SU850639A1

SU850639A1 - Method of acetone solution acidity control

Info

Publication number: SU850639A1
Application number: SU792833572A
Authority: SU
Inventors: Тофик Махмур Керимов; Владимир Степанович Глухов
Original assignee: Грозненское Научно-Производственноеобъединение "Промавтоматика"
Priority date: 1979-10-26
Filing date: 1979-10-26
Publication date: 1981-07-30

Description

Изобретение относится к способам контроля кислотности ацетонового раствора и может быть применено в системах управления процессом ацетонирования L сорбозы, например, в производстве аскарбиновой кислоты.The invention relates to methods for controlling the acidity of an acetone solution and can be used in control systems for the process of acetonation of L sorbose, for example, in the production of ascarboxylic acid.

Процесс ацетонирования L -сорбозы осуществляют путем растворения сорбозы в кислом ацетоновом-растворе, получае мом путем смешения олеума и ацетона.The process of acetonation of L-adsorption is carried out by dissolving sorbose in an acidic acetone solution, obtained by mixing oleum and acetone.

Известные способы контроля кислот ности различных растворов по косвенным параметрам: плотности, pH, удельной электропроводносги и т.п. используются при анализе бинарных сред И· 15Known methods for controlling the acidity of various solutions by indirect parameters: density, pH, electrical conductivity, etc. used in the analysis of binary environments And · 15

В многокомпонентных средах использование известных способов невозможно. Наиболее близким к предлагаемому по технической сущности и достигаемому результату является способ контроля кис— а лотности ацетонового раствора, содержащего олеум и ацетон, заключающийся в измерении концентрации олеума, темпера туры олеума и ацетона до растворения, температуры полученной смеси и определения кислотности ацетонового раствора по измеренным параметрам [2 ],In multicomponent environments, using known methods is not possible. Closest to the proposed technical essence and the achieved result is a method of controlling the acidity of an acetone solution containing oleum and acetone, which consists in measuring the concentration of oleum, the temperature of oleum and acetone before dissolution, the temperature of the mixture and determining the acidity of the acetone solution from the measured parameters [2]

В предлагаемом способе на конечный результат измерения кислотности ацетонового раствора существенное влияние оказывает измерение содержания влаги в ацетоне даже при стабильном его расходе. Это связано с тем, что в процессе ацетонирования L -сорбозы используется ре., т генерируемый ацетон, содержание влаги которого колеблется от 0,2 до 2,0масс.%. При анализе зависимостей содержания влаги в ацетоне и кислотности ацетонового раствора от температуры реакции смешивания, которые указаны в предлагаемом способе, а также полученные экспериментально по ВНИИПИ 'Промавтоматика', выяснилось, что изменение содержания влаги в ацетоне на + 0,2% приводит к изменению температуры реакции смешения на 1,2 С. Это приводит к погрешности измерения кислотности ацетонового раствора равной 3,8 г/л, что составляет 19% от диапазона измерения (85 ; 105 г/л). Такая погрешность в измерении кислотности ацетонового раствора приводит к образованию избытка воды, не связанной олеумом и увеличению кислотности ацето- 5 нового раствора, что, в свою очередь, приводит к образованию побочных продуктов, снижающих выход целевого продукта. Это требует дополнительного измерения и стабилизации содержания влаги в ацетоне, 10 что в свою очередь усложняет способ из^· мереная. Кроме того, предлагаемый способ не дает ясной картины о качестве киалого ацетонового раствора, находящегося непосредственно в ацетонаторе. 15In the proposed method, the final result of measuring the acidity of an acetone solution is significantly affected by measuring the moisture content in acetone even at a stable flow rate. This is due to the fact that, in the process of L-adsorption acetonation, re., T generated acetone is used, the moisture content of which ranges from 0.2 to 2.0 mass%. When analyzing the dependences of the moisture content in acetone and the acidity of the acetone solution on the temperature of the mixing reaction, which are indicated in the proposed method, as well as obtained experimentally by VNIIIPI Promavtomatika, it was found that a change in the moisture content in acetone of + 0.2% leads to a change in temperature mixing reaction at 1.2 C. This leads to an error in measuring the acidity of the acetone solution equal to 3.8 g / l, which is 19% of the measuring range (85; 105 g / l). Such an error in the measurement of the acidity of an acetone solution leads to the formation of an excess of water not bound by oleum and an increase in the acidity of the acetone 5 solution, which, in turn, leads to the formation of by-products that reduce the yield of the target product. This requires additional measurement and stabilization of the moisture content in acetone, 10 which, in turn, complicates the method of ^ · measured. In addition, the proposed method does not give a clear picture of the quality of the kialic acetone solution located directly in the acetonator. fifteen

Цель изобретения - повышение точности измерения за счет исключения влияния изменения содержания влаги в ацетоне.The purpose of the invention is to improve the measurement accuracy by eliminating the influence of changes in the moisture content in acetone.

Поставленная цель достигается тем, 20 что дополнительно отбирают пробу кислого ацетонового раствора (КАР) из ацето кагора, измеряют ее температуру, смешивают с олеумом в диапазоне соотношений от 20 :This goal is achieved by the fact that 20 additionally take a sample of an acidic acetone solution (CAR) from acetone cahors, measure its temperature, mix with oleum in the range of ratios from 20:

1,5 до 20 :1.5 to 20:

8 ^КДР ’ мл олеума) калориметре, измеряют температуру получаемой смеси и по известным и вновь измёряемым параметрам определяют кислотность ацетонового раствора. ³⁰ 8 ^KDR 'ml oleum) calorimeter, the temperature of the resulting mixture is measured and the acidity of the acetone solution is determined by known and newly measured parameters. ^thirty

Для выявления возможности определения кислотности ацетоновых растворов термохимическим способом проведена серия опытов, заключающаяся в смешении кислых ацетоновых растворов концентра- ³⁵цией в диапазоне от 80 до 110 г/л с олеумом (концентрацией 20% св. 50^ и 2% св. SO j) и определении температуры, термохимической реакции смешения.To identify the possibility of determining the acidity of acetone solutions by the thermochemical method, a series of experiments was carried out, consisting in mixing acidic acetone solutions with a concentration of ³⁵ in the range from 80 to 110 g / l with oleum (concentration of 20% St. 50 ^ and 2% St. SO j) and determination of temperature, thermochemical mixing reaction.

Анализ ацетоновых растворов в преде- ⁴⁰лах концентрации от 80 до 110 г/л можно определить термохимическим способом с точностью, не уступающей методу титрования. При этом, на конечный результат измерения температуры термохимической ⁴⁵реакции заметное влияние оказывают концентрация олеума и исходные температуры олеума и кислого ацетонового раствора.Analysis acetone solutions in the limit concentration of ⁴⁰ crystals of from 80 to 110 g / l can be determined by thermochemical means with accuracy not inferior titration method. Moreover, the final result of measuring the temperature of the thermochemical reaction ⁴⁵ is significantly affected by the concentration of oleum and the initial temperatures of oleum and acidic acetone solution.

На фиг. 1 приведен график зависимости, температур термохимических реакций сме- ^1,50шения кислых ацетоновых растворов с концентрациями 85г/л-(а) и 105 г/л-(б) и олеума концентрацией 20% св. SO₂ot их соотношения объемов;In FIG. Figure 1 shows a plot of the temperature and thermochemical reactions of mixing ^1.50 mixtures of acidic acetone solutions with concentrations of 85 g / l- (a) and 105 g / l- (b) and oleum with a concentration of 20% St. SO ₂ ot their volume ratios;

на фиг. 2 - график зависимости температур термохимических реакций смешения кислых ацетоновых растворов с концентрациями. 83 г/л -(В) и 105г/л-(2).in FIG. 2 is a graph of the temperature dependence of thermochemical reactions of mixing acidic acetone solutions with concentrations. 83 g / l - (B) and 105 g / l - (2).

и олеума концентрацией 2% св, 50 от из? соотношения объемов;and oleum concentration of 2% sv, 50 from volume ratios;

на фиг. 3 показан график зависимости температур термохимических реакций смешения кислых ацетоновых растворов с олеумом концентрацией 28% св. SCj при соотношении их объемов 20:2,5 от концентрации кислых ацетоновых растворов в диапазоне от 80 до 110 г/л при их исходных температурах, равных ^KCtp * С - (d) и ·έ:_Η(φ=27 С;in FIG. Figure 3 shows a graph of the temperature dependence of thermochemical reactions mixing acidic acetone solutions with an oleum concentration of 28% St. SCj at a ratio of their volumes of 20: 2.5 on the concentration of acidic acetone solutions in the range from 80 to 110 g / l at their initial temperatures equal to ^ KCtp * С - (d) and · έ: _{Η (} φ = 27 С;

t_0A=21 С-(е)t _0A = 21 C- (e)

На- фиг. 4 изображена принципиальная схема реализации предлагаемого способа.FIG. 4 shows a schematic diagram of the implementation of the proposed method.

При этом, результаты опытов показали, что увеличение объема олеума концент• рацией 20% св. 5θ} свыше 3 мл, . при постоянном объеме кислых ацетоновых растворов равного 20 мл вызывает интенсификацию образования окиси мезитила и приводит к ухудшению сходимости результатов опытов, а увеличение объема олеума концентрацией 2% св. SO} свыше Змл, при постоянном объеме ацетоновых растворов равного 20 мл, не дает разности температур термохимических реакций при смешении с ацетоновыми растворами кон ценграцией 85 г/л и 105 г/л, которая необходима для контроля кислотности кислых ацетоновых растворов.Moreover, the results of the experiments showed that an increase in oleum volume with a concentration of 20% sv. 5θ} over 3 ml. with a constant volume of acidic acetone solutions equal to 20 ml, it intensifies the formation of mesityl oxide and leads to a deterioration in the convergence of the experimental results, and an increase in the volume of oleum with a concentration of 2% St. SO} above Zl, with a constant volume of acetone solutions equal to 20 ml, does not give the temperature difference of thermochemical reactions when mixed with acetone solutions with a concentration of 85 g / l and 105 g / l, which is necessary to control the acidity of acidic acetone solutions.

Поэтому, для уменьшения погрешности ' измерения при дозировании или изменении концентраций олеума в диапазоне от 2% св.60^ до 20% св. 5О3 диапазоном соотношений объемов кислых ацетоновых растворов и олеума можно считать диапазон, равный от 20 : 1,7 до 20 : 2,7 при котором ' размл олеума)?Therefore, to reduce the measurement error during dosing or changing oleum concentrations in the range from 2% St. 60 ^ to 20% St. 5O3 the range of ratios of volumes of acidic acetone solutions and oleum can be considered a range equal to from 20: 1.7 to 20: 2.7 at which 'milling oleum)?

ность температур термохимических реакций смешения была больше 1,5 С (фиг.1 и 2).the temperature range of thermochemical mixing reactions was more than 1.5 C (Figs. 1 and 2).

Однако, Для экстрагирования влаги, содержащейся в ацетоне, в процессе ацетонирования L -сорбозы подают олеум концентрацией от 20% св. G до 25% св, $0¾.However, To extract moisture contained in acetone, oleum with a concentration of 20% St. G up to 25% sv, $ 0¾.

Поэтому , для использования предлагаемого способа в производственных условиях, целесообразно соотношение кислых ацетоновых растворов (КАР) и олеума (концентрацией 20% св. 50-} +25% св. SO3) иметь в диапазоне от 20 : 1,5 до 20 : . (МД-КДЕ. На фиг. 4 пока-.мл блеума) зан ацетонатор 1, куда поступают технологические потоки ацетона и олеума; тру бопровод 2, по которому непосредственно из ацетонатора 1 с помощью побудителя расхода подается представительная проба кислого ацетонового раствора в калориметр 3. В калориметр 3 также из тех- ₅нологического потока по трубопроводу поступает олеум. Смесь олеума с кислым ацетоновым раствором из калориметра 3 поступает.в ацетонатор 1.Термодатчики 46 служат для измерения температуры, со- ю ответственно, кислого ацетонового раствора до смешения с олеумом, олеума до смешения с кислым ацетоновым раствором, смеси кислого ацетонового раствора с олеумом в калориметре 3,. Датчиком концент- и рации олеума 7 и термодатчики 4-6 связаны с вычислительным устройством 8.Therefore, to use the proposed method under production conditions, it is advisable to have the ratio of acid acetone solutions (CAR) and oleum (concentration of 20% St. 50-} + 25% St. SO3) in the range from 20: 1.5 to 20:. (MD-KDE. In Fig. 4 so far .ml of bleum), acetonator 1 is taken, where the process flows of acetone and oleum; pipeline 2, through which a representative sample of acidic acetone solution is fed directly from the acetonator 1 to the calorimeter 3. Calorimeter 3 also receives oleum from the process flow ₅ through the pipeline. A mixture of oleum with an acidic acetone solution from the calorimeter 3 enters. The acetonator 1. The temperature sensors 46 are used to measure the temperature, respectively, of the acidic acetone solution before mixing with oleum, the oleum before mixing with acidic acetone solution, a mixture of acidic acetone solution with oleum in calorimeter 3. The oleum 7 concentration and walkie-talkie sensors and temperature sensors 4-6 are connected to the computing device 8.

Работа предлагаемой схемы заключается в следующем.The work of the proposed scheme is as follows.

Определенное количество представитёль-20 ной пробы кислого ацетонового раствора из ацетонатора 1 с помощью побудителя расхода по трубопроводу 2 поступает в калориметр 3. При этом измеряют температуру кислого ацетонового раствора термодат-25 чиком 4.A certain amount of a representative sample of an acidic acetone solution from acetonator 1 is supplied to the calorimeter 3 by means of a flow inducer 2 through a flow meter. In this case, the temperature of the acidic acetone solution is measured using a temperature sensor 25.

Из линии технологического потока one—, ума, поступающего в аценатор 1, отбирают определенное количество олеума, измеряют его температуру тёрмодатчиком зо 5, концентрацию датчиком 7 и направляют в гот же калориметр 3 для смешения с кислым ацетоновым раствсром в определенных соотношениях. Термодатчиком 6 измеряют температуру реакции смеше- 35 ния получаемой смеси. Получаемая смесь олеума с кислым оцетоновым раствором из калориметра 3 поступает в ацетонат ор .1.A certain amount of oleum is taken from the line of the one-process flow, the mind entering the acenerator 1, its temperature is measured with a temperature sensor 3, concentration with a sensor 7, and calorimeter 3 is sent to the goth for mixing with an acidic acetone solution in certain proportions. A temperature sensor 6 measures the temperature of the mixing reaction of the resulting mixture. The resulting mixture of oleum with an acidic acetone solution from calorimeter 3 enters the .1 acetonate.

В вычислительном устройстве 8 по тем—· 40 пературе получаемой смеси, с учетом исходных температур кислого ацетонового раствора и олеума, а также концентрации олеума, определяют кислотность ацетонового раствора в ацегонаторе 1.In computing device 8, the temperature of the resulting mixture, taking into account the initial temperatures of the acidic acetone solution and oleum, as well as the concentration of oleum, determines the acidity of the acetone solution in the acegonator 1.

Использование предлагаемого способа обеспечивает повышение точности измерения за счет исключения влияния изменения содержания влаги в ацетоне и увеличение выхода целевого продукта более чем на 1,5%. В денежном выражении экономический эффект от внедрения предлагаемого способа на одном ацегонаторе ориенгировечно составляет 50 тыс. рублей в год.Using the proposed method provides improved measurement accuracy by eliminating the influence of changes in the moisture content in acetone and increasing the yield of the target product by more than 1.5%. In monetary terms, the economic effect of introducing the proposed method on one aggregator is approximately 50 thousand rubles per year.

Claims

The invention relates to methods for controlling the acidity of an acetone solution and can be applied in acetonation acetonation control systems, sorbose, nage, in the production of ascaric acid. The process of acetonation of L-sorbose is carried out by dissolving the sorbose in an acidic, acetone solution, obtained by mixing oleum and acetone. Known methods for controlling the acidity of various solutions by indirect parameters: density, pH, conductivity, etc. used in analyzing binary media ij. In (the use of ear-worn media using known methods is impossible. Closest to the proposed technical essence and the achieved result is a method of controlling the acidity of an acetone solution containing oleum and acetone, consisting in measuring the concentration of oleum, temperature of oleum and acetone until dissolved. the mixture and the temperature of the acidity of the acetone solution by the measured parameters 2. In the proposed method, the final result of measuring the acidity of the acetone solution is The effect is the intent of the moisture content in acetone, even when it is consumed in a stable manner, due to the fact that during the acetonation of L-sorbose, the relative amount of acetone generated is used, whose moisture content varies from 0.2 to 2, Om. When analyzing the dependences of the moisture content in acetone and the acidity of the acetone solution on the temperature of the mixing reaction, which are indicated in the proposed method, as well as experimentally obtained by VNIIPI Promavtomatika, it was noted that the change in the moisture content in acetse is + 0.2% at Odita to a change in reaction temperature mixing 1.2 C. This leads to measurement errors acetone solution acidity equal to 3.8 g / l, which is 19% or 38 measuring range (85; 105 g / l). Such an error in measuring the acidity of the acetone solution leads to the formation of excess water not bound by oleum and an increase in the acidity of the acetone solution, which, in turn, leads to the formation of by-products that reduce the yield of the target product. This requires an additional measure to stabilize the moisture content in acetone, which in turn complicates the measurement method. In addition, the proposed method does not give a clear picture of the quality of KI4OGO acetone solution, located directly in the acetonator. The goal of isophotenia is to increase the measurement accuracy by eliminating the effect of changes in the moisture content in acetone. This goal is achieved by additionally taking a sample of an acidic acetone solution (CAR) from an acetonator, measuring its temperature, and mixing it with oleum in the range of ratios from 20: 1.5 to 2: 2.8. in the 1LL CAeNMCl) calorimeter, the temperature of the resulting mixture is measured and the acidity of the acetone solution is determined from known and newly measured parameters. To reveal the possibility of determining the acidity of acetone solutions by thermochemical method, a series of experiments were carried out, consisting in mixing acidic acetone solutions with a concentration in the range from 8O to HO g / l with oleum (concentration 20% St. 5O, and 2% St. 50 j) and O {temperature, thermochemical mixing reaction. The analysis of acetal solutions in the range of concentrations from 8O to HO g / l can be determined by thermochemical method with an accuracy not inferior to the titration method. At the same time, the final result of measuring the temperature of the thermochemical reaction is significantly affected by the concentration of oleum and the initial temperatures of oleum and acid acetone solution. FIG. Figure 1 shows a plot of the temperatures t of the chemical reactions of 1USNION of acidic acetone solutions with concentrations of 85 g / l- (a) and 1O5 g / l- (b) and ola concentration of 2O% st. SOj, oT their volume ratio; in fig. 2 is a graph of thermochemical temperatures of the mixtures of acidic acetone solutions with conditrations. 83 g / l- (B) and 1O5g / l. (2) -. 9 and oleum with a concentration of 2%, 50%, from JK of the ratio of volumes; on fi1. 3 shows a plot of the temperatures of thermochemical reactions of mixing acidic acetone solutions with ole. mind concentration of 28% of sv. SCj with a ratio of their volumes of 20: 2.5 to the concentration of acidic acetone solutions in the range from 80 to НO g / l at their initial temperatures equal to Char –Lol 17s - (d) and i ,, 27 С; C- (e) FIG. 4 shows a schematic diagram of the implementation of the proposed method. When sToiv, the results of experiments showed that an increase in ogum ogum concentration of 20% St. 50-j over 3 ml,. at a constant volume of acidic acetone solutions equal to 2O ml, the formation of mesityl oxide is intensified and results in deterioration of the results of experiments, but an increase in oleum concentration of 2% c5O over 3 ml, with a constant volume of acetone dilutions of BqjOB equal to 20 ml, temperature differences of thermochemical reactions when mixed with acetone solutions with a concentration of 85 g / l and 1O5 g / l, which is necessary to control the acidity of acidic acetone pacTBqioB. Therefore, to reduce the measurement error when dosing or changing the concentrations of oleum in dp-output, from 2% b.p., to 2O%. 503 the range of ratios of obl, ems of acidic acetone solutions and oleum can be considered a range of 20: 1.7 to 20: 2.7 2.7 JJJlliLii.iE-. at which grind oleum). The thermopolymer mixing thermoprotection was greater than 1.5 ° C (Figs. 1 and 2). However, in order to extract the moisture contained in the acetone, in the process of acetonation of the L-phosphorus, oleum is fed at the center of 2O% st. S O- up to 25% of sv. $ 0. Therefore, in order to use the proposed method under production conditions, it is advisable that the ratio of acidic acetic solutions (CAR) and oleum (concentration of 2O% St. 50h + 25% St. 90h) be in the range from 2O: 1.5 to 2O:. 2.8 UVWIJIAP. In FIG.: 4 Poka-ml (Brieum), an acetonator 1, where the technolysical flows of acetone and oleum are fed; Pipeline 2, through which a representative sample of the acidic acetone solution is fed to the calorimeter 3 by means of a flow rate booster to the calorimeter 3. Oleum is also supplied from the process stream through the pipeline 3. A mixture of oleum with an acidic acetone solution from calorimeter 3 flows into acetonator 1. Thermal sensors 46 serve to measure the temperature, respectively, of an acidic acetone solution before mixing with oleum, oleum before mixing with an acidic acetone solution of a mixture of an acidic acetone solution with an oligome in a calorimeter 3, . The oleum concentration sensor 7 and the temperature sensors 4-6 are associated with the computing device 8. The operation of the proposed scheme is as follows. A certain amount of G1Repedual sample of an acidic acetone solution and an acotonator 1 with a flow metering device through line 2 enters the calorimeter 3. At the same time, the temperature of the acidic acetone solution is measured by a thermal sensor}, From the process flow of the oleum entering the accenter 1, the temperature indicator is removed the amount of oleum is measured by its temperature gauge 5, the concentration by sensor 7, and the calorimeter O is sent to that o to be mixed with an acidic acetone solution in specific ratios. The temperature in the HONTopRKT is the temperature of the reaction for displacing the resulting mixture. The resulting mixture of oleum with an acidic ocetal solution from calorimeter 3 enters acetonator 1. In computing device 8, the acidity of the acetone solution in acets is determined by taking into account the initial temperatures of the acidic acetone solution to oleum, as well as the concentration of oleum. Ator 1. The use of the prearranged method ensures that measurement accuracy is increased by eliminating the effect of a change in the moisture content in acetone and an increase in the yield of the target product by more than 1.5%. In monetary terms, the economic effect of the implementation of the proposed method on one acetonator is approximately 5 thousand rubles a year. The invention of the method of controlling the acidity of an acetone solution containing oleum and acetone by measuring the concentration and temperature of the oleum and temperature of the acetone solution in the calorimeter entering the acetonator, characterized in that, in order to improve the accuracy of the measurement by eliminating the effect / change in content moisture in acetone; in addition, a sample of the acetic solution is taken from the acetonate; it is mixed with oleum in a calorimeter in a ratio of 2: 1.5-2.8 and the acidity of acetone is determined by the indicated parameters. th solution. Sources of information taken into account in the examination 1. M. V. Kulakov. Technological measurements and tests for chemical production. Mechanical Engineering, M., 19G6,. 373-479.

2. Authors certificate of the USSR 562543, cl. C 07 V 3/00, O1 N-31 / OO, 1976 (prototype).

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