% phosphoric acid (a mixture of 85% phosphoric acid and 105% of superphosphate can be prepared) at 60 ⁇ The reaction is carried out at 5 ° C, and the heat of reaction is carried out from the reactor by vaporization of cyclopentanyl, cooled by 10-20 ° C cooling water, condensed and returned to the reactor, and the acceleration of 100% phosphoric acid is controlled for 1-2 hours.
  • 100% phosphoric acid a mixture of 85% phosphoric acid and 105% of superphosphate can be prepared
  • Example 3 In the reactor, anhydrous sodium formate was added, sodium methoxide was added in an amount of 8% isopropyl ether, 100% phosphoric acid was metered in, and the reaction was carried out at 80 ° C or lower, and the reaction heat was vaporized by isopropyl ether. The device is cooled by 20 ° C cooling water, condensed and returned to the reactor. The 100% phosphoric acid drop acceleration is controlled for 1-2 hours. After the addition, the reaction is continued for 20-30 minutes, and the erect is not reflowed at 80.
  • the isopropyl ether is distilled off below C, and a small amount of isopropyl ether is distilled off under the absolute pressure of 50 MPa until the formic acid is distilled off, and the isopropyl ether is recovered for the next reaction.
  • the solvent recovery rate is greater than 96%, and the reaction material after the solvent is removed.
  • the formic acid is distilled off under the absolute pressure of 0.03-0.04 MPa, the formic acid content is greater than 96%, and the yield is greater than 98%.
  • Example 4 According to the process of Example 1, adding 8% sodium formate feed amount of isopropyl formate, adding 102% of superphosphate, and controlling the reaction temperature to be less than 80 ° C under the pressure of 40-50 MPa absolute pressure, The hexachloroformate was distilled off at 80 ° C in the same manner as in the previous example, until the formic acid was distilled off, the solvent recovery was more than 95%, and the formic acid was 0.03-0.04 after the solvent was removed. The formic acid is distilled off under MPa absolute pressure, the formic acid yield is greater than 98%, and the formic acid content is greater than 98%.
  • Example 5 In the reactor, adding anhydrous sodium formate, adding a stoichiometric isopropyl ether and a concentration of wet-process phosphoric acid extract, wherein the phosphoric acid content is 42 %, and the heat of reaction is distilled away from the isopropyl ether, with After cooling at 20 ° C cooling water, the reaction temperature is controlled to be less than 80 ° C, and 1-2 hours of hydrazine is added dropwise.
  • the isopropyl ether and formic acid are recovered by the above examples.
  • the formic acid content is greater than 98%, and the formic acid yield is greater than 98%.
  • sodium dihydrogen phosphate can reach food grade standards.
  • Example 6 In the reactor, add anhydrous sodium formate, add 8% sodium formate, the amount of isopropyl ether mixed with cyclopentanium mixed solvent, volume ratio of 1:1, add 100% phosphoric acid, 100% phosphoric acid was added dropwise at 80 ° C, the dropping rate was 1-2 hours, and the mixed solvent was distilled off at 80 ° C in the same manner as in the previous examples. The solvent recovery rate was greater than 96%, and the solvent was removed after 0.03-0.04. Formic acid is distilled off under MPa, and the yield of formic acid is greater than 98%.

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Abstract

A process for producing formic acid by acidifying sodium formate with acidifying agent, which comprises, adding an inhibitor which is at least one of alkanes, cycloalkanes, ethers or formates with a boiling point less than 80ºC.The process not only has controllable reaction temperature and side reaction, and may obtain 98% high concentration formic acid which yield is 98%, but also has expedient operation, safety, economical and controllable reduced environmental pollution.

Description

说明书 用酸化助剂酸化甲酸钠制备甲酸的方法 技术领域  Method for preparing formic acid by acidification of sodium formate with acidification aid
[1] 本发明涉及一种甲酸的制备方法， 具体地说是釆用酸化助剂酸化甲酸钠制备甲 酸的方法。  [1] The present invention relates to a process for producing formic acid, and more particularly to a process for preparing formic acid by acidifying sodium formate with an acidifying assistant.
背景技术  Background technique
[2] 已知的是， 由甲酸钠制备甲酸， 可加入硫酸、 磷酸、 过磷酸或聚合磷酸、 五氧 化二磷等酸化助剂酸化制备甲酸， 中国专利 97103209.2、 200610124470.4、 2006 [2] It is known that formic acid is prepared from sodium formate, and acidification can be carried out by acidification with an acidification aid such as sulfuric acid, phosphoric acid, perphosphoric acid or polyphosphoric acid or phosphorus pentoxide. Chinese patents 97103209.2, 200610124470.4, 2006
10200857.3公开了各种酸化助剂酸化甲酸钠制备甲酸的方法， 这些方法已经被生 产实践检验过是切实有效的。 但是， 由于酸化是放热反应， 而甲酸在局部过热 下又容易分解， 产生一氧化碳和水； 如果分解温度大于 100°C， 甲酸会被氧化生 成二氧化碳和水， 生成的水导致甲酸的浓度不高， 不能得到 95%以上的高浓度甲 酸； 进一步还会产生碳酸钠， 不仅会大大降低甲酸的浓度， 更会带来副产物多 、 甲酸品质下降和三废严重的问题。 10200857.3 discloses various acidification auxiliaries for the acidification of sodium formate to prepare formic acid. These methods have been tested and proven to be effective. However, since acidification is an exothermic reaction, formic acid is easily decomposed under local overheating to produce carbon monoxide and water; if the decomposition temperature is greater than 100 ° C, formic acid is oxidized to form carbon dioxide and water, and the resulting water causes the concentration of formic acid to be low. , can not get more than 95% of high concentration of formic acid; further produce sodium carbonate, not only will greatly reduce the concentration of formic acid, but also bring more problems of by-products, degradation of formic acid quality and serious three wastes.
[3] 中国专利 200610200857.3公开了一种制备 95%高浓度甲酸的方法， 它是通过釆 用含有还原性多组分聚合磷酸混合物为酸化剂来酸化甲酸钠生产 95%高浓度的甲 酸， 其原理是利用聚合磷酸混合物的高吸附性能吸收反应体系内的水分， 从而 提高甲酸的浓度， 但是， 该工艺的缺点是聚合磷酸混合物的使用量要增大， 也 可能吸附一定量的甲酸， 虽然其称能得到 95%高浓度的甲酸， 但是在现实的生产 过程中， 是远远达不到这种浓度的， 此外， 其后续处理工艺相对于传统技术来 讲， 更加复杂。 [3] Chinese Patent No. 200610200857.3 discloses a method for preparing 95% high concentration formic acid by acidifying sodium formate to produce 95% high concentration of formic acid by using a reducing multicomponent polymeric phosphoric acid mixture as an acidifying agent, the principle is The high adsorption property of the mixed phosphoric acid mixture absorbs the moisture in the reaction system, thereby increasing the concentration of formic acid. However, the disadvantage of the process is that the amount of the polymerization phosphoric acid mixture is increased, and a certain amount of formic acid may be adsorbed, although it is capable of adsorbing 95% high concentration of formic acid is obtained, but in the actual production process, this concentration is far from being reached. Moreover, the subsequent treatment process is more complicated than the conventional technology.
对发明的公开  Disclosure of invention
技术问题  technical problem
[4] 本发明的目的在于克服上述现有技术的不足而提供一种制备高浓度甲酸的方法 [4] The object of the present invention is to provide a method for preparing a high concentration of formic acid by overcoming the above deficiencies of the prior art.
， 该方法能够控制反应温度， 限制副反应的发生， 且操作简便。 The method can control the reaction temperature, limit the occurrence of side reactions, and is easy to operate.
技术解决方案  Technical solution
[5] 考虑到甲酸钠酸化过程中需要控制反应温度在 80°C以下， 如果能使反应过程中 的大量热量能够均匀地带走， 即可实现， 为此， 本发明基于以下几个方面考虑 ， 添加一种或多种抑制剂控制反应的温度： [5] Considering that the reaction temperature needs to be controlled below 80 ° C during the acidification of sodium formate, if the reaction can be The large amount of heat can be uniformly taken away, and the present invention is based on the following considerations: adding one or more inhibitors to control the temperature of the reaction:
[6] 一是该抑制剂不和反应体系中的任何物质发生反应；  [6] First, the inhibitor does not react with any substance in the reaction system;
[7] 二是该抑制剂的沸点低于 80°C;  [7] Second, the inhibitor has a boiling point below 80 ° C;
[8] 三是该抑制剂无毒， 对产品品质没有任何影响。  [8] Third, the inhibitor is non-toxic and has no effect on product quality.
[9] 为此， 本发明的技术方案是在用酸化助剂酸化甲酸钠制备甲酸的反应过程中加 入抑制剂， 所述的抑制剂是沸点低于 80°C的垸烃、 环垸烃、 醚或甲酸酯中的至少 一种。  [9] For this reason, the technical scheme of the present invention is to add an inhibitor during the reaction of acidifying a sodium formate to prepare formic acid, which is an anthracene hydrocarbon, a hydrocarbon, a hydrocarbon having a boiling point of less than 80 ° C. Or at least one of formic acid esters.
[10] 其中， 所述的抑制剂的加入量最好不低于甲酸钠重量的 5%， 通过多次实验发 现， 加入量少于 5%吋， 甲酸容易发生分解， 反应不容易控制； 而高于 10% , 不 仅加长了抑制剂蒸发吋间， 也容易造成抑制剂的损失， 因此， 最好的方案是抑 制剂的加入量是甲酸钠重量的 5-10%。  [10] wherein, the inhibitor is preferably added in an amount of not less than 5% by weight of sodium formate. It has been found through repeated experiments that the amount of addition is less than 5%, the formic acid is easily decomposed, and the reaction is not easily controlled; At 10%, not only the inhibitor evaporating time is prolonged, but also the loss of the inhibitor is easily caused. Therefore, the best solution is that the inhibitor is added in an amount of 5-10% by weight of sodium formate.
[11] 所述的垸烃包括戊垸、 已垸或沸点低于 80°C溶剂油；  [11] The terpene hydrocarbons include pentamidine, hydrazine or solvent oil having a boiling point of less than 80 ° C;
[12] 所述的环垸烃包括环已垸、 环戊垸或环丙垸；  [12] The cyclic hydrocarbon includes cyclohexene, cyclopentamidine or cyclopropene;
[13] 所述的醚包括异丙醚、 乙醚或丙醚；  [13] The ether includes isopropyl ether, diethyl ether or propyl ether;
[14] 所述的甲酸酯包括甲酸异丙酯、 甲酸丙酯或甲酸异丁酯。  [14] The formic acid ester includes isopropyl formate, propyl formate or isobutyl formate.
有益效果  Beneficial effect
[15] 本发明相比于现有技术有如下优点：  [15] The present invention has the following advantages over the prior art:
[16] 因为本发明在酸化反应体系中选择了不与反应体系中任何物质反应的、 无毒的 且沸点在低于 80°C的抑制剂， 一旦反应体系过热， 这些低沸点的抑制剂即吸热挥 发， 带走大量酸化反应放出的热量， 从而有效地控制了反应体系的温度， 避免 局部温度过高而造成甲酸分解， 避免了水解、 氧化等副反应的发生， 可以使甲 酸收得率大于 98%、 制得甲酸含量大于 98%的高浓度甲酸； 此外， 正是由于选择 了这种抑制剂， 使得酸化反应能够再常温常压下进行， 无须添加任何辅助设备 ， 操作十分方便； 无毒的抑制剂， 对于保证产品的质量， 优化操作环境， 控制 污染也有很明显地作用。 此外， 还可以将挥发后的抑制剂经冷凝后又返回反应 器中使用， 既节约了资源， 又降低了生产成本。  [16] Since the present invention selects an inhibitor in the acidification reaction system which does not react with any substance in the reaction system and is non-toxic and has a boiling point of less than 80 ° C, once the reaction system is overheated, these low boiling point inhibitors are The heat is volatilized, taking away a large amount of heat released by the acidification reaction, thereby effectively controlling the temperature of the reaction system, avoiding the decomposition of formic acid caused by excessive local temperature, avoiding the occurrence of side reactions such as hydrolysis and oxidation, and making the yield of formic acid More than 98%, a high concentration of formic acid with a formic acid content of more than 98%; in addition, because of the choice of this inhibitor, the acidification reaction can be carried out under normal temperature and pressure, without adding any auxiliary equipment, the operation is very convenient; Toxic inhibitors have a significant effect on ensuring the quality of the product, optimizing the operating environment, and controlling pollution. In addition, the volatilized inhibitor can be condensed and returned to the reactor for use, which saves resources and reduces production costs.
本发明的实施方式 [17] 下面结合实施例对本发明作进一步地详细说明， 但本发明的保护范围并不只限 于这些例子： Embodiments of the invention [17] The present invention will be further described in detail below with reference to the embodiments, but the scope of the present invention is not limited to these examples:
[18] 实施例 1 : 在反应器中， 加入无水甲酸钠， 加入甲酸钠投料量 6%的沸程 40-60°C 的戊垸， 计量加入 98%的硫酸， 反应热由戊垸气化带出反应器， 经 10-20°C冷却 水降温， 冷凝后又返回反应器。 当计量的 98%的硫酸滴加速度控制 1-2小吋， 加 完后继续反应 20-30分钟， 直到无回馏， 在 80°C下蒸出溶剂， 后期低真空蒸至甲 酸出馏， 回收的戊垸和少量甲酸， 用于下一批甲酸钠酸化反应， 溶剂回收率大 于 96%。 脱完溶剂的反应物料在 0.03-0.04MPa绝对压力下蒸出甲酸， 甲酸含量大 于 94% , 收得率大于 98%。  [18] Example 1: In the reactor, anhydrous sodium formate was added, and a 6% boiling point of 40-60 ° C of pentamidine was added, and 98% of sulfuric acid was metered in. The heat of reaction was determined by the gasification zone of pentamidine. The reactor was cooled down by cooling water at 10-20 ° C, condensed and returned to the reactor. When the measured 98% sulfuric acid drop acceleration is controlled for 1-2 hours, the reaction is continued for 20-30 minutes after the addition, until there is no reflux, the solvent is distilled off at 80 ° C, and the later vacuum is distilled to the formic acid to be distilled off. The pentamidine and a small amount of formic acid are used in the next batch of sodium formate acidification reaction, and the solvent recovery rate is greater than 96%. The solvent-removed reaction material is distilled off formic acid at an absolute pressure of 0.03-0.04 MPa, and the formic acid content is greater than 94%, and the yield is greater than 98%.
[19] 实施例 2: 在反应器中， 加入无水甲酸钠， 加入甲酸钠投料量 6%的环戊垸， 计 量加入 100%磷酸 （可用 85%磷酸与 105%的过磷酸混合配制） 在 60±5°C反应， 反 应热由环戊垸汽化带出反应器， 由 10-20°C冷却水降温， 冷凝后又返回反应器， 1 00%磷酸滴加速度控制 1-2小吋， 加完后继续反应 20-30分钟， 直立无回馏， 在 80 °C下蒸出溶剂， 后期低真空至甲酸出馏， 回收环戊垸和少量甲酸， 用于下一批甲 酸钠酸化反应， 溶剂回收率大于 96% , 脱完溶剂的反应物料在 0.03-0.04MPa绝压 下蒸出甲酸， 甲酸含量大于 96% , 收得率大于 98%。  [19] Example 2: In the reactor, add anhydrous sodium formate, add sodium methoxide to feed 6% of cyclopentanyl, metered in 100% phosphoric acid (a mixture of 85% phosphoric acid and 105% of superphosphate can be prepared) at 60± The reaction is carried out at 5 ° C, and the heat of reaction is carried out from the reactor by vaporization of cyclopentanyl, cooled by 10-20 ° C cooling water, condensed and returned to the reactor, and the acceleration of 100% phosphoric acid is controlled for 1-2 hours. Continue the reaction for 20-30 minutes, erect without reflux, distill the solvent at 80 °C, and then low vacuum to formic acid distillation, recover cyclopentanone and a small amount of formic acid, and use it for the next batch of sodium formate acidification reaction. The solvent recovery rate is greater than 96%, the solvent-removed reaction material was distilled off formic acid under the absolute pressure of 0.03-0.04 MPa, the formic acid content was greater than 96%, and the yield was greater than 98%.
[20] 实施例 3: 在反应器中， 加入无水甲酸钠， 加入甲酸钠投料量 8%异丙醚， 计量 加入 100%磷酸， 在 80°C以下反应， 反应热由异丙醚汽化带出反应器， 由 20°C冷 却水降温， 冷凝后又返回反应器， 100%磷酸滴加速度控制 1-2小吋， 加完后继续 反应 20-30分钟， 直立无回馏， 在 80。C以下蒸出异丙醚， 后期在 50MPa绝压下蒸 出少量异丙醚， 直至甲酸出馏， 回收异丙醚用于下次反应， 溶剂回收率大于 96% ， 脱完溶剂后的反应物料在 0.03-0.04MPa绝压下蒸出甲酸， 甲酸含量大于 96% , 收得率大于 98%。  [20] Example 3: In the reactor, anhydrous sodium formate was added, sodium methoxide was added in an amount of 8% isopropyl ether, 100% phosphoric acid was metered in, and the reaction was carried out at 80 ° C or lower, and the reaction heat was vaporized by isopropyl ether. The device is cooled by 20 ° C cooling water, condensed and returned to the reactor. The 100% phosphoric acid drop acceleration is controlled for 1-2 hours. After the addition, the reaction is continued for 20-30 minutes, and the erect is not reflowed at 80. The isopropyl ether is distilled off below C, and a small amount of isopropyl ether is distilled off under the absolute pressure of 50 MPa until the formic acid is distilled off, and the isopropyl ether is recovered for the next reaction. The solvent recovery rate is greater than 96%, and the reaction material after the solvent is removed. The formic acid is distilled off under the absolute pressure of 0.03-0.04 MPa, the formic acid content is greater than 96%, and the yield is greater than 98%.
[21] 实施例 4: 按实施例 1的工艺， 加入 8%的甲酸钠投料量甲酸异丙酯， 滴加 102% 的过磷酸， 在 40-50MPa绝压下反应控制反应温度小于 80°C， 过磷酸滴加速度 1-2 小吋， 釆用前述实例同样方法， 在 80°C下蒸出甲酸异丙酯， 直至甲酸出馏， 溶剂 回收率大于 95% , 脱完溶剂后甲酸在 0.03-0.04MPa绝压下蒸出甲酸， 甲酸收率大 于 98% , 甲酸含量大于 98%。 [22] 实施例 5: 在反应器中， 加入无水甲酸钠， 滴加化学计量异丙醚与浓度湿法磷 酸萃取液， 其中磷酸含量 42%， 反应热由异丙醚蒸出带走， 用 20°C冷却水冷却后 回收， 控制反应温度小于 80°C， 滴加吋间 1-2小吋， 釆用上述实例回收异丙醚和 甲酸， 甲酸含量大于 98% , 甲酸得率大于 98% , 磷酸二氢钠能达食品级标准。 [21] Example 4: According to the process of Example 1, adding 8% sodium formate feed amount of isopropyl formate, adding 102% of superphosphate, and controlling the reaction temperature to be less than 80 ° C under the pressure of 40-50 MPa absolute pressure, The hexachloroformate was distilled off at 80 ° C in the same manner as in the previous example, until the formic acid was distilled off, the solvent recovery was more than 95%, and the formic acid was 0.03-0.04 after the solvent was removed. The formic acid is distilled off under MPa absolute pressure, the formic acid yield is greater than 98%, and the formic acid content is greater than 98%. [22] Example 5: In the reactor, adding anhydrous sodium formate, adding a stoichiometric isopropyl ether and a concentration of wet-process phosphoric acid extract, wherein the phosphoric acid content is 42 %, and the heat of reaction is distilled away from the isopropyl ether, with After cooling at 20 ° C cooling water, the reaction temperature is controlled to be less than 80 ° C, and 1-2 hours of hydrazine is added dropwise. The isopropyl ether and formic acid are recovered by the above examples. The formic acid content is greater than 98%, and the formic acid yield is greater than 98%. , sodium dihydrogen phosphate can reach food grade standards.
[23] 实施例 6: 在反应器中， 加入无水甲酸钠， 加入 8%的甲酸钠投料量的异丙醚与 环戊垸的混合溶剂混合， 体积比 1:1， 滴加 100%磷酸， 在 80°C以下滴加 100%磷酸 ， 滴加速度 1-2小吋， 釆用前述实例同样方法， 在 80°C下蒸出混合溶剂， 溶剂回 收率大于 96% , 脱完溶剂后在 0.03-0.04MPa下蒸出甲酸， 甲酸收率大于 98% , 甲  [23] Example 6: In the reactor, add anhydrous sodium formate, add 8% sodium formate, the amount of isopropyl ether mixed with cyclopentanium mixed solvent, volume ratio of 1:1, add 100% phosphoric acid, 100% phosphoric acid was added dropwise at 80 ° C, the dropping rate was 1-2 hours, and the mixed solvent was distilled off at 80 ° C in the same manner as in the previous examples. The solvent recovery rate was greater than 96%, and the solvent was removed after 0.03-0.04. Formic acid is distilled off under MPa, and the yield of formic acid is greater than 98%.

Claims

权利要求书 Claim
[1] 1、 用酸化助剂酸化甲酸钠制备甲酸的方法， 其特征在于在反应过程中加入 抑制剂， 所述的抑制剂是沸点低于 80°C的垸烃、 环垸烃、 醚或甲酸酯中的 至少一种。  [1] 1. A method for preparing formic acid by acidifying a sodium formate with an acidifying assistant, characterized in that an inhibitor is added during the reaction, and the inhibitor is an anthracene hydrocarbon, a cyclic hydrocarbon, an ether or a methyl group having a boiling point lower than 80 °C. At least one of the acid esters.
[2] 2、 根据权利要求 1所述的方法， 其特征在于抑制剂的加入量大于或等于甲 酸钠重量的 5%。  [2] 2. A method according to claim 1, characterized in that the inhibitor is added in an amount greater than or equal to 5% by weight of sodium formate.
[3] 3、 根据权利要求 2所述的方法， 其特征在于抑制剂的加入量是甲酸钠重量 的 5- 10%。  [3] 3. The method according to claim 2, characterized in that the inhibitor is added in an amount of from 5 to 10% by weight based on the weight of sodium formate.
[4] 4、 根据权利要求 1或 2所述的方法， 其特征在于所述的垸烃包括戊垸、 已垸 或沸点低于 80°C溶剂油。  [4] 4. Process according to claim 1 or 2, characterized in that the terpene hydrocarbon comprises pentamidine, ruthenium or mineral spirits having a boiling point below 80 °C.
[5] 5、 根据权利要求 1或 2所述的方法， 其特征在于所述的环垸烃包括环已垸、 环戊垸或环丙垸。 [5] 5. The method according to claim 1 or 2, characterized in that the cyclic hydrocarbon includes cyclohexene, cyclopentamidine or cyclopropene.
[6] 6、 根据权利要求 1或 2所述的方法， 其特征在于所述的醚包括异丙醚、 乙醚 或丙醚。  [6] 6. Process according to claim 1 or 2, characterized in that the ether comprises isopropyl ether, diethyl ether or propyl ether.
[7] 7、 根据权利要求 1或 2所述的方法， 其特征在于所述的甲酸酯包括甲酸异丙 酯、 甲酸丙酯或甲酸异丁酯。  [7] 7. Process according to claim 1 or 2, characterized in that the formate comprises isopropyl formate, propyl formate or isobutyl formate.
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CN106800505A (en) * 2015-11-25 2017-06-06 衡阳屹顺化工有限公司 A kind of method for preparing concentration formic acid and high
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DE3114312A1 (en) * 1981-04-09 1982-10-21 Davy McKee AG, 6000 Frankfurt Process for the preparation of formic acid
CN1153767A (en) * 1995-12-09 1997-07-09 陈广生 Formic acid and sodium sulfate producing method
CN1821205A (en) * 2006-03-21 2006-08-23 尚微 Process for producing formic acid
CN1915823A (en) * 2006-08-23 2007-02-21 湖北宜化集团有限责任公司 Method for preparing sodium sulfate in high purity
CN1915954A (en) * 2006-09-07 2007-02-21 湖北兴发化工集团股份有限公司 Method for producing formic acid through phosphoric acid and sodium formate
CN1994999A (en) * 2006-09-11 2007-07-11 左建国 95% high concentration formic acid production method

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Publication number Priority date Publication date Assignee Title
DE3114312A1 (en) * 1981-04-09 1982-10-21 Davy McKee AG, 6000 Frankfurt Process for the preparation of formic acid
CN1153767A (en) * 1995-12-09 1997-07-09 陈广生 Formic acid and sodium sulfate producing method
CN1821205A (en) * 2006-03-21 2006-08-23 尚微 Process for producing formic acid
CN1915823A (en) * 2006-08-23 2007-02-21 湖北宜化集团有限责任公司 Method for preparing sodium sulfate in high purity
CN1915954A (en) * 2006-09-07 2007-02-21 湖北兴发化工集团股份有限公司 Method for producing formic acid through phosphoric acid and sodium formate
CN1994999A (en) * 2006-09-11 2007-07-11 左建国 95% high concentration formic acid production method

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