RU2129540C1 - Succinic acid or its salts production method - Google Patents

Abstract

FIELD: industrial organic synthesis. SUBSTANCE: succinic acid or its salts are produced via hydrogenation of maleic anhydride or maleic acid or its salts in water in presence of palladium-containing catalyst on carrier, more particularly palladium-nickel catalyst with Pd:Ni ratio 1:(0.5-5) or palladium-iron catalyst with Pd-Fe ratio 1:(0.1-6). EFFECT: significantly increased productivity of process per unit weight of palladium component. 1 tbl, 16 ex

Description

 The invention relates to a method for producing succinic acid or its salts by catalytic hydrogenation of maleic anhydride, or maleic acid, or maleic acid salts.

 Succinic acid is used in the manufacture of food additives, medicines, insecticides, dyes, some plastics, elastomers, polyester and alkyd resins, succinates, photographic materials, as well as for the synthesis of polynuclear hydrocarbons and analytical chemistry.

 Being a natural product of the body’s vital functions and a regulator of its protective functions, succinic acid and its derivatives improve physical condition, mood, memory and well-being, which is especially important under adverse and extreme conditions, prolonged stress, fatigue and a decrease in the body’s resistance to diseases, during prevention and treatment diseases.

 Along with the preparations of succinic acid proper, many of its derivatives are used, in particular, sodium, potassium, calcium and ammonium salts. Almost all succinic acid preparations activate the synthesis of steroid hormones in the adrenal glands and genital glands, have diuretic and cardiotonic effects, increase radiation resistance, are specific antidotes for poisoning with barbiturates, alcohol, and slow the development of atherosclerosis (see The therapeutic effect of succinic acid. Ed. Kondrasheva M.N., Pushchino, 1980).

 Known methods for producing succinic acid (UC) by chemical reduction of maleic anhydride (MA) in alkaline aqueous or alcoholic media in the presence of hydrazine hydrate (see Allen BB, Wyatt BW, Herze HR, J. Am. Chem. Soc., 1939, v 61, p. 843-846; Schwent E. ea J. Org. Chem., 1944, v. 9., p. 175-177. Hjelte NS Acta Chem. Scand, 1961, v. 15, N 5, p 1200. Pietra S., Ann Chimica, 1956, v. 46, p. 477-482.

 In this case, Raney nickel, 5% palladium on carbon, is used as catalysts. The resulting solutions of UC salts are neutralized, the solvent is evaporated, and the precipitate is recrystallized to obtain UC with a yield of 90/93% of theory.

 A known method of producing UC and its salts by hydrogenation of MA on Raney nickel at relatively high pressure (40-100 atm) in an alkaline medium (pH> 7) (see Japan patent N 64-24954, NKI 16 B 621, publ. 1964).

 A number of methods are known for producing UC by catalytic hydrogenation of MA in water at elevated temperature and pressure. As the catalysts in the known methods use metals of group VIII of the Periodic system (nickel, ruthenium, rhodium, palladium, platinum) in the form of a skeletal catalyst (skeletal nickel) (see US patent 2198153, NKI 260-341, publ. 1936), black ( palladium) (see Germany patent N 1259869, NKI 126 11, publ. 1968), oxides (platinum dioxide) (see Japan application N 69-29246, NKI 16 B 62, publ. 1969), or on a carrier (activated carbon ) (German patent N 1259869, NKI 12 B 11, publ. 1968, Japanese application N 61-204149, C 07 C 55/10, publ. 1986, Japanese application N 69-29246, NKI 16 B 62, publ. 1969) , kieselguhr (see Germany patent N 1259869, NKI 12 B 11, publ. 1968), aluminum oxide (see German patent N 1259869, NKI 12 B 11, publ. 1968).

 The use of skeletal nickel is possible only at high temperatures and pressure. The use of precious metals as catalysts allows one to obtain UC with a rather high yield (83-97%) under milder conditions than in the case of nickel contact, however, the catalyst productivity, expressed as the ratio of the weight of the UC to the weight of the metal per unit time, is not high enough .

 The conditions and results of hydrogenation in known methods are presented in the table.

 General disadvantages of the known methods are the use of contacts having a high content of precious metals, and their low productivity.

при этом норма расхода палладия - 1,04 • 10^-2 г палладия на 1 г ЯК.As a prototype, a method for producing succinic acid by hydrogenating maleic anhydride or maleic acid in water at a temperature of 80-100 ^o C and a hydrogen pressure of 4-20 atm in the presence of a catalyst - 5% palladium on carbon (see Japanese application N 69-29246, NKI 16 B 62, publ. 1969). The catalyst is used in an amount of 0.2% by weight of maleic anhydride, the initial concentration of which is 30-40 wt.%. The duration of hydrogenation is 2 hours. The product is isolated by crystallization after removal of the catalyst by filtration. The yield of succinic acid 95%, so melted. 186 ^o C, the performance of the process using this catalyst per unit mass of precious metal is 95.3

the rate of palladium consumption is 1.04 • 10 ^-2 g of palladium per 1 g of UC.

 The disadvantage of this method is the use of a catalyst having relatively low activity with a high palladium content in it, which leads to its low productivity, and in the production conditions - a high rate of consumption of precious metal per unit of production and, as a consequence, its high cost.

 The invention is aimed at solving the problem - without complicating the technology of the hydrogenation process, to significantly increase its productivity, i.e., removing the target product from a unit mass of precious metal per unit time, which leads to a proportional reduction in the cost of the product.

 This problem is solved by hydrogenation of maleic anhydride or maleic acid or maleic acid salts in water in the presence of a palladium-containing catalyst on a support. In this case, palladium-nickel catalyst is used as a catalyst with a palladium: nickel ratio of 1: 0.5-5, or palladium - an iron catalyst with a palladium: iron ratio of 1: 0.1-6.

при норме расхода палладия 0,4•10^-5 г на 1 г ЯК и снизить стоимость целевого продукта.Distinctive features of the process is that it is conducted in the presence of a palladium-nickel catalyst with a palladium: nickel ratio of 1: 0.5-5 or a palladium-iron catalyst with a palladium: iron ratio of 1: 0.1-6. The proposed catalysts have high activity at a relatively low palladium content, which allows to increase the productivity of the process (removal of succinic acid or its salt from a unit mass of precious metal per unit time) to 820

at a rate of palladium consumption of 0.4 • 10 ^-5 g per 1 g of UC and reduce the cost of the target product.

 The palladium content in the contacts is 0.05-0.5% by weight of the carrier (oxides, for example, aluminum, silicon, activated carbons, asbestos, etc.).

The process of hydrogenation of maleic anhydride, maleic acid and its salts is carried out in water in a wide range of temperature and pressure of hydrogen, however, exceeding the temperature of 90 ^o C and a pressure of hydrogen of 20 ati is irrational, because it does not give visible advantages.

 Hydrogenation on the proposed catalysts is carried out in an acidic, neutral or slightly alkaline medium (i.e., at pH≤7), which is preferable, since in an alkaline medium it is possible to convert maleic acid to its isomeric fumaric acid, which requires much more stringent conditions for hydrogenation.

 The catalyst preparation technique involves suspending the support in an alkaline aqueous medium and treating it with solutions of active metal compounds — nickel or iron salts and palladium polychlorohydroxo complexes. As salts of nickel and iron, their acetates, nitrates, sulfates, chlorides, palladium polychlorohydroxocomplexes are obtained by alkaline hydrolysis of palladium chloride in the presence of sodium chloride with an alkali metal hydroxide: palladium ratio of 0.25-0.65 (wt.).

 During the hydrogenation of salts (ammonium, sodium, potassium, etc.) of maleic acid, a preliminary reduction of the catalyst is not required; if, in order to obtain succinic acid, the process is forcedly carried out in an acidic medium, the catalyst must first be restored under conditions (temperature, hydrogen pressure) of the subsequent hydrogenation. Moreover, studies have shown that known catalysts containing palladium in reduced form exhibit significantly lower (10-20 times) activity than the proposed palladium-nickel and palladium-iron.

 The possibility of carrying out the invention is illustrated by the following examples.

 A. Preparation of catalysts.

Example 1a A catalyst with a content of (calculated) palladium - 0.2 wt.% And nickel - 1.0 wt.% Is prepared in a laboratory setup consisting of a round bottom flask with a capacity of 0.5 dm ³ , equipped with a stirrer, thermometer, dropping funnel, refrigerator and heated using a heating mantle, as well as a Bunsen flask with a funnel for filtering under vacuum.

A solution of nickel acetate is preliminarily prepared by dissolving 0.424 g of nickel acetate (Ni (CH ₃ COO) ₂ • 4H ₂ O) in 15 cm ^{3 of} distilled water at room temperature.

A solution of polychlorohydroxocomplexes of palladium (PHC Pd) is also preliminarily prepared. For this purpose, 1 cm ^{3 of} distilled water, 0.0028 cm ^{3 of} concentrated hydrochloric acid, 0.0336 g of palladium chloride (59.5% Pd) and 0.0333 g of potassium chloride are loaded into a 10 cm beaker. The mixture is heated to 65-70 ^o C, stirred on a magnetic stirrer until the palladium salt is completely dissolved. The resulting solution was cooled to 40-50 ^o C and hydrolyzed, slowly, dropwise, dosing a solution of potassium hydroxide (1N) to a mass ratio of KOH: Pd = 0.65, followed by exposure for two hours.

A suspension of 10 g (calculated on dry basis) of finely dispersed KSK silica gel in 100 cm ^{3 of} distilled water (silica gel is suspended in water at room temperature) is loaded into the flask for catalyst preparation. A suspension of silica gel is heated to 65-70 ^o C, and alkalinized 1N. a solution of potassium hydroxide to pH ≥ 10, then a solution of nickel acetate is dosed and the suspension is kept at a temperature of 65-70 ^o C with constant stirring for 0.5 hours. After exposure to the suspension, a previously prepared solution of PHC Pd is dosed, followed by a half-hour exposure. The catalyst suspension is filtered under vacuum on a Buchner funnel, the paste is washed with distilled water to the absence of chlorine ions in the wash water and dried to a residual moisture content of 20-30%.

 According to atomic absorption analysis, the finished catalyst contains (based on the dry weight of the product) 0.195% palladium and 0.975% nickel.

Example 2a A catalyst containing (calculated) 0.2% palladium and 0.2% nickel is prepared in a pilot plant consisting of a catalyst synthesis reactor with a capacity of 6.3 m ³ , a reactor for preparing a PHC Pd solution with a capacity of 0.63 m ³ , reactors preparing a solution of alkali with a capacity of 0.4 m ³ and a solution of nickel salt with a capacity of 0.1 m ³ , and for filtering and washing the catalyst - filter press type FPAKM.

Desalted water in the amount of 3.5-4.0 m ^{3 is} pumped into the catalyst synthesis reactor from the measuring unit and ~ 1000 kg of ACB-O coal with a humidity of 50% wt. Is loaded with stirring. The coal suspension is heated to 60-70 ^o C, then dosed 1N. an aqueous solution of sodium hydroxide (180-200 dm ³ ), after which a solution of nickel chloride (4 kg of NiCl ₂ • 6H ₂ O in 60-80 dm ³ desalted water) is slowly fed over a period of 30-40 minutes and holding for 30- 40 min with constant stirring and a temperature of ~ 65 ^o . Then, the contents of the reactor are cooled to 30-40 ^° and a solution of PChC Pd is dosed for 50-60 minutes. After an hour of exposure and filtration, the precipitate is washed with ten times the amount of water.

To obtain a solution of PHC Pd in the reactor (V = 0.63 m ³ ), 100-120 dm ³ desalted water, 130-140 cm ³ hydrochloric acid, 1.7 kg of palladium chloride and 0.6 kg of sodium chloride are loaded with stirring. Heated to 60-70 ^o C the mixture is stirred until complete dissolution of palladium chloride, then after cooling to 30-40 ^o slowly dose 1N. sodium hydroxide solution to a mass ratio of NaOH: Pd = 0.55.

 The catalyst according to atomic absorption analysis contains 0.19 wt.% Palladium and 0.18 wt.% Nickel.

 Example 3a A catalyst with a content (calculated) of 0.2 wt.% Palladium and 0.5 wt.% Nickel is prepared in the laboratory setup described in example 1a.

 A PdHC Pd solution is preliminarily prepared (as in Example 1a, but instead of potassium chloride, 0.0262 g of sodium chloride is added, hydrolysis is carried out with sodium hydroxide to a NaOH: Pd ratio of 0.25, and the exposure of the Pd. PCA solution is increased to five hours).

A solution of nickel sulfate is obtained by dissolving 0.243 g of NiSO ₄ • 7H ₂ O in 15 cm ^{3 of} distilled water.

10 g of finely dispersed chromatographic γ-alumina are suspended in 200 cm ^{3 of} distilled water, heated to ~ 65 ^° and 0.5N. NaOH solution, adjust the pH of the suspension to a value of 10-11, then the nickel sulfate solution is dosed and the hot suspensions are held for 30-60 minutes. Then the suspension is cooled to ~ 50 ^o , after which a solution of Pghq Pd is dosed, followed by exposure for 20-30 minutes.

The catalyst is filtered off and washed from chlorine ions, then dried to a residual moisture content of ~ 30 wt.%
According to the analysis, the finished catalyst contains 0.21 wt.% Palladium and 0.48% wt. Nickel (calculated on the dry product).

Example 4a The catalyst containing, by calculation, 0.1 wt.% Palladium and 0.05 wt.% Nickel is prepared in a plant consisting of an enameled synthesis reactor with a capacity of 160 dm ³ , equipped with a heating jacket, stirrer and refrigerator, a suction filter and a glass container dispenser.

With stirring, 80-100 dm ^{3 of} distilled water and 10 kg (in terms of dry) of OU-B coal are loaded. The suspension is heated to 65-70 ^o C and the pH is adjusted to 10.5 with a dosage of 0.5N. a solution of sodium hydroxide, then a solution of nickel chloride obtained by dissolving 21 g of NiCl ₂ • 6H ₂ O in 150-200 cm ^{3 of} water is dosed into the reactor for 10-15 minutes, followed by exposure for 30-40 minutes. The contents of the reactor are cooled to 50 ^o C and for 5-10 minutes the dosage of the previously prepared solution of PHC Pd is carried out.

A solution of PHC Pd is prepared by heating to a temperature of 65-70 ^o C with stirring a mixture of 17 g of palladium chloride, 11 g of sodium chloride, 1.3 cm ^{3 of} hydrochloric acid in 500 cm ^{3 of} distilled water, followed by cooling of the resulting solution to 50 ^o C with a dosage of 1N. sodium hydroxide solution to a mass ratio of NaOH: Pd = 0.45 and holding the solution for 2 hours.

After dosing the solution of PCHC Pd, the suspension is held at 50 ^° C for 30 minutes, then the catalyst precipitate is filtered and washed.

 The analysis catalyst contains 0.105% palladium and 0.055% nickel (calculated on the weight of the dry product).

 Example 5a A catalyst with a calculated content of 0.05 wt.% Palladium and 0.05 wt.% Nickel is prepared in the laboratory setup described in example 1A.

While stirring, 150 cm ^{3 of} distilled water and 20 g (calculated on dry basis) of Sibunit carbon powder carrier are loaded into the flask; the pH of the resulting suspension is adjusted to 12 by adding 0.25N. a solution of sodium hydroxide, then the suspension is heated to 90 ^o and a solution of nickel nitrate [0.05 g Ni (No ₃ ) ₂ • 6H ₂ O in 10 cm ^{3 of} distilled water] is dosed, followed by exposure during spontaneous cooling to 30-40 ^o . To a cooled suspension, a solution of PHC Pd prepared as follows: is dissolved with stirring and heating to ~ 70 ^o 0.017 g of palladium chloride and 0.011 g of sodium chloride in 5 cm ^{3 of} distilled water, add 0.001 cm ³ hydrochloric acid, cool the resulting solution to 50 ^o C and hydrolyze 0.25n. a solution of sodium hydroxide to a mass ratio of NaOH: Pd = 0.5. A solution of PHC Pd was incubated for 24 hours.

 After dosing a solution of PCHC Pd and holding for one hour, the catalyst is separated on a filter and washed with water until no chlorine ions are present.

 According to atomic absorption analysis, the finished catalyst contains 0.055 wt.% Palladium and 0.05 wt.% Nickel (calculated on the dry product).

 Example 6a A catalyst with a calculated content of 0.1 wt.% Palladium and 0.1 wt.% Iron is prepared in the installation described in example 4A.

A solution of PHC Pd is prepared preliminarily by dissolving 16.8 g of palladium chloride and 11.36 g of sodium chloride in 500 cm ^{3 of} distilled water, acidified with 1.3 cm ^{3 of} concentrated hydrochloric acid, after which the mixture is hydrolyzed for 0.5 N. a solution of sodium hydroxide to a ratio of NaOH: Pd = 0.45 and incubated for 3.5 hours. The resulting solution is dosed to a suspension of 10 kg of KSK silica gel in 80 dm ^{3 of} water at room temperature and neutral pH.

After a half-hour exposure of the suspension, a solution of iron chloride (48.5 g of FeCl ₃ • 6H ₂ O in 4-5 dm ^{3 of} water) is dosed, then 4 dm ^{3 of a} 2% solution of sodium carbonate and 28.5 dm ^{3 of a} 10% solution of sodium bicarbonate, followed by holding for 30-40 minutes The suspension is filtered, the catalyst paste is washed and squeezed on the filter to a residual moisture content of 20-30 wt.%.

 The finished catalyst contains 0.1% palladium and 0.12% iron based on the dry weight of the product.

 Example 7a A catalyst with a calculated content of 0.05 wt.% Palladium and 0.3 wt.% Iron is prepared in the laboratory setup described in example 1A.

20 g (calculated on dry) of OU-B coal containing 0.3 wt. % iron, and suspended in 200 cm ^{3 of} distilled water at room temperature.

 A solution of PChC Pd (as in Example 5a) is preliminarily prepared, which, after daily exposure, is dosed to a suspension of coal and incubated for 30-40 minutes. The suspension of the catalyst is processed as in example 1A and get a paste of the catalyst with a moisture content of 20-30% and a content of palladium and iron, which coincides according to atomic absorption analysis with the calculated one.

 Example 8a A catalyst with a calculated content of 0.5 wt.% Palladium and 0.05 wt. % iron is prepared in a pilot plant described in Example 2a.

3.5-4.0 m ^{3 of} demineralized water are pumped into the catalyst synthesis reactor from the measuring unit and ~ 500 kg of active cellolignin (ACB-O) is loaded with stirring, calculated on the weight of dry matter. 1N was added to the suspension of dry carrier at room temperature. sodium hydroxide solution to a pH of ~ 9.0, the contents of the reactor are heated to ~ 50 ^o C and a pre-prepared solution of iron sulfate (1.25 kg of FeSO ₄ • 7H ₂ O in 50-60 dm ^{3 of} water) is dosed, then ~ 10% solution sodium carbonate (6 kg of Na ₂ CO ₃ in 50-60 dm ^{3 of} water) and hold for 30-40 minutes at a temperature of 50-60 ^o C. At this temperature, pre-prepared solution of PHC Pd (4.2 kg of chloride palladium, 1.5 kg of sodium chloride, 250-300 dm ³ desalted water, 325-350 cm ³ hydrochloric acid) and incubated for 30-40 minutes.

 Washing and drying of the catalyst is carried out as in example 2A. The finished catalyst contains 0.52 wt.% Palladium and 0.05 wt.% Iron (according to atomic absorption analysis).

 B. Synthesis of succinic acid and its salts.

For the synthesis of succinic acid and its salts, three types of plants are used:
Type 1 - laboratory kinetic hydrogenation unit at constant temperature and pressure of hydrogen.

The reactor is a glass ampoule with a volume of 45-55 cm ³ , sealed in a steel, thermostatic casing of the shaking device, connected through a valve system with hydrogen and nitrogen cylinders, a buffer tank and a measuring system.

After the process is completed, hydrogen is replaced in the system with nitrogen, the catalyst is separated from the reaction mixture by "hot" vacuum filtration into an ice-cooled receiver, where succinic acid or its salt is isolated while cooling to 0 - (-5 ^° C). (In the case of the synthesis of salts of succinic acid after partial distillation of water from the mother liquor and cooling, an additional portion of the hydrogenation product can be isolated). The mother liquor is returned to recycling - to the hydrogenation stage.

 Type II - an autoclave with a capacity of 1 liter, equipped with a shielded motor and high-speed stirrer (n = 2700 rpm), equipped with hermetically connected heated drum filter (V = 0.5 l), a crystallizer (V = 1 l) with a feed jacket coolant and an automatic system for recording absorbed hydrogen.

The process in the reactor is carried out in polythermal conditions and in a narrow (3-5 ati) interval within the specified pressure. After the absorption of hydrogen has ceased, the catalysate is kept in an autoclave for 15-20 minutes with constant stirring, then the catalyzate is pressurized through a heated Druck filter into a crystallizer, into the jacket of which brine is fed. When cooled to 0 - (- 5 ^o C) crystallize succinic acid or its salts. The suspension is filtered, washed with chilled water and dried at a temperature of ~ 60 ^o C. The resulting mother liquor and wash water are recycled.

 Type III - a batch pilot plant consisting of a hydrogenation reactor, a heated filter to separate the catalyst, a crystallizer with a cooling jacket and a stirrer, a filter for the separation of succinic acid (or its salts) and a steam-heated dryer.

 A 25-liter reactor with a turbine stirrer (n = 2800 rpm), a jacket for heating (or cooling) and a lower outlet of the product.

 Heated filter with a filter surface of 0.14 m.

 A mold with an enameled inner surface, a frame stirrer (n = 43 rpm) and a jacket for cooling with brine.

Natch filter with a filter surface of 0.2 m ² .

 The calculated amount of water, maleic anhydride (acid) and catalyst are charged to the reactor. Upon receipt of the sodium or potassium salts of succinic acid, sodium hydroxide or potassium hydroxide, respectively, is charged into the reactor. Upon receipt of ammonium succinate, the dissolution of maleic anhydride (acid) is carried out in ~ 24% ammonia solution.

Hydrogenation is carried out at a constant pressure of hydrogen in polythermal mode. The hydrogenation temperature is maintained by supplying steam or cooling water to the reactor jacket. After the absorption of hydrogen and 10-15 minutes of exposure, the reaction mass is pushed through a heated filter into a mold, in the shirt of which brine is fed. Crystallization is carried out while cooling to O - (- 5 ^o C). The suspension is filtered on a suction filter, the precipitate is washed with chilled water and dried on baking sheets in a steam-heated dryer at a temperature of 60 ^° C. The mother liquor, wash water and catalyst are returned for reuse.

Upon receipt of succinic acid salts, the mother liquor and the wash water are subjected to additional stripping at a boiling point of not> 60 ^° C, as a result of which the salts are concentrated and more completely separated during subsequent crystallization and filtration.

 Example 1b The hydrogenation of maleic anhydride is carried out on a laboratory kinetic installation of type 1.

12 ml of distilled water, 3 g of maleic anhydride, 0.03 g of the catalyst prepared according to example 1a (soda Pd - 0.195 wt.%, Ni - 0.975 wt.%), The suspension of which was previously aged for water, were loaded into the reactor 30-40 minutes at a temperature of 50 ^o With constant stirring in a hydrogen atmosphere (1 at).

После отделения катализатора и вымораживания катализата (0^oC) получают 3,6 г (99,71% теор.) янтарной кислоты (Т_пл.-187,7-188,0^o), что соответствует производительности 308

при норме расхода 1,6 • 10^-5 г палладия на 1 г Я.к.The hydrogenation process at an excess pressure of hydrogen of 1 at and a temperature of 50 ^o C ends (with the absorption of hydrogen, corresponding to theoretical) in 200 minutes The activity of the catalyst is 5.85 • 10 ⁴

After separation of the catalyst and freezing of the catalyzate (0 ^° C.), 3.6 g (99.71% of theory) of succinic acid are obtained (T _pl. -187.7-188.0 ^° ), which corresponds to a productivity of 308

at a consumption rate of 1.6 • 10 ^-5 g palladium per 1 g Ya.k.

 Example 2b The hydrogenation of maleic acid is carried out in the type III plant described above using the catalyst prepared in Example 2 a.

 12 l of water, 4.0 kg of potassium hydroxide are charged into the reactor, stirred until dissolved, then 4 kg of maleic acid and 32 g of catalyst are charged.

The hydrogenation process is carried out at a constant hydrogen pressure of 10 atm and in a polythermal mode (T _beg. 25-30 ^o C, T _final. 95-105 ^o C).

при норме расхода 1,49•10^-5 г Pd на г янтарной кислоты (или ~ 0,9•10^-5 г Pd на 1 г дикалиевой соли янтарной кислоты).Theoretical absorption of hydrogen is achieved in 90 minutes. The activity of the catalyst is 14, .1 • 10 ⁴

at a rate of consumption of 1.49 • 10 ^-5 g Pd per g of succinic acid (or ~ 0.9 • 10 ^-5 g Pd per 1 g of dipotassium salt of succinic acid).

After the absorption of hydrogen has ceased and the reaction takes place for 15 minutes (with constant stirring, the catalyzate is pumped through a filter into the crystallizer, where it is cooled to 0 - (- 5 ^° C with stirring), after which precipitated crystals of succinic acid salt are separated. Mother liquor and catalyst they are returned from the Druk filter to the hydrogenation reactor for reuse, 3.9 kg of potassium hydroxide and 4 kg of maleic acid are loaded in. The hydrogenation process is repeated under the same conditions, the hydrogenation time in the second cycle is practically unchanged camping, in the third - it increased to two hours.

(или 1222,2

, а после трех циклов использования катализатора этот показатель незначительно снижается (до 669,2 и 1100 соответственно) при резком (втрое) снижении нормы расхода драгметалла - ~0,5 • 10^-5 г Pd на 1 г Я.к. (или ~0,3•10^-5 г палладия на 1 г диКсоли Я.к.).After three cycles of hydrogenation, ~ 20 kg is obtained (in terms of the dry weight of the dipotassium salt of succinic acid, which practically corresponds to the theoretical yield. The productivity in the first cycle is 743.5

(or 1222.2

, and after three cycles of using the catalyst, this indicator slightly decreases (to 669.2 and 1100, respectively) with a sharp (three-fold) decrease in the rate of consumption of precious metals - ~ 0.5 • 10 ^-5 g Pd per 1 g Ya.k. (or ~ 0.3 • 10 ^-5 g of palladium per 1 g of Ya.

 Elemental composition (%) of the hydrogenation product: C - 24.56; H 1.90; O - 33.06; K - 40.48 (p calculated: C - 24.73; H - 2.06; O - 32.94; K - 40.26).

, производительность (по первому циклу) - 418,2

и 386,1

(после трех циклов при тех же нормах расхода палладия (1 цикл 1,49•10^-5, 3 цикла - ~ 0,5•10^-5 г палладия на 1 г Я.к.).If, under the same conditions, hydrogenation of maleic acid (i.e., in the absence of potassium hydroxide) is carried out using the same catalyst, but pre-saturated with hydrogen under conditions close to the hydrogenation conditions (50 ^o C, 10 ati), then the time for complete hydrogenation will increase up to 2 hours 40 minutes in the first cycle. The activity of the catalyst is 7.9 • 10 ⁴

, productivity (on the first cycle) - 418.2

and 386.1

(after three cycles at the same rates of palladium consumption (1 cycle 1.49 • 10 ^-5 , 3 cycles - ~ 0.5 • 10 ^-5 g palladium per 1 g of ya).

The yield of succinic acid (after three cycles) is 99.5% (of theory), T _pl. - 185.2 - 186.0 ^o C.

 Example 3b The hydrogenation of maleic acid is carried out in a type 1 plant.

11 ml of water, 3.6 g of maleic acid, 0.06 g of the catalyst prepared according to Example 3 a and previously incubated in a hydrogen atmosphere (15 at) with constant stirring and a temperature of 90 ^° for 60 minutes are loaded into the ampoule.

.Hydrogenation under the same conditions (90 ^o and 15 at) is completed in 1 hour 20 minutes after the absorption of 695 ml (NTD) of hydrogen (100% of theory.). The activity of the catalyst 6.89 • 10 ⁴

.

при норме расхода 3,47 • 10^-5 г палладия на 1 г Я.к.After filtration, 3.63 g (99.1% of theory) of succinic acid (Tm _. - 186.5 - 187.2 ^o C) are isolated to separate the catalyst and cool the catalysis to ~ 0 ^° C, which corresponds to a capacity of ~ 360

at a consumption rate of 3.47 • 10 ^-5 g palladium per 1 g Ya.k.

 Example 4b. The hydrogenation of maleic anhydride is carried out in the type II unit described above.

 A solution of 114.3 g of sodium hydroxide in 550 ml of distilled water, 140 g of maleic anhydride and 2.1 g of the catalyst prepared according to example 4a is loaded into the reactor.

Air is displaced from the system with nitrogen, then it is filled with hydrogen, the suspension is heated to 30-35 ^o C and hydrogenation is carried out at a pressure of 10-15 atm.

Due to the heat of the reaction, the contents of the reactor are heated and by the end of the hydrogenation reaction, the temperature rises to 90-97 ^o C. After the reaction is completed (1 hour 25 minutes) and held for 15-20 minutes, the catalyst is separated by hot filtration, the catalyzate is cooled in a crystallizer, and analyze the hydrogenation product. The mother liquor and catalyst are returned to reload. The hydrogenation time in the second cycle is 1 hour 30 minutes, in the third - 1 hour 45 minutes.

(после 1 цикла) и 15,5•10⁴

(средняя, по трем циклам), производительность (после трех циклов) - 819,1

(или 1124,0

при норме расхода ~0,43•10^-5 г палладия на 1 г Я.к. (или 0,31•10^-5 г Pd на 1 г динатриевой соли Я.к.)
Суммарный выход динатриевой соли Я.к. после трех циклов - 694 г (т.е. практически количественный). Элементный состав продукта гидрирования:
Найдено (мас.%): C-29,70; Н-2,45; O-39,46; Na - 28,39
Рассчитано (мас.%): C-29,65; Н-2,48; O - 39,50; Na - 28,37
Когда гидрирование малеинового ангидрида проводят в вышеописанных условиях, но без добавления гидроксида натрия и в присутствии катализатора, восстановленного как в примерах 1 а и 2 а - время гидрирования уже в первом цикле увеличивается до 140 мин, активность катализатора составляет 1,04•10⁴

, производительность 546,0

при той же норме расхода катализатора.The activity of the catalyst is ~ 17.1 • 10 ⁴

(after 1 cycle) and 15.5 • 10 ⁴

(average, in three cycles), productivity (after three cycles) - 819.1

(or 1124.0

at a consumption rate of ~ 0.43 • 10 ^-5 g of palladium per 1 g of ya. (or 0.31 • 10 ^-5 g Pd per 1 g of disodium salt Ya.K.)
The total yield of disodium salt after three cycles, 694 g (i.e., practically quantitative). Elemental composition of the hydrogenation product:
Found (wt.%): C-29.70; H-2.45; O-39.46; Na - 28.39
Calculated (wt.%): C-29.65; H-2.48; O - 39.50; Na - 28.37
When the hydrogenation of maleic anhydride is carried out under the above conditions, but without the addition of sodium hydroxide and in the presence of a catalyst reduced as in examples 1 a and 2 a, the hydrogenation time in the first cycle increases to 140 minutes, the activity of the catalyst is 1.04 • 10 ⁴

, performance 546.0

at the same rate of catalyst consumption.

Total yield after three cycles - quantitative, T _pl. - 185.5 - 186.2 ^o C.

 Example 5b. The hydrogenation of the diammonium salt of maleic acid is carried out in a type I installation.

 10 ml of distilled water, 6 g of the diammonium salt of maleic acid and 0.12 g of the catalyst prepared according to Example 5 a are loaded into the ampoule.

, что соответствует производительности 505

и норме расхода ~1,1•10⁵ г палладия на 1 г диаммонийной соли Я.к.Hydrogenation at a hydrogen pressure of 5 at and a temperature of 80 ^{o is} completed 3 hours after the absorption of the hydrogen volume corresponding to the calculated one. The activity of the catalyst is 7.54 • 10 ⁴

that corresponds to a performance of 505

and consumption rate ~ 1.1 • 10 ⁵ g of palladium per 1 g of diammonium salt Ya.k.

After a partial “soft” distillation of water and subsequent freezing out of the catalysis with a yield of 98.9%, the diammonium salt Ya.k., with T _pl. - 162.4 - 163.1 ^o C.

 Example 6b. The hydrogenation of maleic anhydride is carried out on a type II plant.

1 цикл); 7,6•10⁴

(II цикл); 5,71•10⁴

(III цикл). Суммарная производительность по трем циклам - 375

при норме расхода 0,55•10^-5 г палладия на 1 г Я.к.The catalyst prepared in accordance with Example 6 a in an amount of 3.2 g is suspended in 500 ml of distilled water and kept in a hydrogen atmosphere (10-15 ati) at 70-80 ^° C under continuous stirring for an hour, then 160 g of maleic anhydride are charged and hydrogenate at a hydrogen pressure of 10-12 atmospheres. The initial hydrogenation temperature is 40 ^o C, increases by the moment of complete absorption of hydrogen (after 130 minutes) up to 90-95 ^o C. The activity of the catalyst is 8.79 • 10 ⁴

1 cycle); 7.6 • 10 ⁴

(II cycle); 5.71 • 10 ⁴

(III cycle). Total performance in three cycles - 375

at a consumption rate of 0.55 • 10 ^-5 g palladium per 1 g Ya.k.

After three cycles, a total of 576 g of succinic acid was isolated (T _mp 186.6-187.1 ^° C), which is ~ 99.7% (theory).

 Example 7b The hydrogenation of maleic anhydride is carried out on a type 1 plant.

16 ml of an aqueous solution of ammonia (ρ = 0.91 g / cm ³ ) containing ~ 24 wt.% NH ₃ , 10 g of the catalyst prepared according to Example 7 a are loaded into the ampoule.

, его производительность - 505,2

при норме расхода 0,65•10^-5 г палладия на 1 г диаммонийной соли Я.к.Hydrogenation at a constant pressure of hydrogen (15 at) and a temperature of 80 ^{o is} completed after 5 hours of theoretical absorption of hydrogen. The activity of the catalyst is 7.6 • 10 ⁴

Its performance is 505.2

at a consumption rate of 0.65 • 10 ^-5 g palladium per 1 g of diammonium salt

The salt isolated in 97.8% yield has T _pl. = 161.8-162.2 ^o .

 Example 8b. The hydrogenation of maleic anhydride is carried out in a type III plant using the catalyst obtained in example 8a.

что соответствует производительности 367

(в расчете на 100 % выход) и норму расхода 0,29•10^-4 г палладия на 1 г Я.к.14 l of distilled water and 28 g of catalyst are charged into the reactor; the suspension with constant stirring and a temperature of 90 ^o C is incubated for one hour under a hydrogen pressure of 15 MPa. Then, 4.0 kg of maleic anhydride is charged into the reactor and hydrogenation is carried out at a pressure of 15 atm in a temperature range of 60-95 ^° C, which is completed ~ 90 min after absorption of ~ 915 m ³ H ₂ (NTD). The activity of the catalyst is 6.98 • 10 ⁴

which corresponds to a performance of 367

(per 100% yield) and consumption rate of 0.29 • 10 ^-4 g of palladium per 1 g Ya.k.

 The mother liquor after separation of the precipitate and the catalyst is returned to the hydrogenation reactor for rehydrogenation. Then, as described in example 2b, the procedure for returning the catalyst and mother liquor is repeated again.

, средняя активность катализатора ~5,4•10⁴

, норма расхода 0,9•10^-5 г Pd на 1 г Я.к.The total productivity (in three cycles) is 285.7

, average catalyst activity ~ 5.4 • 10 ⁴

, the consumption rate of 0.9 • 10 ^-5 g Pd per 1 g Ya.k.

Dedicated in 99.6% of theory. succinic acid has a T _pl. - 186.8 - 187.0 ^o C.

Claims (1)

 A method of producing succinic acid or its salts by liquid-hydrogenation of maleic anhydride, or maleic acid, or maleic acid salts in water in the presence of a palladium-containing catalyst on a support, characterized in that the catalyst used is a palladium-nickel catalyst with a palladium: nickel ratio of 1: 0.5 - 5, or a palladium-iron catalyst with a palladium: iron ratio of 1: 0.1 - 6.

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