WO2009026773A1 - Procédé de fabrication d'acide formique par acidification de formiate de sodium par un agent acidifiant - Google Patents

Procédé de fabrication d'acide formique par acidification de formiate de sodium par un agent acidifiant Download PDF

Info

Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
formic acid
acidifying
sodium formate
formate
inhibitor
Prior art date
Application number
PCT/CN2007/071086
Other languages
English (en)
Chinese (zh)
Inventor
Yun Luo
Zhengxiang Cao
Min Deng
Original Assignee
Yibin Tianyuan Group Company Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yibin Tianyuan Group Company Limited filed Critical Yibin Tianyuan Group Company Limited
Publication of WO2009026773A1 publication Critical patent/WO2009026773A1/fr

Links

Classifications

    • 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

Definitions

  • 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%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention porte sur un procédé de fabrication d'acide formique par acidification de formiate de sodium par un agent acidifiant. Ce procédé comprend l'addition d'un inhibiteur qui est au moins l'un parmi des alcanes, cycloalcanes, éthers ou formiates avec un point d'ébullition inférieur à 80 °C. Le procédé non seulement a une température de réaction contrôlable et une réaction secondaire contrôlable, et permet d'obtenir de l'acide formique à une concentration élevée de 98 %, lequel rendement est de 98 %, mais encore possède un fonctionnement avantageux, est sans danger et économique, et entraîne une pollution de l'environnement réduite de façon contrôlable.
PCT/CN2007/071086 2007-08-24 2007-11-17 Procédé de fabrication d'acide formique par acidification de formiate de sodium par un agent acidifiant WO2009026773A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CNB2007100498375A CN100560557C (zh) 2007-08-24 2007-08-24 用酸化助剂酸化甲酸钠制备甲酸的方法
CN200710049837.5 2007-08-24

Publications (1)

Publication Number Publication Date
WO2009026773A1 true WO2009026773A1 (fr) 2009-03-05

Family

ID=39191410

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2007/071086 WO2009026773A1 (fr) 2007-08-24 2007-11-17 Procédé de fabrication d'acide formique par acidification de formiate de sodium par un agent acidifiant

Country Status (2)

Country Link
CN (1) CN100560557C (fr)
WO (1) WO2009026773A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106800505A (zh) * 2015-11-25 2017-06-06 衡阳屹顺化工有限公司 一种制备高浓度甲酸的方法
KR101985444B1 (ko) * 2016-09-30 2019-06-03 한국화학연구원 개미산염 수용액으로부터 고농도 개미산 및 고순도 황산염의 회수방법, 및 회수 장치

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3114312A1 (de) * 1981-04-09 1982-10-21 Davy McKee AG, 6000 Frankfurt Verfahren zur herstellung von ameisensaeure
CN1153767A (zh) * 1995-12-09 1997-07-09 陈广生 一种生产甲酸和硫酸钠的方法
CN1821205A (zh) * 2006-03-21 2006-08-23 尚微 甲酸的生产工艺
CN1915954A (zh) * 2006-09-07 2007-02-21 湖北兴发化工集团股份有限公司 用磷酸和甲酸钠生产甲酸的方法
CN1915823A (zh) * 2006-08-23 2007-02-21 湖北宜化集团有限责任公司 高纯度硫酸钠的制备方法
CN1994999A (zh) * 2006-09-11 2007-07-11 左建国 一种95%高浓度甲酸的生产方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3114312A1 (de) * 1981-04-09 1982-10-21 Davy McKee AG, 6000 Frankfurt Verfahren zur herstellung von ameisensaeure
CN1153767A (zh) * 1995-12-09 1997-07-09 陈广生 一种生产甲酸和硫酸钠的方法
CN1821205A (zh) * 2006-03-21 2006-08-23 尚微 甲酸的生产工艺
CN1915823A (zh) * 2006-08-23 2007-02-21 湖北宜化集团有限责任公司 高纯度硫酸钠的制备方法
CN1915954A (zh) * 2006-09-07 2007-02-21 湖北兴发化工集团股份有限公司 用磷酸和甲酸钠生产甲酸的方法
CN1994999A (zh) * 2006-09-11 2007-07-11 左建国 一种95%高浓度甲酸的生产方法

Also Published As

Publication number Publication date
CN101139279A (zh) 2008-03-12
CN100560557C (zh) 2009-11-18

Similar Documents

Publication Publication Date Title
KR101583331B1 (ko) 시클로헥산 산화로 제조하는 시클로헥산올과 시클로헥사논의 공정 및 그 설비
US20150044741A1 (en) Carboxylate acidification
RU2014143514A (ru) Способ окислительного дегидрирования с низкими выбросами для получения буиадиена
CN102030755B (zh) 一种制备高纯度三乙烯二胺的方法
TWI362377B (en) Acetic anhydride and acetate ester co-production
CN101440015A (zh) 一种用稀盐酸生产一氯甲烷的方法
CN100348603C (zh) 羟基亚乙基二膦酸的合成方法
WO2009026773A1 (fr) Procédé de fabrication d'acide formique par acidification de formiate de sodium par un agent acidifiant
US4215056A (en) Formation, purification and recovery of phthalic anhydride
JPS6316369B2 (fr)
JP2541628B2 (ja) 過酢酸の製法
US3694171A (en) Method for purifying cyclic phosphonitrilic chlorides
CN106588584A (zh) 一种醚类溶剂的除水方法
CN103112968B (zh) 苯氧羧酸类生产废水中高cod成分的处理方法
CN115504874A (zh) 一种苯甲醇的制备方法
US7321060B2 (en) Method for production of acrylic acid
WO2009026774A1 (fr) Procédé de fabrication d'acide formique par de l'acide phosphorique extrait et du formiate de sodium
JP2005060241A (ja) 溶剤の精製方法およびそれに用いる装置
CN106800505A (zh) 一种制备高浓度甲酸的方法
KR100365023B1 (ko) 메틸아세테이트로부터 초산을 회수하는 공정
CN101485999A (zh) 一种路易斯酸催化剂及其制备方法和其在醋酸异丙烯酯转位法生产乙酰丙酮工艺中的应用
CN101665423B (zh) 一种用磷酸酸化甲酸钾制备甲酸的方法
JP6100442B1 (ja) 無水酢酸の製造方法
KR20160076996A (ko) 흡착 공정에서의 변성방지를 통한 고순도 무수당 알코올의 제조방법
CN116514695A (zh) 一种膦盐组合物及维生素a醋酸酯的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07817276

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07817276

Country of ref document: EP

Kind code of ref document: A1