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WO2009048355A1 - Method for producing isothiocyanates - Google Patents

Method for producing isothiocyanates Download PDF

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Publication number
WO2009048355A1
WO2009048355A1 PCT/RU2008/000648 RU2008000648W WO2009048355A1 WO 2009048355 A1 WO2009048355 A1 WO 2009048355A1 RU 2008000648 W RU2008000648 W RU 2008000648W WO 2009048355 A1 WO2009048355 A1 WO 2009048355A1
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WO
WIPO (PCT)
Prior art keywords
water
mustard
isothiocyanates
steam
minutes
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/RU2008/000648
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French (fr)
Russian (ru)
Inventor
San Gyn Che
Vladimir Alekseevich Groshev
Andrey Evgenevich Nikitin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Society Volgograd Mustard Creamery 'sarepta' W L L
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Society Volgograd Mustard Creamery 'sarepta' W L L
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Application filed by Society Volgograd Mustard Creamery 'sarepta' W L L filed Critical Society Volgograd Mustard Creamery 'sarepta' W L L
Publication of WO2009048355A1 publication Critical patent/WO2009048355A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/02—Recovery or refining of essential oils from raw materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
    • C07C331/16—Isothiocyanates

Definitions

  • the invention relates to the food industry and can be used to obtain flavorings of essential mustard oils - isothiocyanates from by-products of mustard and oil production.
  • a known method of producing isothiocyanates in which an aqueous suspension is prepared from products of processing mustard-oil production in a ratio of 1: 6. The prepared suspension is subjected to extraction at a temperature of 75-9O 0 C for 30 minutes, then the phases are separated. The solid phase is washed with water and enzymatic hydrolysis of the thioglycosides contained in the liquid phase is carried out at a temperature of 40-60 0 C, followed by treatment with hot steam to obtain isothiocyanates (see RF patent N ° 2196811, IPC CI lB 13/00, 2002).
  • RF patent JTs 2196812, IPC CI lB 13/00, 2002 describes a method for producing isothiocyanates, comprising preparing an aqueous suspension of solid by-products of mustard and oil production, taken in relation to water 1: 10, followed by heating the suspension to a temperature of 45-50 ° C, in which the suspension is incubated for 15 minutes. In the process of 15-minute exposure, hydrolysis of synigrin occurs, from which isothiocyanates or ether are formed mustard oil. To extract isothiocyanates after their formation, the suspension is treated with hot steam for 40 minutes. After this, an aqueous emulsion of isothiocyanates is fed to condensation and separation with water.
  • the reasons that impede the achievement of the following technical result when using the known method include the energy intensity and duration of the process, which provides for the preparation of an aqueous suspension using a large volume of water and the need to heat it to a temperature of 45-50 0 C.
  • Energy costs require subsequent processing during 40 minutes of cooked volume with hot steam.
  • the process of hot steam treatment involves blowing off a product with steam, which must be heated up to 100 0 C through the apparatus wall to start evaporation.
  • the duration of the heat treatment stage in the known method affects the duration of the whole process, which accordingly indicates its costs.
  • the technical result of the invention is to increase efficiency by reducing energy costs and reducing the duration of the process.
  • the specified technical result in the implementation of the invention is achieved by the fact that in the known method for producing isothiocyanates from solid by-products, mustard oil production, introduced into the container with water with the formation of a dispersed system with stirring, which is heated to a temperature of 45-50 0 C, kept at this temperature for 15 minutes, then subjected to further processing, after which, the resulting isothiocyanates are fed to condensation and separation with water, according to the invention, the solid phase is mixed with water, the content of which does not exceed 30%, and additional processing is carried out under vacuum.
  • processing under vacuum allows one to reduce the time at this stage and, accordingly, to reduce the duration of the process, and also, not bringing the boiling point to the limit value (100 0 C), to generate water vapor.
  • the distillation of the essential oil from the dispersed system is carried out at the same temperature at which the 15-minute hydrolysis of sinigrin was carried out. In this case, unlike the prototype, it is not necessary to heat the dispersed system through the jacket of the apparatus to 100 0 C.
  • the flakes are heated to 54 0 C and incubated for 15 minutes, during which enzymatic hydrolysis of sinigrin occurs.
  • mustard flakes are also steamed with hot steam for 30 minutes.
  • deaf steam is supplied to the steam jacket to quickly heat the flakes to 102 ° C and to distill the essential oil.
  • steam for entrainment of the formed isothiocyanates is not supplied from the outside, steam is used which is released during boiling water during processing under vacuum.
  • the raw material for the production of essential oil is ground mustard seeds, the oil content (fat) of which is 38%, while the raw material in the present method is cake - a by-product of oil and fat production. After pressing the oil, the residual oil content of the cake is 8%.
  • processing under vacuum allows you to fully collect the essential oil due to the fact that in the line there is no atmospheric air trapping light fraction, which complicates the subsequent process of oil condensation.
  • the method is as follows. 1000 kg of by-products of mustard and oil production (cake) and 300 kg of water are loaded into the mixer. Constantly mixing, the resulting mass is fed into the hydrolyzer dryer. In the apparatus, the temperature of the mixture is brought to 50 0 C and incubated for 15 minutes. Then, at a pressure of 0.1 atm. create a vacuum in the hydrolyzer. The mixture heated to 50 0 C is kept under vacuum for 20 minutes, while the water evaporates intensively, since when the pressure is released, the boiling point of the water is much lower than the limit value and is ⁇ 50 0 C. The mustard essential oils contained in water vapor are removed through isothiocyanates capture system, and then served for condensation and separation.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)

Abstract

The inventive method can be used in the food industry. Said isothiocyanate producing method consists in intensively agitating solid side-products of mustard-oil pressing production, simultaneously adding not more than 30% of water thereto and in holding the thus produced paste for 15 minutes at a temperature of 45-50°C. Volatile oils of mustard are vacuum extracted together with water steam. Once the steam has been condensed, the oils are separated from water.

Description

СПОСОБ ПОЛУЧЕНИЯ ИЗОТИОЦИАНАТОВ METHOD FOR PRODUCING ISOTHYOCIOCANATES

Изобретение относится к пищевой промышленности и может быть использовано для получения ароматизаторов эфирных горчичных масел - изотиоцианатов из побочных продуктов горчично-маслобойного производства.The invention relates to the food industry and can be used to obtain flavorings of essential mustard oils - isothiocyanates from by-products of mustard and oil production.

Известен способ получения изотиоцианатов, при котором из продуктов переработки горчично-маслобойного производства соотношением 1 :6 готовят водную суспензию. Приготовленную суспензию подвергают экстракции при температуре воды 75- 9O0C, в течение 30 мин, затем фазы разделяют. Твердую фазу промывают водой и при температуре 40-600C осуществляют ферментативный гидролиз тиогликозидов, содержащихся в жидкой фазе, с последующей обработкой острым паром для получения изотиоцианатов (см. патент РФ N° 2196811, МПК CI lB 13/00, 2002).A known method of producing isothiocyanates, in which an aqueous suspension is prepared from products of processing mustard-oil production in a ratio of 1: 6. The prepared suspension is subjected to extraction at a temperature of 75-9O 0 C for 30 minutes, then the phases are separated. The solid phase is washed with water and enzymatic hydrolysis of the thioglycosides contained in the liquid phase is carried out at a temperature of 40-60 0 C, followed by treatment with hot steam to obtain isothiocyanates (see RF patent N ° 2196811, IPC CI lB 13/00, 2002).

В патенте РФ JTs 2196812, МПК CI lB 13/00, 2002 описан способ получения изотиоцианатов, включающий подготовку водной суспензии твердых побочных продуктов горчично- маслобойного производства, взятых по отношению к воде 1 :10, с последующим подогревом суспензии до температуры 45-50° С, при которой суспензию выдерживают в течение 15 минут. В процессе 15-тиминyтнoй выдержки происходит гидролиз синигрина, из которого образуются изотиоцианаты или эфирное горчичное масло. Для извлечения изотиоцианатов после их образования в течение 40 минут проводят обработку суспензии острым паром. После этого водную эмульсию изотиоцианатов подают на конденсацию и разделение с водой.RF patent JTs 2196812, IPC CI lB 13/00, 2002 describes a method for producing isothiocyanates, comprising preparing an aqueous suspension of solid by-products of mustard and oil production, taken in relation to water 1: 10, followed by heating the suspension to a temperature of 45-50 ° C, in which the suspension is incubated for 15 minutes. In the process of 15-minute exposure, hydrolysis of synigrin occurs, from which isothiocyanates or ether are formed mustard oil. To extract isothiocyanates after their formation, the suspension is treated with hot steam for 40 minutes. After this, an aqueous emulsion of isothiocyanates is fed to condensation and separation with water.

К причинам, препятствующим достижению указанного ниже технического результата, при использовании известного способа относится энергоемкость и длительность процесса, в котором предусмотрено приготовление водной суспензии с использованием большого объема воды и необходимость ее нагрева до температуры 45-500C. Энергетических затрат требует последующая обработка в течение 40 минут приготовленного объема острым паром. Процесс обработки острым паром подразумевает продувку паром продукта, который для начала испарения должен быть нагрет через стенку аппарата до 1000C. Длительность стадии тепловой обработки в известном способе, влияет на длительность всего процесса в целом, что соответственно свидетельствует и о его затратах.The reasons that impede the achievement of the following technical result when using the known method include the energy intensity and duration of the process, which provides for the preparation of an aqueous suspension using a large volume of water and the need to heat it to a temperature of 45-50 0 C. Energy costs require subsequent processing during 40 minutes of cooked volume with hot steam. The process of hot steam treatment involves blowing off a product with steam, which must be heated up to 100 0 C through the apparatus wall to start evaporation. The duration of the heat treatment stage in the known method affects the duration of the whole process, which accordingly indicates its costs.

Техническим результатом изобретения является повышение экономичности за счет снижения энергетических затрат и сокращения длительности процесса.The technical result of the invention is to increase efficiency by reducing energy costs and reducing the duration of the process.

Указанный технический результат при осуществлении изобретения достигается тем, что в известном способе получения изотиоцианатов из твердых побочных продуктов горчично- маслобойного производства, введенных в емкость с водой с образованием при перемешивании дисперсной системы, которую нагревают до температуры 45-500C, выдерживают при данной температуре в течение 15 минут, затем подвергают дополнительной обработке, после чего , образовавшиеся изотиоцианаты подают на конденсацию и разделение с водой, согласно изобретению твердую фазу смешивают с водой, содержание которой не превышает 30%, а дополнительную обработку проводят под вакуумом.The specified technical result in the implementation of the invention is achieved by the fact that in the known method for producing isothiocyanates from solid by-products, mustard oil production, introduced into the container with water with the formation of a dispersed system with stirring, which is heated to a temperature of 45-50 0 C, kept at this temperature for 15 minutes, then subjected to further processing, after which, the resulting isothiocyanates are fed to condensation and separation with water, according to the invention, the solid phase is mixed with water, the content of which does not exceed 30%, and additional processing is carried out under vacuum.

Пары воды, испаряющейся из системы в процессе дополнительной обработки, как острым паром, так и под вакуумом насыщены образовавшимися изотиоцианатами. Однако обработка под вакуумом позволяет сократить на данной стадии время и соответственно уменьшить длительность процесса, а также, не доводя до предельного значения (1000C) температуру кипения, осуществить образование водяного пара. В заявляемом техническом решении отгонка эфирного масла из дисперсной системы осуществляется при той же температуре, при которой проводился 15-ти минутный гидролиз синигрина. При этом в отличие от прототипа не требуется проводить нагрев дисперсной системы через рубашку аппарата до 1000C. В отличие от известных способов получения изотиоцианатов для осуществления процесса достаточно произвести небольшое увлажнение твердого продукта. Необходимое содержание воды составляет не более 30% вместо 85-90%. Из уровня техники известен способ переработки семян горчицы (Мustаkаs G., Кirk L., Sohns V. апd Gгiffiп E. Мustаrd sееd рrосеssiпg: imрrоvеd mеthоds fоr isоlаtiпg thе рuпgепt fасtоr апd сопtrоlliпg рrоtеiп quаlitу // Thе jоurήаl оf Аmеriсап оil сеmists' sосiеtу. 1965. vоl. 12). При осуществлении данного способа горчичные хлопья загружают в аппарат для гидролиза и доводят до влажности 30%. Во время перемешивания хлопья нагревают до 540C и выдерживают 15 минут, в течение которых происходит энзиматический гидролиз синигрина. Однако после гидролиза также осуществляется пропаривание горчичных хлопьев острым паром в течение 30 минут. Одновременно при этом в паровую рубашку подается глухой пар для быстрого нагрева хлопьев до 1020C, и отгонки эфирного масла. В заявляемом техническом решении пар для уноса образовавшихся изотиоцианатов не подается извне, используется пар, выделяющийся при кипении воды при обработке под вакуумом. Кроме того, сырьем для получения эфирного масла являются измельченные семена горчицы, масличность (жир) которых составляет 38%, в то время, как сырьем в заявляемом способе является жмых - побочный продукт масложирового производства. После прессового отжима масла остаточная масличность жмыха - 8 %. По сравнению с известными способами обработка под вакуумом позволяет в полной мере собрать эфирное масло за счет того, что в линии улавливания легкой фракции отсутствует атмосферный воздух, который затрудняет последующий процесс конденсации масла.Vapors of water evaporating from the system during the additional processing, both with sharp steam and under vacuum, are saturated with the formed isothiocyanates. However, processing under vacuum allows one to reduce the time at this stage and, accordingly, to reduce the duration of the process, and also, not bringing the boiling point to the limit value (100 0 C), to generate water vapor. In the claimed technical solution, the distillation of the essential oil from the dispersed system is carried out at the same temperature at which the 15-minute hydrolysis of sinigrin was carried out. In this case, unlike the prototype, it is not necessary to heat the dispersed system through the jacket of the apparatus to 100 0 C. In contrast to the known methods for producing isothiocyanates, it is sufficient to slightly moisten the solid product to carry out the process. Water Required It is not more than 30% instead of 85-90%. The method of processing mustard seeds is known from the prior art (Mustakas G., Kirk L., Sohns V. apd Giffiff E. Mustard séd rössessipg: imréved method régépulépélépélépélépélépélépélépélipépélipélépélipélégépélipélipélipélipélipélipélipélégépélipélipélipet 1965. vol. 12). When implementing this method, mustard flakes are loaded into a hydrolysis apparatus and brought to a moisture content of 30%. During mixing, the flakes are heated to 54 0 C and incubated for 15 minutes, during which enzymatic hydrolysis of sinigrin occurs. However, after hydrolysis, mustard flakes are also steamed with hot steam for 30 minutes. At the same time, deaf steam is supplied to the steam jacket to quickly heat the flakes to 102 ° C and to distill the essential oil. In the claimed technical solution, steam for entrainment of the formed isothiocyanates is not supplied from the outside, steam is used which is released during boiling water during processing under vacuum. In addition, the raw material for the production of essential oil is ground mustard seeds, the oil content (fat) of which is 38%, while the raw material in the present method is cake - a by-product of oil and fat production. After pressing the oil, the residual oil content of the cake is 8%. Compared with known methods, processing under vacuum allows you to fully collect the essential oil due to the fact that in the line there is no atmospheric air trapping light fraction, which complicates the subsequent process of oil condensation.

Способ осуществляется следующим образом. В смеситель загружают 1000 кг побочных продуктов горчично-маслобойного производства (жмых) и 300 кг воды. Постоянно перемешивая, образовавшуюся массу подают в гидролизер-сушилку. В аппарате температуру смеси доводят до 500C и выдерживают 15 минут. Затем при давлении 0,1 атм. в гидролизере создают вакуум. Нагретую до 500C смесь под вакуумом выдерживают в течение 20 минут, при этом вода интенсивно испаряется, так как при сбросе давления значение температуры кипения воды значительно ниже предельного и составляет ~ 500C. Содержащиеся в парах воды эфирные горчичные масла - изотиоцианаты удаляют через систему улавливания, а затем подают на конденсацию и разделение.The method is as follows. 1000 kg of by-products of mustard and oil production (cake) and 300 kg of water are loaded into the mixer. Constantly mixing, the resulting mass is fed into the hydrolyzer dryer. In the apparatus, the temperature of the mixture is brought to 50 0 C and incubated for 15 minutes. Then, at a pressure of 0.1 atm. create a vacuum in the hydrolyzer. The mixture heated to 50 0 C is kept under vacuum for 20 minutes, while the water evaporates intensively, since when the pressure is released, the boiling point of the water is much lower than the limit value and is ~ 50 0 C. The mustard essential oils contained in water vapor are removed through isothiocyanates capture system, and then served for condensation and separation.

Энергетические затраты при осуществлении заявляемого технического решения по сравнению с известными способами получения изотиоцианатов, в процессе осуществления которых проводят продувку острым паром водной суспензии побочных продуктов горчично-маслобойного производства, снизились в 2 раза, а длительность процесса составляет 1 час 20 минут, то есть сократилась в 1,5 раза. Energy costs in the implementation of the proposed technical solution compared with the known methods for producing isothiocyanates, during the implementation of which are carried out by blowing with steam the aqueous suspension of by-products of mustard and oil production, decreased by 2 times, and the duration of the process is 1 hour 20 minutes, that is, decreased 1.5 times.

Claims

ФОРМУЛА ИЗОБРЕТЕНИЯ. CLAIM. Способ получения изотиоцианатов из твердых побочных продуктов горчично-маслобойного производства, введенных в емкость с водой с образованием при перемешивании дисперсной системы, которую после нагрева и 15 минутной выдержки при температуре нагрева подвергают дополнительной обработке для образования паровой фазы с подачей последней на конденсацию и разделение, отличающийся тем, что твердые продукты смешивают с водой, содержание которой в системе не превышает 30%, а дополнительную обработку проводят под вакуумом. A method of producing isothiocyanates from solid by-products of mustard and oil production, introduced into a container with water with the formation of a dispersed system with stirring, which, after heating and 15 minutes at a heating temperature, is subjected to additional processing to form a vapor phase with the latter being fed to condensation and separation, which differs the fact that solid products are mixed with water, the content of which in the system does not exceed 30%, and additional processing is carried out under vacuum.
PCT/RU2008/000648 2007-10-12 2008-10-14 Method for producing isothiocyanates Ceased WO2009048355A1 (en)

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RU2007138047/13A RU2346980C1 (en) 2007-10-12 2007-10-12 Isothiocyanate production method
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RU2562522C1 (en) * 2014-06-10 2015-09-10 Общество с ограниченной ответственностью "Волгоградский горчичный завод "Родос" (ООО "Волгоградский горчичный завод "Родос") Essential mustard oil production method
RU2598263C2 (en) * 2014-12-08 2016-09-20 Общество с ограниченной ответственностью "Группа Юджи" Method and apparatus for processing by-products of mustard and oil processing production (versions)

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