WO2011040700A2 - Method for producing alkyl lactate directly from ammonium lactate - Google Patents
Method for producing alkyl lactate directly from ammonium lactate Download PDFInfo
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- WO2011040700A2 WO2011040700A2 PCT/KR2010/005137 KR2010005137W WO2011040700A2 WO 2011040700 A2 WO2011040700 A2 WO 2011040700A2 KR 2010005137 W KR2010005137 W KR 2010005137W WO 2011040700 A2 WO2011040700 A2 WO 2011040700A2
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
- C12P7/56—Lactic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P41/00—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture
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- the present invention relates to a method for producing alkyl lactate directly from the ammonium lactate produced in the fermentation process.
- Ethyl lactate has low volatility, does not smell much, is not only stable at over 150 °C, but also has excellent dissolving power and biodegradability. It is not only toxic to food additives and fragrances, but also toxic.
- As an environmentally friendly solvent that can replace the halogenated solvent is a demand that is increasing. It can also be used as a raw material of lactide, a monomer of polylactic acid, which has recently been spotlighted as a biodegradable polymer material.
- ethyl lactate can be prepared relatively easily through the distillation of lactic acid with ethanol.
- the lactic acid is generally prepared from the fermentation process of carbohydrates such as glucose by anaerobic bacteria.
- Lactic acid produced from the fermentation process is generally present in the form of ammonium, sodium, calcium, potassium lactate, since the corresponding cation hydrate is added to maintain the neutral conditions required for bacteria during the fermentation process. Therefore, in order to convert the lactate obtained from the fermentation process into lactic acid, it is usually required to acidify the lactate with an inorganic acid such as sulfuric acid after the fermentation process.
- an inorganic acid such as sulfuric acid
- the concentration of ammonium lactate obtained from the fermentation process is 20% by weight or less, so that it contains excess water.
- lacamide is produced as a reaction by-product through the reaction of ammonia and lactic acid generated from decomposition of ammonium lactate.
- the inventors of the present invention while studying an economical manufacturing method to increase the conversion rate to ethyl lactate without by-products, to prepare a mixture containing an aqueous solution of ammonium lactate and trialkyl phosphate-based organic solvent extract, and heated it After the lactic acid is prepared, the lactic acid is esterified with alcohol, and the pre-treatment process such as the addition of sulfuric acid required to prepare the lactic acid is not carried out, and the lactic acid is produced simultaneously with the alcohol to prepare the alkyl lactate.
- the present invention was completed by finding that the alkyl lactate can be prepared more easily than the process of producing the alkyl lactate from the lactate salt produced in the fermentation process.
- An object of the present invention is to provide a method for producing alkyl lactate directly from the ammonium lactate produced in the fermentation process.
- the present invention is to prepare a mixture containing an aqueous solution of ammonium lactate and trialkyl phosphate-based organic solvent extractant produced in the fermentation process, heating it to produce lactic acid, and then lactic acid to alcohol and ester It provides a method for producing an alkyl lactate directly from ammonium lactate comprising the step of preparing an alkyl lactate by the reaction.
- an alkyl lactate is prepared by esterification with alcohol while preparing lactic acid without performing a pretreatment step such as adding sulfuric acid to prepare lactic acid.
- Alkyl lactate can be prepared more easily than the process for producing alkyl lactate from the resulting lactate salt, as well as the water produced as a reaction by-product when the esterification reaction with lactic acid, lactic acid included in the organic solvent or Through efficient separation of the alkyl lactate, it is possible to improve the reaction rate and yield, so that high efficiency, high purity alkyl lactate can be prepared.
- FIG. 1 is a schematic diagram of a process for directly preparing an alkyl lactate from ammonium lactate according to the present invention.
- the present invention provides a process for preparing alkyl lactate directly from ammonium lactate.
- alkyl lactate of the present invention More specifically, the alkyl lactate of the present invention
- the lactic acid obtained in step 1 may be prepared by a process comprising the step of esterifying the alcohol with an alcohol to produce an alkyl lactate (step 2).
- step 1 prepares a mixture containing an aqueous solution of ammonium lactate produced in the fermentation process and a trialkyl phosphate organic solvent extractant capable of acting as an acid catalyst, and heats the ammonium lactate to lactic acid. After decomposition with ammonia, lactic acid is extracted to an organic layer to prepare lactic acid.
- the aqueous ammonium lactate solution may be obtained by adding ammonia or amine to neutralize the fermentation broth to a fermentation broth containing sugar such as glucose and then using a fermentation process using microorganisms.
- the microorganism that can be used in the fermentation process includes all microorganisms that can ferment the usual glucose.
- the concentration of the ammonium lactate aqueous solution is preferably 5 to 70% by weight.
- the trialkyl phosphate organic solvent extractant is a solvent for extracting lactic acid, and its boiling point is very high at 190 ° C. or higher, so that the trialkyl phosphate organic solvent extractant hardly evaporates even during decomposition of ammonium lactate.
- a trialkyl phosphate organic solvent containing an alkyl group of C 1 to C 20 is preferably used, and a trialkyl phosphate organic solvent containing an alkyl group of C 1 to C 14 is used. It is more preferable to use.
- the weight ratio of the aqueous ammonium lactate solution and the trialkyl phosphate organic solvent extractant is preferably 1: 1 to 1:50.
- the weight ratio is less than 1: 1, there is a problem in that lactic acid extraction efficiency is reduced, and when it exceeds 1:50, there is a problem in that a lot of energy is consumed in the solvent separation process after lactic acid conversion of ammonium lactate.
- Step 1 may be performed by additionally adding trialkylamine to increase the extraction efficiency of lactic acid.
- the amount of the trialkylamine added is preferably 20% by weight or less. If the amount of trialkylamine exceeds 20% by weight, a problem may occur that inhibits the activity of the acid catalyst used in the esterification reaction carried out in step 2.
- Ammonium lactate may be decomposed into lactic acid and ammonia by heating a mixture of the aqueous ammonium lactate solution and the trialkyl phosphate organic solvent extractant.
- the alkyl lactate is prepared by directly esterifying an aqueous solution of ammonium lactate and alcohol, the yield of the resulting alkyl lactate is very low, such as 20% or less due to the moisture contained in the reactant ammonium lactate in a large amount.
- lactic acid is produced by reacting ammonia and lactic acid generated from decomposition of ammonium lactate.
- alkyl lactate by esterifying a high concentration of lactic acid and alcohol from which water is removed after primary conversion of ammonium lactate to lactic acid.
- the ammonium lactate can be decomposed into lactic acid and ammonia, and the resulting ammonia and water can be removed from the lactic acid.
- the reaction is carried out at a high temperature, the decomposition of ammonium lactate and the removal of ammonia and water are easier, but it is preferably performed in the range of 100 to 150 ° C.
- reaction temperature is less than 100 °C, there is a problem that the removal of ammonia and water is not easy, if the reaction temperature exceeds 150 °C, the production of lactamide by the reaction of ammonia and lactic acid generated during the decomposition of ammonium lactate Problems such as evaporation of organic solvents and side reactions may occur.
- the reaction is preferably carried out at 1 atm or less, and more preferably at a reduced pressure of 10 to 400 mmHg in order to increase the removal efficiency of the ammonia and water produced.
- step 2 is a step of preparing an alkyl lactate by esterifying the lactic acid obtained in step 1 with an alcohol.
- the alcohol is preferably C 1 to C 4 lower alcohol, the molar ratio of lactic acid and alcohol is preferably 1: 1 to 1:10.
- the molar ratio of lactic acid and alcohol is less than 1: 1, there is a problem that the reaction rate is reduced, and when it exceeds 1:10, there is a problem that ethanol is consumed in excess.
- step 2 In order to increase the esterification rate of step 2, it is preferable to carry out under pressurized conditions of atmospheric pressure or higher.
- the reaction is preferably carried out in the range of 70 to 150 °C.
- the reaction temperature is less than 70 °C has a problem of low reaction rate, when the reaction temperature exceeds 150 °C there is a problem that the initial alcohol input concentration is increased due to the increase in the amount of evaporation of alcohol.
- Step 2 may further include a distillation process step to separate the alkyl lactate and trialkyl phosphate.
- reaction can be carried out in an alcohol recirculation system to minimize alcohol consumption.
- an alkyl lactate is prepared by esterification with alcohol while preparing lactic acid without performing a pretreatment step such as adding sulfuric acid to prepare lactic acid.
- Alkyl lactate can be prepared more easily than the process for producing alkyl lactate from the resulting lactate salt, as well as the water produced as a reaction by-product when the esterification reaction with lactic acid, lactic acid included in the organic solvent or Through efficient separation of the alkyl lactate, it is possible to improve the reaction rate and yield, so that high efficiency, high purity alkyl lactate can be prepared.
- Ethyl lactate was obtained in the same manner as in Example 1, except that 0.5 g of Amberlyst catalyst was used instead of sulfuric acid and reacted for 20 hours while recycling ethanol. After the reaction was completed, gas chromatograph analysis showed that the final yield of ethyl lactate was 55%, lactamide was not confirmed.
- Ethyl lactate was obtained in the same manner as in Example 1, except that 1.0 g of an Amberlyst catalyst was used instead of sulfuric acid and reacted for 10 hours while recycling ethanol. After the reaction was completed, gas chromatograph analysis showed that the final yield of ethyl lactate was 70%.
- Ethyl lactate was obtained in the same manner as in Example 1, except that 0.5 g of Nafion catalyst was used instead of sulfuric acid and reacted for 15 hours while recycling ethanol. After the reaction was completed, gas chromatograph analysis showed that the final yield of ethyl lactate was 15%.
- Example 5 Except that in Example 5 using 12g of 10% by weight ammonium lactate solution instead of 40% by weight ammonium lactate solution and 50g of triethyl phosphate was heated at 110 °C for 2 hours, Ethyl lactate was obtained in the same manner as in Example 5. After the reaction was completed, gas chromatograph analysis showed that the yield of the final ethyl lactate was 71%.
- Propanol was used in place of methanol in Example 9, and propyl lactate was obtained in the same manner as in Example 10, except that the reaction solution was reacted for 10 hours while maintaining the temperature of the reaction solution at 95 ° C instead of 60 ° C. . After the reaction was completed, gas chromatograph analysis showed that the final yield of propyllactate was 73%.
- Butylol was used in the same manner as in Example 10, except that Butanol was used instead of methanol in Example 9, and the reaction solution was reacted for 10 hours while maintaining the temperature of the reaction solution at 110 ° C instead of 60 ° C. . After the reaction was completed, gas chromatograph analysis showed that the final yield of butyl lactate was 68%.
- alkyl lactate was prepared using only trialkylamine without using a trialkyl phosphate organic solvent extractant.
- Example 7 in which the alkyl lactate was prepared by adding trialkylamine to the trialkyl phosphate organic solvent extractant according to the present invention, the yield was 10%, and only trialkylamine alone was used to give alkyl. In the case of Comparative Example 1 in which the lactate was prepared, the yield was 5%. Thus, it can be seen that the yield of alkyl lactate can be increased by additionally adding trialkylamine to increase the extraction efficiency of lactic acid.
Abstract
The present invention relates to a method for producing alkyl lactate directly from ammonium lactate generated in a fermentation process. In detail, the present invention relates to a method for producing alkyl lactate directly from ammonium lactate, comprising a first step of producing a mixture comprising an aqueous solution of ammonium lactate generated in a fermentation process and trialkyl phosphate-based organic solvent extractants, and heating the mixture to prepare lactic acid; and a second step of performing an esterification reaction between the lactic acid prepared in the first step and alcohol to prepare alkyl lactate. According to the method of the present invention, a pretreatment process such as the addition of sulfuric acid required for preparing lactic acid is eliminated, and an esterification reaction between lactic acid and alcohol is performed simultaneously with the preparation of lactic acid in order to produce alkyl lactate, thereby producing alkyl lactate in an easier manner than conventional processes for producing alkyl lactate from lactate salts generated in a fermentation process, and, during an esterification reaction with lactic acid, effectively separating, from lactic acid or alkyl lactate contained in an organic solvent, water to be derived as a by-product, such that the reaction speed and yield rate can be improved and high-efficiency and high-purity alkyl lactate can be produced.
Description
본 발명은 발효공정에서 생성되는 암모늄락테이트로부터 알킬락테이트를 직접 제조하는 방법에 관한 것이다.The present invention relates to a method for producing alkyl lactate directly from the ammonium lactate produced in the fermentation process.
에틸락테이트는 휘발성이 낮으며 냄새도 많이 나지 않고, 150 ℃이상에서도 안정할 뿐만 아니라 우수한 용해력을 동시에 가지고 있으며, 아울러 생분해가 가능한 특징을 가지고 있어 음식물 첨가제, 향료로서의 응용성이 있을 뿐만 아니라, 독성이 있는 할로겐화 용매를 대체할 수 있는 친환경용매로서 그 수요가 증가하고 있는 추세이다. 또한 최근 생분해성 고분자물질로서 각광을 받고 있는 폴리락트산의 모노머인 락타이드의 원료물질로도 사용될 수 있다.Ethyl lactate has low volatility, does not smell much, is not only stable at over 150 ℃, but also has excellent dissolving power and biodegradability. It is not only toxic to food additives and fragrances, but also toxic. As an environmentally friendly solvent that can replace the halogenated solvent is a demand that is increasing. It can also be used as a raw material of lactide, a monomer of polylactic acid, which has recently been spotlighted as a biodegradable polymer material.
일반적으로 에틸락테이트는 락트산을 에탄올과의 반응증류를 통해서 상대적으로 쉽게 제조할 수 있다. 상기 락트산은 일반적으로 혐기 박테리아에 의한 글루코스와 같은 탄수화물의 발효공정으로부터 제조된다. 발효공정으로부터 제조되는 락트산은 일반적으로 암모늄, 나트륨, 칼슘, 칼륨 락테이트의 형태로 존재하게 되는데, 이는 발효공정 중 박테리아에 필요한 중성조건을 유지하기 위해 해당 양이온 수화물이 첨가되기 때문이다. 따라서 발효공정으로부터 얻어진 락테이트를 락트산으로 전환하기 위해서는 통상적으로 발효공정 후 락테이트를 황산과 같은 무기산을 이용하여 산성화하는 단계를 필요로 한다. 하지만 이러한 락트산 전환 과정에서 부산물로서 암모늄, 나트륨, 칼슘, 칼륨 설페이트가 필연적으로 발생하는 문제점이 있다. In general, ethyl lactate can be prepared relatively easily through the distillation of lactic acid with ethanol. The lactic acid is generally prepared from the fermentation process of carbohydrates such as glucose by anaerobic bacteria. Lactic acid produced from the fermentation process is generally present in the form of ammonium, sodium, calcium, potassium lactate, since the corresponding cation hydrate is added to maintain the neutral conditions required for bacteria during the fermentation process. Therefore, in order to convert the lactate obtained from the fermentation process into lactic acid, it is usually required to acidify the lactate with an inorganic acid such as sulfuric acid after the fermentation process. However, there is a problem that inevitably occurs ammonium, sodium, calcium, potassium sulfate as a by-product in the lactic acid conversion process.
이러한 산성화 부산물을 발생하지 않는 방법으로서 암모늄락테이트 수용액을 고압분해법(USP-6291708), 전기투석법 및 분리막기술(USP-5723639) 등을 이용하여 락트산을 제조하는 방법이 제시되고 있으나, 고압 반응 장치 및 분리막 관련 설비투자 비용이 크고 반응속도도 느릴 뿐만 아니라 최종 락트산의 농도가 낮은 문제점이 있다. As a method of not generating such acidification by-products, a method of preparing lactic acid using an ammonium lactate aqueous solution using a high pressure decomposition method (USP-6291708), an electrodialysis method, and a membrane technology (USP-5723639) has been proposed. And a large investment in equipment related to the membrane and a slow reaction rate, as well as a low concentration of the final lactic acid.
한편, 암모늄락테이트 수용액과 에탄올의 에스테르화 반응을 통한 직접적인 에틸락테이트 제조방법의 경우 발효공정으로부터 얻을 수 있는 암모늄락테이트의 농도가 20 중량% 이하로서 과량의 수분을 포함하고 있기 때문에 역반응에 의해 에틸락테이트로의 전환율이 낮을 뿐 아니라 암모늄락테이트의 분해로부터 생성되는 암모니아와 락트산의 반응을 통해서 반응부산물로서 락트아마이드가 생성되는 문제점이 있다.On the other hand, in the case of the direct method of producing ethyl lactate through esterification of aqueous solution of ammonium lactate and ethanol, the concentration of ammonium lactate obtained from the fermentation process is 20% by weight or less, so that it contains excess water. In addition to low conversion to ethyl lactate, there is a problem that lacamide is produced as a reaction by-product through the reaction of ammonia and lactic acid generated from decomposition of ammonium lactate.
따라서, 글루코스의 발효로부터 생성되는 락테이트 수용액으로부터 부산물 없이 에틸락테이트로의 전환율을 높일 수 있는 경제적인 제조방법이 요구되고 있다.Therefore, there is a need for an economical production method capable of increasing the conversion rate of the lactate aqueous solution generated from the fermentation of glucose to ethyl lactate without by-products.
이에, 본 발명자들은 부산물 없이 에틸락테이트로의 전환율을 높일 수 있는 경제적인 제조방법을 연구하던 중, 암모늄락테이트 수용액과 트리알킬포스페이트계 유기용매 추출제를 포함하는 혼합물을 제조하고, 이를 가열하여 락트산을 제조한 후, 락트산을 알코올과 에스테르화 반응시킴으로써 락트산을 제조하는데 필요한 황산 첨가와 같은 전처리 공정을 수행하지 않고, 락트산을 제조함과 동시에 알코올과 에스테르화 반응시켜 알킬락테이트를 제조함으로써 기존의 발효공정에서 생성되는 락테이트염으로부터 알킬락테이트를 생성하는 공정보다 용이하게 알킬락테이트를 제조할 수 있음을 알아내고 본 발명을 완성하였다. Therefore, the inventors of the present invention while studying an economical manufacturing method to increase the conversion rate to ethyl lactate without by-products, to prepare a mixture containing an aqueous solution of ammonium lactate and trialkyl phosphate-based organic solvent extract, and heated it After the lactic acid is prepared, the lactic acid is esterified with alcohol, and the pre-treatment process such as the addition of sulfuric acid required to prepare the lactic acid is not carried out, and the lactic acid is produced simultaneously with the alcohol to prepare the alkyl lactate. The present invention was completed by finding that the alkyl lactate can be prepared more easily than the process of producing the alkyl lactate from the lactate salt produced in the fermentation process.
본 발명의 목적은 발효공정에서 생성되는 암모늄락테이트로부터 알킬락테이트를 직접 제조하는 방법을 제공하는 데 있다.An object of the present invention is to provide a method for producing alkyl lactate directly from the ammonium lactate produced in the fermentation process.
상기 목적을 달성하기 위하여, 본 발명은 발효공정에서 생성되는 암모늄락테이트 수용액과 트리알킬포스페이트계 유기용매 추출제를 포함하는 혼합물을 제조하고, 이를 가열하여 락트산을 제조한 후, 락트산을 알코올과 에스테르화 반응시켜 알킬락테이트를 제조하는 단계를 포함하는 암모늄락테이트로부터 알킬락테이트를 직접 제조하는 방법을 제공한다.In order to achieve the above object, the present invention is to prepare a mixture containing an aqueous solution of ammonium lactate and trialkyl phosphate-based organic solvent extractant produced in the fermentation process, heating it to produce lactic acid, and then lactic acid to alcohol and ester It provides a method for producing an alkyl lactate directly from ammonium lactate comprising the step of preparing an alkyl lactate by the reaction.
본 발명에 따른 알킬락테이트의 제조방법은 락트산을 제조하는데 필요한 황산 첨가와 같은 전처리 공정을 수행하지 않고, 락트산을 제조함과 동시에 알코올과 에스테르화 반응시켜 알킬락테이트를 제조함으로써 기존의 발효공정에서 생성되는 락테이트염으로부터 알킬락테이트를 생성하는 공정보다 용이하게 알킬락테이트를 제조할 수 있을 뿐만 아니라, 락트산과 에스테르화 반응 수행시 반응부산물로 생성되는 물과, 유기용매에 포함되어 있는 락트산 또는 알킬락테이트의 효과적인 분리를 통해서 반응속도 및 수율을 향상시킬 수 있으므로 고효율, 고순도의 알킬락테이트를 제조할 수 있다.In the method for preparing alkyl lactate according to the present invention, in the existing fermentation process, an alkyl lactate is prepared by esterification with alcohol while preparing lactic acid without performing a pretreatment step such as adding sulfuric acid to prepare lactic acid. Alkyl lactate can be prepared more easily than the process for producing alkyl lactate from the resulting lactate salt, as well as the water produced as a reaction by-product when the esterification reaction with lactic acid, lactic acid included in the organic solvent or Through efficient separation of the alkyl lactate, it is possible to improve the reaction rate and yield, so that high efficiency, high purity alkyl lactate can be prepared.
도 1은 본 발명에 따른 암모늄락테이트로부터 알킬락테이트를 직접 제조하는 공정의 모식도이다.1 is a schematic diagram of a process for directly preparing an alkyl lactate from ammonium lactate according to the present invention.
본 발명은 암모늄락테이트로부터 알킬락테이트를 직접 제조하는 방법을 제공한다.The present invention provides a process for preparing alkyl lactate directly from ammonium lactate.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
보다 구체적으로 본 발명의 알킬락테이트는More specifically, the alkyl lactate of the present invention
발효공정에서 생성되는 암모늄락테이트 수용액과 트리알킬포스페이트계 유기용매 추출제를 포함하는 혼합물을 제조하고, 이를 가열하여 락트산을 제조하는 단계(단계 1); 및Preparing a mixture including an aqueous ammonium lactate solution and a trialkyl phosphate organic solvent extractant produced in the fermentation process, and heating the same to prepare lactic acid (step 1); And
상기 단계 1에서 얻은 락트산을 알코올과 에스테르화 반응시켜 알킬락테이트를 제조하는 단계(단계 2)를 포함하여 이루어지는 공정에 의해 제조될 수 있다.The lactic acid obtained in step 1 may be prepared by a process comprising the step of esterifying the alcohol with an alcohol to produce an alkyl lactate (step 2).
이하, 본 발명에 따른 상기 제조방법을 단계별로 더욱 구체적으로 설명한다.Hereinafter, the manufacturing method according to the present invention will be described in more detail step by step.
먼저, 본 발명에 따른 상기 단계 1은 발효공정에서 생성되는 암모늄락테이트 수용액과 산 촉매가 작용할 수 있는 트리알킬포스페이트계 유기용매 추출제를 포함하는 혼합물을 제조하고 이를 가열하여 암모늄락테이트를 락트산과 암모니아로 분해한 후, 락트산을 유기층으로 추출하여 락트산을 제조하는 단계이다.First, step 1 according to the present invention prepares a mixture containing an aqueous solution of ammonium lactate produced in the fermentation process and a trialkyl phosphate organic solvent extractant capable of acting as an acid catalyst, and heats the ammonium lactate to lactic acid. After decomposition with ammonia, lactic acid is extracted to an organic layer to prepare lactic acid.
상기 암모늄락테이트 수용액은 글루코스와 같은 설탕이 포함된 발효액에 발효액을 중성화하기 위해서 암모니아 또는 아민을 첨가한 후 미생물을 이용한 발효공정을 이용하여 얻을 수 있다. 이때, 발효공정에 사용될 수 있는 미생물은 통상의 글루코스를 발효할 수 있는 모든 미생물을 포함한다. 상기 암모늄락테이트 수용액의 농도는 5 내지 70 중량%인 것이 바람직하다.The aqueous ammonium lactate solution may be obtained by adding ammonia or amine to neutralize the fermentation broth to a fermentation broth containing sugar such as glucose and then using a fermentation process using microorganisms. At this time, the microorganism that can be used in the fermentation process includes all microorganisms that can ferment the usual glucose. The concentration of the ammonium lactate aqueous solution is preferably 5 to 70% by weight.
상기 트리알킬포스페이트계 유기용매 추출제는 락트산을 추출하기 위한 용매로서, 끓는점이 190 ℃ 이상으로 매우 높아 암모늄락테이트의 분해반응시에도 거의 증발하지 않는 장점이 있다. 상기 트리알킬포스페이트계 유기용매 추출제로는 C1 내지 C20의 알킬기를 포함하는 트리알킬포스페이트계 유기용매를 사용하는 것이 바람직하며, C1 내지 C14의 알킬기를 포함하는 트리알킬포스페이트계 유기용매를 사용하는 것이 더욱 바람직하다.The trialkyl phosphate organic solvent extractant is a solvent for extracting lactic acid, and its boiling point is very high at 190 ° C. or higher, so that the trialkyl phosphate organic solvent extractant hardly evaporates even during decomposition of ammonium lactate. As the trialkyl phosphate organic solvent extractant, a trialkyl phosphate organic solvent containing an alkyl group of C 1 to C 20 is preferably used, and a trialkyl phosphate organic solvent containing an alkyl group of C 1 to C 14 is used. It is more preferable to use.
상기 암모늄락테이트 수용액과 트리알킬포스페이트계 유기용매 추출제의 중량비는 1:1 내지 1:50인 것이 바람직하다. 상기 중량비가 1:1 미만인 경우 락트산 추출효율이 감소하는 문제가 있으며, 1:50을 초과하는 경우 암모늄락테이트의 락트산 전환 후 용매분리공정에서 많은 에너지가 소요되는 문제가 있다.The weight ratio of the aqueous ammonium lactate solution and the trialkyl phosphate organic solvent extractant is preferably 1: 1 to 1:50. When the weight ratio is less than 1: 1, there is a problem in that lactic acid extraction efficiency is reduced, and when it exceeds 1:50, there is a problem in that a lot of energy is consumed in the solvent separation process after lactic acid conversion of ammonium lactate.
상기 단계 1은 락트산의 추출효율을 증가시키기 위해 추가적으로 트리알킬아민을 첨가하여 수행할 수 있다. 이때, 첨가되는 트리알킬아민의 양은 20 중량% 이하인 것이 바람직하다. 트리알킬아민의 양이 20 중량%를 초과하는 경우에는 단계 2에서 수행하는 에스테르화 반응에 사용되는 산 촉매의 활성을 저해하는 문제점이 발생할 수 있다.Step 1 may be performed by additionally adding trialkylamine to increase the extraction efficiency of lactic acid. At this time, the amount of the trialkylamine added is preferably 20% by weight or less. If the amount of trialkylamine exceeds 20% by weight, a problem may occur that inhibits the activity of the acid catalyst used in the esterification reaction carried out in step 2.
상기 암모늄락테이트 수용액과 트리알킬포스페이트계 유기용매 추출제의 혼합물을 가열하여 암모늄락테이트를 락트산과 암모니아로 분해할 수 있다. 암모늄락테이트 수용액과 알코올을 직접 에스테르화 반응시켜 알킬락테이트를 제조하는 경우, 생성되는 알킬락테이트의 수율은 반응물인 암모늄락테이트에 다량으로 포함되어 있는 수분으로 인해 20% 이하로 매우 낮다. 또한, 이러한 경우 암모늄락테이트의 분해로부터 생성되는 암모니아와 락트산이 반응하여 락트아마이드가 생성되는 문제점이 있다. 따라서, 암모늄락테이트를 락트산으로 1차 전환한 후 수분이 제거된 고농도의 락트산과 알코올을 에스테르화 반응시켜 알킬락테이트를 제조하는 것이 바람직하다. 상기 암모늄락테이트 수용액과 트리알킬포스페이트계 유기용매 추출제의 혼합물을 가열함으로써 암모늄락테이트를 락트산과 암모니아로 분해할 수 있을 뿐만 아니라, 생성되는 암모니아와 물을 락트산으로부터 제거할 수 있다. 상기 반응은 높은 온도에서 수행할수록 암모늄락테이트의 분해 및 암모니아와 물의 제거가 용이하나, 100 내지 150 ℃의 범위에서 수행하는 것이 바람직하다. 상기 반응온도가 100 ℃ 미만인 경우에는 암모니아와 물의 제거가 용이하지 않은 문제가 있으며, 반응온도가 150 ℃를 초과하는 경우에는 암모늄락테이트의 분해시 생성되는 암모니아와 락트산의 반응에 의한 락트아마이드의 생성, 유기용매의 증발, 부반응 등의 문제점이 발생할 수 있다.Ammonium lactate may be decomposed into lactic acid and ammonia by heating a mixture of the aqueous ammonium lactate solution and the trialkyl phosphate organic solvent extractant. When the alkyl lactate is prepared by directly esterifying an aqueous solution of ammonium lactate and alcohol, the yield of the resulting alkyl lactate is very low, such as 20% or less due to the moisture contained in the reactant ammonium lactate in a large amount. In addition, in this case, there is a problem in that lactic acid is produced by reacting ammonia and lactic acid generated from decomposition of ammonium lactate. Therefore, it is preferable to prepare alkyl lactate by esterifying a high concentration of lactic acid and alcohol from which water is removed after primary conversion of ammonium lactate to lactic acid. By heating the mixture of the aqueous ammonium lactate solution and the trialkyl phosphate organic solvent extractant, the ammonium lactate can be decomposed into lactic acid and ammonia, and the resulting ammonia and water can be removed from the lactic acid. As the reaction is carried out at a high temperature, the decomposition of ammonium lactate and the removal of ammonia and water are easier, but it is preferably performed in the range of 100 to 150 ° C. If the reaction temperature is less than 100 ℃, there is a problem that the removal of ammonia and water is not easy, if the reaction temperature exceeds 150 ℃, the production of lactamide by the reaction of ammonia and lactic acid generated during the decomposition of ammonium lactate Problems such as evaporation of organic solvents and side reactions may occur.
상기 반응은 생성되는 암모니아와 물의 제거 효율을 높이기 위해 1 기압 이하에서 수행하는 것이 바람직하며, 10 내지 400 ㎜Hg의 감압 조건에서 수행하는 것이 더욱 바람직하다. The reaction is preferably carried out at 1 atm or less, and more preferably at a reduced pressure of 10 to 400 mmHg in order to increase the removal efficiency of the ammonia and water produced.
다음으로, 상기 단계 2는 상기 단계 1에서 얻은 락트산을 알코올과 에스테르화 반응시켜 알킬락테이트를 제조하는 단계이다. Next, step 2 is a step of preparing an alkyl lactate by esterifying the lactic acid obtained in step 1 with an alcohol.
상기 알코올은 C1 내지 C4의 저급 알코올을 사용하는 것이 바람직하며, 상기 락트산과 알코올의 몰비는 1:1 내지 1:10인 것이 바람직하다. 상기 락트산과 알코올의 몰비가 1:1 미만인 경우에는 반응속도가 감소하는 문제가 있으며, 1:10을 초과하는 경우에는 에탄올이 과량으로 소모되는 문제가 있다.The alcohol is preferably C 1 to C 4 lower alcohol, the molar ratio of lactic acid and alcohol is preferably 1: 1 to 1:10. When the molar ratio of lactic acid and alcohol is less than 1: 1, there is a problem that the reaction rate is reduced, and when it exceeds 1:10, there is a problem that ethanol is consumed in excess.
상기 단계 2의 에스테르화 반응속도를 높이기 위해 산 촉매를 사용하여 수행할 수 있다. 상기 촉매로는 황산, 엠버리스트(Amberlyst), 나피온(Nafion), 나피온-실리카 복합물(Nafion-Silica Composite), Keggin형 헤테로폴리 산(Keggin-type heteropoly acid, H(8-x)XM12O40(X = Si4+, P5+ , M = W6+ 또는 Mo6+)), Nb2O5, HNbMoO6, 제올라이트(Zeolite) 등을 사용할 수 있다.It can be carried out using an acid catalyst to increase the rate of esterification in step 2. The catalyst includes sulfuric acid, Amberlyst, Nafion, Nafion-Silica Composite, Keggin-type heteropoly acid, H (8-x) XM 12 O 40 (X = Si 4+ , P 5+ , M = W 6+ or Mo 6+ ), Nb 2 O 5 , HNbMoO 6 , zeolite, and the like can be used.
상기 단계 2의 에스테르화 반응속도를 높이기 위해 대기압 이상의 가압 조건에서 수행하는 것이 바람직하다.In order to increase the esterification rate of step 2, it is preferable to carry out under pressurized conditions of atmospheric pressure or higher.
상기 반응은 70 내지 150 ℃의 범위에서 수행하는 것이 바람직하다. 상기 반응온도가 70 ℃ 미만인 경우에는 반응 속도가 낮은 문제가 있으며, 반응온도가 150 ℃를 초과하는 경우에는 알코올의 증발량 증가로 인하여 초기 알코올 투입 농도가 증가하는 문제가 있다.The reaction is preferably carried out in the range of 70 to 150 ℃. When the reaction temperature is less than 70 ℃ has a problem of low reaction rate, when the reaction temperature exceeds 150 ℃ there is a problem that the initial alcohol input concentration is increased due to the increase in the amount of evaporation of alcohol.
상기 단계 2는 알킬락테이트와 트리알킬포스페이트를 분리하기 위해 추가적으로 증류공정 단계를 더 포함할 수 있다. Step 2 may further include a distillation process step to separate the alkyl lactate and trialkyl phosphate.
또한, 상기 반응은 알코올 소모량을 최소화하기 위하여 알코올 재순환시스템에서 수행할 수 있다.In addition, the reaction can be carried out in an alcohol recirculation system to minimize alcohol consumption.
본 발명에 따른 알킬락테이트의 제조방법은 락트산을 제조하는데 필요한 황산 첨가와 같은 전처리 공정을 수행하지 않고, 락트산을 제조함과 동시에 알코올과 에스테르화 반응시켜 알킬락테이트를 제조함으로써 기존의 발효공정에서 생성되는 락테이트염으로부터 알킬락테이트를 생성하는 공정보다 용이하게 알킬락테이트를 제조할 수 있을 뿐만 아니라, 락트산과 에스테르화 반응 수행시 반응부산물로 생성되는 물과, 유기용매에 포함되어 있는 락트산 또는 알킬락테이트의 효과적인 분리를 통해서 반응속도 및 수율을 향상시킬 수 있으므로 고효율, 고순도의 알킬락테이트를 제조할 수 있다.In the method for preparing alkyl lactate according to the present invention, in the existing fermentation process, an alkyl lactate is prepared by esterification with alcohol while preparing lactic acid without performing a pretreatment step such as adding sulfuric acid to prepare lactic acid. Alkyl lactate can be prepared more easily than the process for producing alkyl lactate from the resulting lactate salt, as well as the water produced as a reaction by-product when the esterification reaction with lactic acid, lactic acid included in the organic solvent or Through efficient separation of the alkyl lactate, it is possible to improve the reaction rate and yield, so that high efficiency, high purity alkyl lactate can be prepared.
이하, 본 발명을 실시예에 의해 더욱 구체적으로 설명한다. 단, 하기의 실시예는 본 발명을 예시하기 위한 것일 뿐, 본 발명의 내용이 하기의 실시예에 의해 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are only for illustrating the present invention, and the content of the present invention is not limited by the following examples.
<실시예 1> 에틸락테이트의 제조 1Example 1 Preparation of Ethyl Lactate 1
20 중량% 암모늄락테이트 용액 12 g, 트리부틸포스페이트 50 g을 250 ㎖ 플라스크에 넣고 진공펌프를 연결하여 반응기 내의 진공도를 200 ㎜Hg 정도로 유지하였다. 이후 반응물이 포함된 플라스크를 가열하여 반응액의 최종온도가 110 ℃가 유지될 수 있도록 조절하였다. 1시간 동안 반응시킨 후, 진공펌프를 끄고 반응액의 온도를 80 ℃이하로 유지한 상태에서 99 중량% 에탄올 20 g과 98 중량% 0.45 g의 황산을 추가로 첨가하였다. 이후 반응액의 온도를 85 ℃로 유지하고 에탄올을 재순환하면서 3시간 동안 반응을 진행하여 에틸락테이트를 수득하였다. 반응이 완료된 후, 기체크로마토그래프 분석 결과 에틸락테이트의 최종 수율은 60%이었으며, 락트아마이드는 확인되지 않았다.12 g of a 20% by weight ammonium lactate solution and 50 g of tributylphosphate were placed in a 250 ml flask, and a vacuum pump was connected to maintain a vacuum degree of about 200 mmHg. After that, the flask containing the reactant was heated to adjust the final temperature of the reaction solution to maintain 110 ℃. After reacting for 1 hour, 20 g of 99% by weight ethanol and 98% by weight 0.45 g of sulfuric acid were further added while the vacuum pump was turned off and the temperature of the reaction solution was maintained at 80 ° C or lower. Thereafter, the reaction solution was maintained at 85 ° C. and ethanol was recycled for 3 hours to obtain ethyl lactate. After the reaction was completed, gas chromatograph analysis showed that the final yield of ethyl lactate was 60%, lactamide was not confirmed.
<실시예 2> 에틸락테이트의 제조 2Example 2 Preparation of Ethyl Lactate 2
상기 실시예 1에서 황산 대신에 0.5 g의 엠버리스트(amberlyst) 촉매를 사용하고 에탄올을 재순환하면서 20시간 동안 반응하는 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 에틸락테이트를 수득하였다. 반응이 완료된 후, 기체크로마토그래프 분석 결과 에틸락테이트의 최종 수율은 55%이었으며, 락트아마이드는 확인되지 않았다.Ethyl lactate was obtained in the same manner as in Example 1, except that 0.5 g of Amberlyst catalyst was used instead of sulfuric acid and reacted for 20 hours while recycling ethanol. After the reaction was completed, gas chromatograph analysis showed that the final yield of ethyl lactate was 55%, lactamide was not confirmed.
<실시예 3> 에틸락테이트의 제조 3Example 3 Preparation of Ethyl Lactate 3
상기 실시예 1에서 황산 대신에 1.0 g의 엠버리스트(amberlyst) 촉매를 사용하고 에탄올을 재순환하면서 10시간 동안 반응하는 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 에틸락테이트를 수득하였다. 반응이 완료된 후, 기체크로마토그래프 분석 결과 에틸락테이트의 최종 수율은 70%이었다.Ethyl lactate was obtained in the same manner as in Example 1, except that 1.0 g of an Amberlyst catalyst was used instead of sulfuric acid and reacted for 10 hours while recycling ethanol. After the reaction was completed, gas chromatograph analysis showed that the final yield of ethyl lactate was 70%.
<실시예 4> 에틸락테이트의 제조 4Example 4 Preparation of Ethyl Lactate 4
상기 실시예 1에서 황산 대신에 0.5 g의 나피온(nafion) 촉매를 사용하고 에탄올을 재순환하면서 15시간 동안 반응하는 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 에틸락테이트를 수득하였다. 반응이 완료된 후, 기체크로마토그래프 분석 결과 에틸락테이트의 최종 수율은 15%이었다.Ethyl lactate was obtained in the same manner as in Example 1, except that 0.5 g of Nafion catalyst was used instead of sulfuric acid and reacted for 15 hours while recycling ethanol. After the reaction was completed, gas chromatograph analysis showed that the final yield of ethyl lactate was 15%.
<실시예 5> 에틸락테이트의 제조 5Example 5 Preparation of Ethyl Lactate 5
40 중량% 암모늄락테이트 용액 12 g, 트리에틸포스페이트 120 g을 250 ㎖ 플라스크에 넣고 진공펌프를 연결하여 반응기 내의 진공도를 200 ㎜Hg 정도로 유지하였다. 이후 반응물이 포함된 플라스크 가열을 시작하여 최종적인 반응액의 온도가 120 ℃가 유지될 수 있도록 조절하였다. 30분 동안 반응시킨 후, 진공펌프를 끄고 반응액의 온도를 80 ℃이하로 유지한 상태에서 99 중량% 에탄올 20 g과 1.0 g의 엠버리스트(amberlyst) 촉매를 추가로 첨가하였다. 이후 반응액의 온도를 85 ℃로 유지하고 10시간 동안 반응을 진행하여 에틸락테이트를 수득하였다. 반응이 완료된 후, 기체크로마토그래프 분석 결과 최종 에틸락테이트의 수율은 72%이었다.12 g of 40% by weight ammonium lactate solution and 120 g of triethylphosphate were placed in a 250 ml flask, and a vacuum pump was connected to maintain a vacuum degree of about 200 mmHg. After the heating of the flask containing the reactants was started so that the temperature of the final reaction solution was maintained to 120 ℃. After reacting for 30 minutes, the vacuum pump was turned off and 20 g of 99 wt% ethanol and 1.0 g of Amberlyst catalyst were further added while maintaining the temperature of the reaction solution at 80 ° C. or lower. Thereafter, the reaction solution was maintained at 85 ° C. and reacted for 10 hours to obtain ethyl lactate. After the reaction was completed, gas chromatograph analysis showed that the yield of the final ethyl lactate was 72%.
<실시예 6> 에틸락테이트의 제조 6Example 6 Preparation of Ethyl Lactate 6
상기 실시예 5에서 40 중량% 암모늄락테이트 용액 대신에 10 중량% 암모늄락테이트 용액 12g을 사용하고, 트리에틸포스페이트 50 g을 사용하여 110 ℃에서 2시간 동안 가열반응시키는 것을 제외하고는, 상기 실시예 5와 동일한 방법으로 에틸락테이트를 수득하였다. 반응이 완료된 후, 기체크로마토그래프 분석 결과 최종 에틸락테이트의 수율은 71%이었다.Except that in Example 5 using 12g of 10% by weight ammonium lactate solution instead of 40% by weight ammonium lactate solution and 50g of triethyl phosphate was heated at 110 ℃ for 2 hours, Ethyl lactate was obtained in the same manner as in Example 5. After the reaction was completed, gas chromatograph analysis showed that the yield of the final ethyl lactate was 71%.
<실시예 7> 에틸락테이트의 제조 7Example 7 Preparation of Ethyl Lactate 7
20 중량% 암모늄락테이트 용액 12 g, 트리부틸포스페이트 40 g, 트리도데실아민 10 g을 250 ㎖ 플라스크에 넣고 진공펌프를 연결하여 반응기 내의 진공도를 200 ㎜Hg 정도로 유지하였다. 이후 반응물이 포함된 플라스크 가열을 시작하여 최종적인 반응액의 온도가 110 ℃가 유지될 수 있도록 조절하였다. 1시간 동안 반응시킨 후, 진공펌프를 끄고 반응액의 온도를 80 ℃이하로 유지한 상태에서 99 중량% 에탄올 20 g과 1.0 g의 엠버리스트(amberlyst) 촉매를 추가로 첨가하였다. 이후 반응액의 온도를 85 ℃로 유지하고 20시간 동안 반응을 진행하여 에틸락테이트를 수득하였다. 반응이 완료된 후, 기체크로마토그래프 분석 결과 최종 에틸락테이트의 수율은 10%이었다.12 g of 20% by weight ammonium lactate solution, 40 g of tributylphosphate, and 10 g of tridodecylamine were placed in a 250 ml flask, and a vacuum pump was connected to maintain a vacuum degree of about 200 mmHg. After the heating of the flask containing the reactants was started to adjust the temperature of the final reaction solution to maintain 110 ℃. After reacting for 1 hour, the vacuum pump was turned off and 20 g of 99 wt% ethanol and 1.0 g of Amberlyst catalyst were further added while maintaining the temperature of the reaction solution at 80 ° C. or lower. Thereafter, the reaction solution was maintained at 85 ° C. and reacted for 20 hours to obtain ethyl lactate. After the reaction was completed, gas chromatograph analysis showed that the yield of the final ethyl lactate was 10%.
<실시예 8> 에틸락테이트의 제조 8Example 8 Preparation of Ethyl Lactate 8
20 중량% 암모늄락테이트 용액 12 g, 트리부틸포스페이트 100 g을 250 ㎖ 플라스크에 넣고 진공펌프를 연결하여 반응기 내의 진공도를 10 ㎜Hg 정도로 유지하였다. 이후 반응물이 포함된 플라스크 가열을 시작하여 최종적인 반응액의 온도가 140 ℃가 유지될 수 있도록 조절하였다. 30분 동안 반응시킨 후, 진공펌프를 끄고 반응액의 온도를 80 ℃이하로 유지한 상태에서 99 중량% 에탄올 20 g과 1.0 g의 엠버리스트(amberlyst) 촉매를 추가로 첨가하였다. 이후 반응액의 온도를 85 ℃로 유지하고 10시간 동안 반응을 진행하여 에틸락테이트를 수득하였다. 반응이 완료된 후, 기체크로마토그래프 분석 결과 최종 에틸락테이트의 수율은 65%이었다.12 g of 20% by weight ammonium lactate solution and 100 g of tributylphosphate were placed in a 250 ml flask, and a vacuum pump was connected to maintain a vacuum of about 10 mmHg. After the heating of the flask containing the reactants was started to adjust the temperature of the final reaction solution to maintain 140 ℃. After reacting for 30 minutes, the vacuum pump was turned off and 20 g of 99 wt% ethanol and 1.0 g of Amberlyst catalyst were further added while maintaining the temperature of the reaction solution at 80 ° C. or lower. Thereafter, the reaction solution was maintained at 85 ° C. and reacted for 10 hours to obtain ethyl lactate. After the reaction was completed, gas chromatograph analysis showed that the yield of the final ethyl lactate was 65%.
<실시예 9> 메틸락테이트의 제조Example 9 Preparation of Methyllactate
20 중량% 암모늄락테이트 용액 12 g, 트리부틸포스페이트 50 g을 250 ㎖ 플라스크에 넣고 진공펌프를 연결하여 반응기 내의 진공도를 200 ㎜Hg 정도로 유지하였다. 이후 반응물이 포함된 플라스크를 가열하여 반응액의 최종온도가 110 ℃가 유지될 수 있도록 조절하였다. 1시간 동안 반응시킨 후, 진공펌프를 끄고 반응액의 온도를 80 ℃이하로 유지한 상태에서 99 중량% 메탄올 20 g과 1.0 g의 엠버리스트(amberlyst) 촉매를 추가로 첨가하였다. 이후 반응액의 온도를 60 ℃로 유지하고 에탄올을 재순환하면서 10시간 동안 반응을 진행하여 메틸락테이트를 수득하였다. 반응이 완료된 후, 기체크로마토그래프 분석 결과 메틸락테이트의 최종 수율은 55%이었다.12 g of a 20% by weight ammonium lactate solution and 50 g of tributylphosphate were placed in a 250 ml flask, and a vacuum pump was connected to maintain a vacuum degree of about 200 mmHg. After that, the flask containing the reactant was heated to adjust the final temperature of the reaction solution to maintain 110 ℃. After reacting for 1 hour, the vacuum pump was turned off and 20 g of 99 wt% methanol and 1.0 g of amberlyst catalyst were further added while maintaining the temperature of the reaction solution at 80 ° C. or lower. Thereafter, the reaction solution was maintained at 60 ° C. and ethanol was recycled for 10 hours to obtain methyl lactate. After the reaction was completed, gas chromatograph analysis showed that the final yield of methyl lactate was 55%.
<실시예 10> 프로필락테이트의 제조Example 10 Preparation of Propyl Lactate
상기 실시예 9에서 메탄올 대신에 프로판올을 사용하고, 반응액의 온도를 60 ℃ 대신에 95 ℃로 유지하면서 10시간 동안 반응하는 것을 제외하고는 상기 실시예 10과 동일한 방법으로 프로필락테이트를 수득하였다. 반응이 완료된 후, 기체크로마토그래프 분석 결과 프로필락테이트의 최종 수율은 73%이었다.Propanol was used in place of methanol in Example 9, and propyl lactate was obtained in the same manner as in Example 10, except that the reaction solution was reacted for 10 hours while maintaining the temperature of the reaction solution at 95 ° C instead of 60 ° C. . After the reaction was completed, gas chromatograph analysis showed that the final yield of propyllactate was 73%.
<실시예 11> 부틸락테이트의 제조Example 11 Preparation of Butyl Lactate
상기 실시예 9에서 메탄올 대신에 부탄올을 사용하고, 반응액의 온도를 60 ℃ 대신에 110 ℃로 유지하면서 10시간 동안 반응하는 것을 제외하고는 상기 실시예 10과 동일한 방법으로 부틸락테이트를 수득하였다. 반응이 완료된 후, 기체크로마토그래프 분석 결과 부틸락테이트의 최종 수율은 68%이었다.Butylol was used in the same manner as in Example 10, except that Butanol was used instead of methanol in Example 9, and the reaction solution was reacted for 10 hours while maintaining the temperature of the reaction solution at 110 ° C instead of 60 ° C. . After the reaction was completed, gas chromatograph analysis showed that the final yield of butyl lactate was 68%.
<비교예 1> 에틸락테이트의 제조 1<Comparative Example 1> Preparation of ethyl lactate 1
트리알킬포스페이트계 유기용매 추출제를 사용하지 않고, 트리알킬아민만을 사용하여 알킬락테이트를 제조하였다.An alkyl lactate was prepared using only trialkylamine without using a trialkyl phosphate organic solvent extractant.
20 중량% 암모늄락테이트 용액 12 g, 트리도데실아민 50 g을 250 ㎖ 플라스크에 넣고 진공펌프를 연결하여 반응기 내의 진공도를 200 ㎜Hg 정도로 유지하였다. 이후 반응물이 포함된 플라스크 가열을 시작하여 최종적인 반응액의 온도가 110 ℃가 유지될 수 있도록 조절하였다. 1시간 동안 반응시킨 후, 진공펌프를 끄고 반응액의 온도를 80 ℃이하로 유지한 상태에서 99 중량% 에탄올 20 g과 1.0 g의 엠버리스트(amberlyst) 촉매를 추가로 첨가하였다. 이후 반응액의 온도를 85 ℃로 유지하고 40시간 동안 반응을 진행하여 에틸락테이트를 수득하였다. 반응이 완료된 후, 기체크로마토그래프 분석 결과 최종 에틸락테이트의 수율은 5%이었다.12 g of 20% by weight ammonium lactate solution and 50 g of tridodecylamine were placed in a 250 ml flask, and a vacuum pump was connected to maintain a vacuum degree of about 200 mmHg. After the heating of the flask containing the reactants was started to adjust the temperature of the final reaction solution to maintain 110 ℃. After reacting for 1 hour, the vacuum pump was turned off and 20 g of 99 wt% ethanol and 1.0 g of Amberlyst catalyst were further added while maintaining the temperature of the reaction solution at 80 ° C. or lower. Thereafter, the reaction solution was maintained at 85 ° C. and reacted for 40 hours to obtain ethyl lactate. After the reaction was completed, gas chromatograph analysis showed that the yield of the final ethyl lactate was 5%.
이를 통해, 본 발명에 따른 트리알킬포스페이트계 유기용매 추출제에 추가적으로 트리알킬아민을 첨가하여 알킬락테이트를 제조한 실시예 7의 경우에는 수율이 10%이며, 트리알킬아민만을 단독으로 사용하여 알킬락테이트를 제조한 비교예 1의 경우에는 수율이 5%를 나타내므로 락트산의 추출효율을 증가시키기 위해 트리알킬아민을 추가적으로 첨가함으로써 알킬락테이트의 수율을 증가시킬 수 있음을 알 수 있다. As a result, in Example 7, in which the alkyl lactate was prepared by adding trialkylamine to the trialkyl phosphate organic solvent extractant according to the present invention, the yield was 10%, and only trialkylamine alone was used to give alkyl. In the case of Comparative Example 1 in which the lactate was prepared, the yield was 5%. Thus, it can be seen that the yield of alkyl lactate can be increased by additionally adding trialkylamine to increase the extraction efficiency of lactic acid.
Claims (18)
- 발효공정에서 생성되는 암모늄락테이트 수용액과 트리알킬포스페이트계 유기용매 추출제를 포함하는 혼합물을 제조하고, 이를 가열하여 락트산을 제조하는 단계(단계 1); 및Preparing a mixture including an aqueous ammonium lactate solution and a trialkyl phosphate organic solvent extractant produced in the fermentation process, and heating the same to prepare lactic acid (step 1); And상기 단계 1에서 얻은 락트산을 알코올과 에스테르화 반응시켜 알킬락테이트를 제조하는 단계(단계 2)를 포함하여 이루어지는 암모늄락테이트로부터 알킬락테이트를 직접 제조하는 방법.A method of directly preparing an alkyl lactate from an ammonium lactate comprising the step (step 2) of esterifying the lactic acid obtained in step 1 with an alcohol to produce an alkyl lactate.
- 제1항에 있어서, 상기 단계 1의 발효공정에서 생성되는 암모늄락테이트 수용액의 농도는 5 내지 70 중량%인 것을 특징으로 하는 암모늄락테이트로부터 알킬락테이트를 직접 제조하는 방법.The method of claim 1, wherein the concentration of the aqueous ammonium lactate solution produced in the fermentation process of step 1 is 5 to 70% by weight, the method for producing alkyl lactate directly from ammonium lactate.
- 제1항에 있어서, 상기 단계 1의 트리알킬포스페이트계 유기용매 추출제는 C1 내지 C20의 알킬기를 포함하는 트리알킬포스페이트계 유기용매인 것을 특징으로 하는 암모늄락테이트로부터 알킬락테이트를 직접 제조하는 방법.According to claim 1, wherein the trialkyl phosphate-based organic solvent extractant of step 1 is an alkyl lactate directly prepared from ammonium lactate, characterized in that the trialkyl phosphate-based organic solvent containing an alkyl group of C 1 to C 20 How to.
- 제3항에 있어서, 상기 트리알킬포스페이트계 유기용매 추출제는 C1 내지 C14의 알킬기를 포함하는 트리알킬포스페이트계 유기용매인 것을 특징으로 하는 암모늄락테이트로부터 알킬락테이트를 직접 제조하는 방법.The method of claim 3, wherein the trialkyl phosphate organic solvent extracting agent is a trialkyl phosphate organic solvent containing an alkyl group of C 1 to C 14 directly from the ammonium lactate.
- 제1항에 있어서, 상기 단계 1의 암모늄락테이트 수용액과 트리알킬포스페이트계 유기용매 추출제의 중량비는 1:1 내지 1:50인 것을 특징으로 하는 암모늄락테이트로부터 알킬락테이트를 직접 제조하는 방법.The method of claim 1, wherein the weight ratio of the aqueous ammonium lactate solution and the trialkyl phosphate organic solvent extractant in step 1 is 1: 1 to 1:50. .
- 제1항에 있어서, 상기 단계 1은 락트산의 추출효율을 증가시키기 위해 추가적으로 트리알킬아민을 첨가하여 수행하는 것을 특징으로 하는 암모늄락테이트로부터 알킬락테이트를 직접 제조하는 방법.The method of claim 1, wherein step 1 is performed directly by adding trialkylamine to increase the extraction efficiency of lactic acid.
- 제6항에 있어서, 상기 트리알킬아민은 20 중량% 이하로 사용하는 것을 특징으로 하는 암모늄락테이트로부터 알킬락테이트를 직접 제조하는 방법.The method of claim 6, wherein the trialkylamine is used in the preparation of alkyl lactate directly from ammonium lactate.
- 제1항에 있어서, 상기 단계 1은 100 내지 150 ℃의 범위에서 수행하는 것을 특징으로 하는 암모늄락테이트로부터 알킬락테이트를 직접 제조하는 방법.The method of claim 1, wherein step 1 is a method for producing alkyl lactate directly from ammonium lactate, characterized in that performed in the range of 100 to 150 ℃.
- 제1항에 있어서, 상기 단계 1은 1 기압 이하에서 수행하는 것을 특징으로 하는 암모늄락테이트로부터 알킬락테이트를 직접 제조하는 방법.The method of claim 1, wherein step 1 is a method for producing alkyl lactate directly from ammonium lactate, characterized in that carried out at 1 atm or less.
- 제1항에 있어서, 상기 단계 1은 10 내지 400 ㎜Hg의 감압 조건에서 수행하는 것을 특징으로 하는 암모늄락테이트로부터 알킬락테이트를 직접 제조하는 방법.The method of claim 1, wherein step 1 is a method for producing alkyl lactate directly from ammonium lactate, characterized in that it is carried out under reduced pressure of 10 to 400 mmHg.
- 제1항에 있어서, 상기 단계 2의 알코올은 C1 내지 C4의 저급 알코올인 것을 특징으로 하는 암모늄락테이트로부터 알킬락테이트를 직접 제조하는 방법.The method of claim 1, wherein the alcohol of step 2 is a process for producing an alkyl lactate directly from the ammonium lactate, characterized in that a lower alcohol of C 1 to C 4.
- 제1항에 있어서, 상기 단계 2의 락트산과 알코올의 몰비는 1:1 내지 1:10인 것을 특징으로 하는 암모늄락테이트로부터 알킬락테이트를 직접 제조하는 방법.The method of claim 1, wherein the molar ratio of lactic acid and alcohol of step 2 is 1: 1 to 1:10, the method for producing alkyl lactate directly from ammonium lactate.
- 제1항에 있어서, 상기 단계 2는 반응속도를 높이기 위해 산 촉매를 사용하는 것을 특징으로 하는 암모늄락테이트로부터 알킬락테이트를 직접 제조하는 방법.The method of claim 1, wherein step 2 is a method for producing alkyl lactate directly from ammonium lactate, characterized in that to use an acid catalyst to increase the reaction rate.
- 제13항에 있어서, 상기 산 촉매는 황산, 엠버리스트(Amberlyst), 나피온(Nafion), 나피온-실리카 복합물(Nafion-Silica Composite), Keggin형 헤테로폴리 산(Keggin-type heteropoly acid, H(8-x)XM12O40(X = Si4+, P5+ , M = W6+ 또는 Mo6+)), Nb2O5, HNbMoO6 및 제올라이트(Zeolite)로 이루어지는 군으로부터 선택되는 어느 하나인 것을 특징으로 하는 암모늄락테이트로부터 알킬락테이트를 직접 제조하는 방법.The method of claim 13, wherein the acid catalyst is sulfuric acid, Amberlyst, Nafion, Nafion-Silica Composite, Keggin-type heteropoly acid, H (8 -x) any one selected from the group consisting of XM 12 O 40 (X = Si 4+ , P 5+ , M = W 6+ or Mo 6+ )), Nb 2 O 5 , HNbMoO 6 and zeolite Method for producing an alkyl lactate directly from ammonium lactate, characterized in that.
- 제1항에 있어서, 상기 단계 2는 반응속도를 높이기 위해 대기압 이상의 가압 조건에서 수행하는 것을 특징으로 하는 암모늄락테이트로부터 알킬락테이트를 직접 제조하는 방법.The method of claim 1, wherein step 2 is a method for producing alkyl lactate directly from ammonium lactate, characterized in that carried out under pressurized conditions of atmospheric pressure or higher to increase the reaction rate.
- 제1항에 있어서, 상기 단계 2는 70 내지 150 ℃의 범위에서 수행하는 것을 특징으로 하는 암모늄락테이트로부터 알킬락테이트를 직접 제조하는 방법.The method of claim 1, wherein step 2 is a method for producing alkyl lactate directly from ammonium lactate, characterized in that performed in the range of 70 to 150 ℃.
- 제1항에 있어서, 알킬락테이트와 트리알킬포스페이트를 분리하기 위해 상기 단계 2는 추가적으로 증류공정 단계를 더 포함하는 것을 특징으로 하는 암모늄락테이트로부터 알킬락테이트를 직접 제조하는 방법.The method of claim 1, wherein the step 2 further comprises a distillation step to separate the alkyl lactate and the trialkyl phosphate.
- 제1항에 있어서, 상기 단계 2는 알코올 소모량을 최소화하기 위하여 알코올 재순환시스템에서 수행하는 것을 특징으로 하는 암모늄락테이트로부터 알킬락테이트를 직접 제조하는 방법.2. The method of claim 1, wherein step 2 is carried out in an alcohol recirculation system to minimize alcohol consumption.
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| KR10-2009-0092950 | 2009-09-30 | ||
| KR1020090092950A KR101140649B1 (en) | 2009-09-30 | 2009-09-30 | Process for preparing alkyl lactate from fermentation-derived ammonium lactate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107522687A (en) * | 2017-08-29 | 2017-12-29 | 沈阳金博地生态环保科技有限公司 | The method of Catalyzed by Phosphotungstic Acid synthesis of lactide from lactic acid |
| KR20180018680A (en) | 2015-06-10 | 2018-02-21 | 미리안트 코포레이션 | A new method for producing acrylic acid by acetaldehyde, which is a major byproduct |
| CN109438228A (en) * | 2018-09-28 | 2019-03-08 | 武汉三江航天固德生物科技有限公司 | The energy-saving processing technique and device of ethyl lactate |
| CN110637005A (en) * | 2017-03-15 | 2019-12-31 | Cj第一制糖株式会社 | Method for preparing alkyl lactate |
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| WO2018169181A1 (en) * | 2017-03-15 | 2018-09-20 | 씨제이제일제당 (주) | Method for producing alkyl lactate |
| KR102422368B1 (en) | 2020-09-29 | 2022-07-18 | 한국화학연구원 | An Esterification Method of Metal Organic Acid Salt and Carbon dioxide Conversion System Using the Same |
| US11607674B2 (en) | 2019-11-19 | 2023-03-21 | Korea Research Institute Of Chemical Technology | Heterogeneous catalyst complex for carbon dioxide conversion |
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| US6534679B2 (en) * | 1997-10-14 | 2003-03-18 | Cargill, Incorporated | Lactic acid processing; methods; arrangements; and, products |
| KR20050084179A (en) * | 2002-12-05 | 2005-08-26 | 아르끄마 | Continuous ethyl lactate preparation method |
| KR20050085397A (en) * | 2002-12-05 | 2005-08-29 | 아르끄마 | Continuous method for preparing ethyl lactate |
| WO2006124633A1 (en) * | 2005-05-13 | 2006-11-23 | Cargill, Incorporated | Production of lactic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6534679B2 (en) * | 1997-10-14 | 2003-03-18 | Cargill, Incorporated | Lactic acid processing; methods; arrangements; and, products |
| KR20050084179A (en) * | 2002-12-05 | 2005-08-26 | 아르끄마 | Continuous ethyl lactate preparation method |
| KR20050085397A (en) * | 2002-12-05 | 2005-08-29 | 아르끄마 | Continuous method for preparing ethyl lactate |
| WO2006124633A1 (en) * | 2005-05-13 | 2006-11-23 | Cargill, Incorporated | Production of lactic acid |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180018680A (en) | 2015-06-10 | 2018-02-21 | 미리안트 코포레이션 | A new method for producing acrylic acid by acetaldehyde, which is a major byproduct |
| CN110637005A (en) * | 2017-03-15 | 2019-12-31 | Cj第一制糖株式会社 | Method for preparing alkyl lactate |
| CN107522687A (en) * | 2017-08-29 | 2017-12-29 | 沈阳金博地生态环保科技有限公司 | The method of Catalyzed by Phosphotungstic Acid synthesis of lactide from lactic acid |
| CN109438228A (en) * | 2018-09-28 | 2019-03-08 | 武汉三江航天固德生物科技有限公司 | The energy-saving processing technique and device of ethyl lactate |
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| WO2011040700A3 (en) | 2011-06-03 |
| KR20110035303A (en) | 2011-04-06 |
| KR101140649B1 (en) | 2012-05-03 |
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