The method of obtaining succinic acid or its salts

 

(57) Abstract:

The invention relates to an improved process for the preparation of succinic acid or its salts, which are widely used in the production of pharmaceuticals, food additives, plastics, elastomers, photos. According to the invention succinic acid or its salt is produced by hydrogenation of maleic anhydride or maleic acid, or the corresponding salts of maleic acid in water in the presence of palladium catalyst on the carrier, which is used as palladium-Nickel catalyst at a ratio of palladium: Nickel, which is 1: 0.5 to 5, or palladium-iron catalyst at a ratio of palladium: iron is 1: 0.1 to 6. The invention allows to significantly improve the performance of the process, i.e. the removal of the target product with a unit mass of palladium per unit of time, which leads to a proportional reduction in the cost of the product. table 1.

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

Succinic acid is used in the production of food additives, Lek of succinate, photographic materials, as well as for the synthesis of polynuclear hydrocarbons and analytical chemistry.

As a natural product of metabolism, and regulation of its protective functions, succinic acid and its derivatives improve the physical condition, mood, memory and feeling, which is especially important under adverse and extreme conditions of prolonged stress, fatigue and lower body resistance to diseases, for the prevention and treatment of diseases.

Along with the drugs actually succinic acid are used in many of its derivatives, in particular, sodium, potassium, calcium and ammonium salts. Virtually all drugs of succinic acid activate the synthesis of steroid hormones in the adrenal glands and gonads, have diuretic and cardiotonic action, increase the resistance to radiation, are specific antidotes for poisoning by barbiturates, alcohol, slow the development of atherosclerosis (see Therapeutic effect of succinic acid. Under. edit Kondrasheva M. N., Pushchino, 1980).

Known methods for producing succinic acid (UC) chemical recovery of maleic anhydride (MA) in alkaline water J. Org. Chem., 1944, v. 9. p. 175-177. Hjelte N. S. Acta Chem. Scand, 1961, v. 15, N 5, p. 1200. Pietra S., Ann Chimica, 1956, v. 46, p. 477-482.

As catalysts for this use Raney Nickel, 5% palladium on coal. The resulting salt solutions YAK neutralized, evaporated the solvent, the residue is recrystallized getting YAK with access 90/93% of theory.

A method of obtaining the YAK and its salts by hydrogenation of MA Raney Nickel at a relatively high pressure (40 to 100 ATM) in alkaline medium (pH > 7) (see Japan patent N 64-24954, NCI 16 B 621, publ. 1964).

The number of known ways to get YAK catalytic hydrogenation of MA in water at elevated temperature and pressure. As catalysts in the known methods using metals of group VIII of the Periodic system (Nickel, ruthenium, rhodium, palladium, platinum) in the form of a skeletal catalyst (skeletal Nickel) (see U.S. patent 2198153, NCI 260-341, publ. 1936), mobiles (palladium) (see patent Germany N 1259869, NCI 126 11, publ. 1968), oxides (platinum dioxide) (see Japan's bid N 69-29246, NCI 16 B 62, publ. 1969), or media (activated carbon) (patent Germany N 1259869, NCI 12 B 11, publ. 1968, Japan's bid N 61-204149, C 07 C 55/10, publ. 1986, Japan's bid N 69-29246, NCI 16 B 62, publ. 1969), kieselgur (see patent Germany N 1259869, NCI 12 B 11, publ. 1968), the oxide aluminati temperatures and pressures. The use of precious metals as catalysts allows to obtain a YAK with a sufficiently high yield (83-97%) under milder conditions than in the case of Nickel contact, however, the performance of the catalyst, expressed as the ratio of a significant part of the YAK to weight parts of metal per unit of time, is not high enough.

Conditions and results of hydrogenation in the known methods is presented in the table.

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

As a prototype of the selected method to produce succinic acid by hydrogenation of maleic anhydride or maleic acid in water at a temperature of 80-100oC and hydrogen pressure, 4-20 ATS in the presence of catalyst (5% palladium on coal (see Japan's bid N 69-29246, NCI 16 B 62, publ. 1969). The catalyst is used in amount of 0.2% by weight of maleic anhydride, the concentration of which is 30-40 wt.%. The duration of the hydrogenation of 2 hours. The product distinguish crystallization after removal of the catalyst by filtration. The yield of succinic acid 95%, so plvl. 186oC, the performance of the process using a-2g of palladium per 1 g of the YAK.

The disadvantage of this method is the use of a catalyst having relatively low activity at high concentration of palladium, which leads to low productivity and production conditions - high rate of consumption of the precious metal per unit of output and, consequently, high costs.

The invention is directed to solution of the problem - not complicating the technology of hydrogenation process, to significantly improve its performance, i.e., removal of the target product per unit mass of the precious metal per unit of time, which leads to a proportional reduction in the cost of the product.

This task is solved by the hydrogenation of maleic anhydride or maleic acid, or salts of maleic acid in water in the presence of palladium catalyst on the carrier, the catalyst used palladium - Nickel catalyst at a ratio of palladium : Nickel, which is 1 : 0.5 to 5, or palladium - iron catalyst at a ratio of palladium : iron is 1 : 0.1 to 6.

Distinctive features of the process is that it is carried out in the presence of palladium-Nickel catalyst when the ratio is 1: 0.1 to 6. The proposed catalysts have high activity at relatively low concentrations of palladium, which allows to increase the efficiency of the process (removal of succinic acid or a salt thereof with a unit mass of the precious metal per unit of time) to 820 with a consumption rate of palladium 0,410-5g per 1 g of the YAK and reduce the cost of the target product.

The palladium content in the contacts is 0.05 to 0.5% by weight of the carrier (oxides, such as aluminum, silicon, activated carbon, asbestos, and so on).

The process of hydrogenation of maleic anhydride, maleic acid and its salts are in the water in a wide range of temperature and hydrogen pressure, but the temperature exceeds 90oC and hydrogen pressure of 20 MPa is irrational, because it will not give visible benefits.

Hydrogenation of the proposed catalysts is carried out in acidic, neutral or slightly alkaline environment (i.e., at pH7), which is preferred because in an alkaline environment may become maleic acid isomeric her fumaric acid, hydrogenation of which require much more stringent conditions.

The method of preparing the catalyst involves the suspension of the carrier in an alkaline aqueous medium and the palladium. As salts of Nickel and iron use their acetates, nitrates, sulfates, chlorides, polihlorirovanie palladium receive the alkaline hydrolysis of palladium chloride in the presence of sodium chloride at a ratio of hydroxide of alkaline metal : palladium equal to 0,25 - 0,65 (wt.).

When the hydrogenation salts (ammonium, sodium, potassium, and D. R.) maleic acid no prior recovery of the catalyst, if the purpose of obtaining succinic acid process internally is conducted in an acidic medium, the catalyst must first be restored to the conditions (temperature, hydrogen pressure) subsequent hydrogenation. Moreover, studies have shown that the known catalysts containing palladium in restored form, show significantly lower (10-20 times) activity than offer the palladium-Nickel and palladium-iron.

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

A. Preparation of catalysts.

Example 1A. The catalyst content (calculated) palladium - 0.2 wt.% and Nickel - 1.0 wt.% prepared in a laboratory setup consisting of a round-bottom flask with a capacity of 0.5 DM3equipped with many Bunsen funnel for filtration under vacuum.

Pre-prepare a solution of Nickel acetate, dissolving 0,424 g of Nickel acetate (Ni(CH3COO)24H2O) in 15 cm3distilled water at room temperature.

Also pre-prepare a solution of polihlorgidratov palladium (PGK Pd). For this purpose in the glass with a capacity of 10 cm load 1 cm3distilled water, 0,0028 cm3concentrated hydrochloric acid, 0,0336 g of palladium chloride (59,5% Pd) and 0.0333 g of potassium chloride. The mixture is heated to 65-70oC, stirred on a magnetic stirrer until complete dissolution of the salts of palladium. The resulting solution was cooled to 40-50oC and hydrolyzing, slowly, dropwise, a dosing solution of potassium hydroxide (1N) until the mass ratio of KOH : Pd = 0,65, followed by exposure for two hours.

Into the flask for the preparation of the catalyst load a suspension of 10 g (dry) of fine silica gel brand "CSC" 100 cm3distilled water (silica gel suspended in water at room temperature). The suspension of the silica gel was heated to 65-70oC, and alkalinized 1H. a solution of potassium hydroxide to pH 10, then dispense a solution of Nickel acetate and maintain the suspension at a temperature of 65-70oC and constant Pd followed a half-hour exposure. The suspension of catalyst was filtered under vacuum on a Buchner funnel, pasta washed with distilled water to the absence of chloride ions in the wash water and dried to a residual moisture content of 20-30%.

According to atomic absorption analysis of the finished catalyst contains (calculated on the weight of dry product) of € 0.195% palladium and 0,975% Nickel.

Example 2A. The catalyst containing (by calculation) of 0.2% of palladium and 0.2% Nickel prepare the experimental narabotany installation, consisting of a synthesis reactor catalyst capacity of 6.3 m3reactor solution PGC Pd capacity 0,63 m3, reactors preparation of a solution of alkali capacity of 0.4 m3and of Nickel salt solution with a capacity of 0.1 m3and for filtration and washing of the catalyst - filter-press type FPAKM.

In the synthesis reactor catalyst from the dipstick pump demineralized water in an amount of 3.5-4.0 m3and load with stirring ~1000 kg of coal, ACB-ON with a humidity of 50% wt. The suspension of the coal is heated to 60-70oC, then dispense 1H. an aqueous solution of sodium hydroxide (180-200 DM3), after which slowly for 30-40 minutes serves a solution of Nickel chloride (4 kg NiCl26H2O 60-80 DM3demineralized water) and carry out exposure for /SUP> and dispense the solution PGC Pd for 50-60 minutes After the time the shutter and the filter residue is washed ten times with water.

To obtain the solution PGC Pd in the reactor (V = 0,63 m3) under stirring download 100-120 DM3demineralized water, 130-140 cm3hydrochloric acid, 1.7 kg of palladium chloride and 0.6 kg of sodium chloride. Heated to 60-70oC the mixture is stirred until complete dissolution of palladium chloride, and then after cooling to 30-40oslowly dispense 1H. the sodium hydroxide solution until the mass ratio of NaOH : Pd = 0,55.

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

Example 3A. The catalyst content (by calculation) 0.2 wt.% palladium and 0.5 wt.% Nickel is prepared in a laboratory setup described in example 1A.

Pre-prepare a solution PGC Pd (as in the example 1A, but instead of potassium chloride added 0,0262 g of sodium chloride, hydrolysis of lead sodium hydroxide to the ratio of NaOH : Pd = 0.25 and the extract solution PGC Pd. increase to five hours).

A solution of Nickel sulfate receive, dissolving 0,243 g with NISO47H2O 15 cm3of distilled water.

10 g of fine chromatograph is or NaOH, bring the pH of the suspension to a value of 10-11, then dispense a solution of Nickel sulfate and withstand hot suspensions 30-60 minutes and Then the suspension is cooled to ~ 50o, and then dispense the solution PGC Pd, followed by exposure for 20 to 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 of the finished catalyst contains at 0.21 wt.% palladium and 0,48% wt. Nickel (calculated on the dry product).

Example 4A. The catalyst containing the rate of 0.1 wt.% palladium and 0.05 wt.% Nickel is prepared for installation, consisting of enameled synthesis reactor with a capacity of 160 DM3equipped with a jacket for heating, stirrer and refrigerator, suction filter and glass container-dispenser.

Charged to the reactor with stirring 80-100 DM3distilled water and 10 kg (in terms of dry) coal OU-b, the Suspension is heated to 65-70oC and pH adjusted to 10.5 with dosage of 0.5 n sodium hydroxide solution, and then into the reactor over a period of 10-15 min dispense a solution of Nickel chloride, obtained by dissolving 21 g NiCl26H2O 150-200 cm3water, followed by exposure for 30-40 minutes the Contents of the reactor is cooled to 50oC and chechenieva to 65-70oC with stirring, a mixture of 17 g of palladium chloride, 11 g of sodium chloride, 1.3 cm3hydrochloric acid in 500 cm3distilled water followed by cooling the resulting solution to 50oC dosage 1H. solution of sodium hydroxide until the mass ratio of NaOH:Pd = 0,45 and the extract solution within 2 hours.

After dosing solution PGC Pd are aging the suspension at 50oC for 30 min, then filtered and washed precipitate the catalyst.

The catalyst according to the analysis contains 0,105% palladium and 0,055% Nickel (calculated on the weight of dry product).

Example 5A. The catalyst with an estimated content of 0.05 wt.% palladium and 0.05 wt.% Nickel is prepared in a laboratory setup described in example 1A.

In the flask is charged with stirring to 150 cm3distilled water and 20 g (dry) powder carbon media Sibunit the pH of the resulting suspension was adjusted to 12 by adding a 0.25 n sodium hydroxide solution, the suspension is then heated to 90oand dispense a solution of Nickel nitrate [0.05 grams Ni(No3)26N2O 10 cm3distilled water], followed by exposure during spontaneous cooling to 30-40o. To a chilled su to ~70o0,017 g of palladium chloride and to 0.011 g of sodium chloride in 5 cm3distilled water, add 0,001 cm3hydrochloric acid, the resulting solution is cooled to 50oC and hydrolyzing of 0.25 N. the sodium hydroxide solution until the mass ratio of NaOH:Pd = 0,5. The solution PGC Pd survive the day.

After dosing solution PGC Pd, and time of exposure of the catalyst is separated on a filter and washed with water until the absence of chloride ions.

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

Example 6a. The catalyst with an estimated content of 0.1 wt.% palladium and 0.1 wt.% iron is prepared with the setup described in example 4A.

Pre-prepare a solution PGC Pd, dissolving of 16.8 g of palladium chloride and 11,36 g of sodium chloride in 500 cm3distilled water, acidified 1.3 cm3concentrated hydrochloric acid, and then hydrolyzing the mixture of 0.5 N. the sodium hydroxide solution until the ratio of NaOH:Pd=0,45 and incubated for 3.5 hours. The resulting solution was dosed to a suspension of 10 kg of silica gel "CSC" 80 DM3water at room temperature and neutral pH.

After a half-hour excerpts of suspensionfront sodium and 28.5 DM310% sodium bicarbonate solution, followed by exposure for 30-40 minutes, the Suspension is filtered, the catalyst paste is rinsed and wring out the filter to a residual moisture content of 20-30 wt.%.

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

Example 7a. The catalyst with an estimated content of 0.05 wt.% palladium and 0.3 wt.% iron is prepared in a laboratory setup described in example 1A.

In the flask is charged with 20 g (dry) coal OS-B containing 0.3 wt. % of iron, and suspended in 200 cm3distilled water at room temperature.

Pre-prepare a solution PGC Pd (as in example 5A), which, after standing for a day to dispense slurry of coal and incubated with stirring for 30-40 minutes, the Suspension of catalyst is treated as in example 1A, and get the catalyst paste with a moisture content of 20-30% and a content of palladium and iron, matching according to atomic absorption analysis with the calculation.

Example 8A. The catalyst with an estimated content of 0.5 wt.% palladium and 0.05 wt. % of iron is prepared on the experimental narabotany installation, as described in example 2A.

In the synthesis reactor catalyst from the measuring device download 3,5-4,0 weight of dry matter. To a suspension of dry media at room temperature add 1H. the sodium hydroxide solution to pH ~ 9,0, the reactor is heated to ~50oC and dispense a pre-prepared solution of ferrous sulfate (1.25 kg FeSO47H2O 50-60 DM3water), then ~10% solution of sodium carbonate (6 kg Na2CO3in 50-60 DM3water) and hold the shutter speed for 30-40 min at a temperature of 50-60oC. At the same temperature dispense a pre-prepared solution PGC Pd (4.2 kg of palladium chloride, 1.5 kg of sodium chloride, 250-300 DM3demineralized water, 325-350 cm3hydrochloric acid) and incubated with stirring for 30-40 minutes

Washing and drying of the catalyst is carried out as in example 2A. The finished catalyst contains of 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 are used three types of installations:

Type 1 - laboratory kinetic installation hydrogenation at constant temperature and hydrogen pressure.

The reactor is a glass ampoule volume 45-55 cm3, being sealed in steel, temperature-controlled enclosure strahovatela system.

After the end of the process the hydrogen is replaced in the system with nitrogen, the catalyst is separated from the reaction mass hot vacuum filtration in a cooled ice receiver, where carried out by cooling to 0-(-5oC) isolation of succinic acid or its salts. (In the case of the synthesis of salts of succinic acid after fractional distillation of water from the mother liquor and cooling is possible to allocate an additional portion of the hydrogenation product). The mother liquor returned to recycling - stage hydrogenation.

Type II - autoclave with a capacity of 1 l, equipped with shielded motor and a high-speed stirrer (n=2700 rpm), equipped with a hermetically attached heated Druk-filter (V=0.5 l), the mould (V= 1 l) jacketed for coolant and automatic registration of absorbed hydrogen.

The process in the reactor are in polythermal conditions and narrow (3-5 MPa) interval within a predetermined pressure. After cessation of hydrogen absorption can produce withstand autoclave 15-20 minutes with constant stirring, then the pressure of the nitrogen perelavlivaet produce through a heated Druk-filter in the mold, in a shirt which serves the brine. When cooled to 0-(-5oC) conduct crystallization >C. the resulting mother liquor and wash water returned to recycling.

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

The reactor volume 25 l with turbine stirrer (n= 2800 rpm), jacketed for heating (or cooling) and the bottom product release.

Heated filter with surface filtration of 0.14 m

Mold with enameled inner surface, frame agitator (n= 43 rpm) and a jacket for cooling the brine.

Suction filter with surface filtration 0.2 m2.

Charged to the reactor, the calculated amount of water, maleic anhydride (acid) and catalyst. When receiving sodium or potassium salts of succinic acid was charged to the reactor caustic soda or caustic potash, respectively. Upon receipt of the succinate of ammonia dissolving maleic anhydride (acid) is carried out in ~24% ammonia solution.

The hydrogenation is carried out at a constant pressure of hydrogen in polythermal regime. The temperature gidada and 10-15 min of exposure of the reaction mass perelavlivaet through a heated filter in the mold, in the shirt which is brine. Crystallization was carried out under cooling to ABOUT-(-5oC). The suspension is filtered on a suction filter, the precipitate washed with cooled water and dried on trays in the dryer, heated with steam at a temperature of 60oC. the mother Liquor, the wash water and the catalyst return for reuse.

Upon receipt of salts of succinic acid to the mother liquor and wash water are subjected to additional Stripping at the boiling temperature of > 60oC, resulting in the concentration of salts and more than their full allocation in the subsequent crystallization and filtration.

Example 1B. Hydrogenation Malinovo anhydride conduct laboratory kinetic installation type 1.

Charged to the reactor 12 ml of distilled water, 3 g of maleic anhydride, 0.03 g of catalyst prepared according to example 1 and sod. Pd of € 0.195 wt.%, Ni is 0.975 wt.%), suspension in water which is pre-incubated for 30-40 min at a temperature of 50oWith and constant stirring in an atmosphere of hydrogen (1 ATA).

The process of hydrogenation at a pressure of hydrogen is 1 and at a temperature of 50oC ends (when the absorption of hydrogen, the corresponding theoretical) is that (0oC) obtain 3.6 g (99,71% of theory.) succinic acid (Tpl.-187,7-188,0o), which corresponds to the output 308 at a rate of flow of 1.6 10-5g of palladium per 1 g Y. K.

Example 2B. The hydrogenation of maleic acid described above lead to the installation of type III by using a catalyst prepared according to example 2 and.

Charged to the reactor 12 l of water, 4.0 kg of potassium hydroxide, stirred to dissolve, then load 4 kg of maleic acid and 32 g of catalyst.

The process of hydrogenation is carried out at constant hydrogen pressure of 10 MPa and polythermal regime (Tstart25-30oC, TConECs.95-105oC).

theoretical uptake of hydrogen is achieved for 90 minutes, the catalyst Activity is 14,.1104with a consumption rate of 1,4910-5g Pd on g succinic acid (or ~ 0,910-5g Pd per 1 g of Pikalevo salt of succinic acid).

After cessation of hydrogen absorption and a 15-minute exposure (with constant stirring, catalysate through Druk air filter perelavlivaet in the mold, which when mixed it is cooled to ABOUT-(-5oC) then separating the precipitated crystals of the salt of succinic acid. The mother liquor and the catalyst with Druk-filter returns the th acid. The hydrogenation process is repeated under the same conditions, the time of the hydrogenation in the second cycle does not practically change, the third is increased to two hours.

After three cycles of hydrogenation get ~20 kg (calculated on the dry weight of Pikalevo salt of succinic acid, which is almost equal to theoretical yield. Performance on the first cycle is 743,5 (or 1222,2 , and after three cycles of use of the catalyst of this indicator is slightly reduced (to 669,2 and 1100 respectively) and sharp (three times) the decline in the rate of consumption of the precious metal - of ~0.5 10-5g Pd per 1 g Y. K. (or ~0,310-5g of palladium per 1 g of dixoni J. K.).

Elemental composition (%) of the product of hydrogenation: C - 24,56; H - 1,90; O - 33,06; K - 40,48 (p Asciano: C - 24,73; H e 2.06; O - 32,94; K - 40,26).

If in the same conditions to carry out the hydrogenation of maleic acid (i.e., in the absence of potassium hydroxide), using the same catalyst, but previously saturated with hydrogen at conditions close to the conditions of hydrogenation (50oC, 10 MPa), a time full of hydrogenation is increased to 2 hours and 40 minutes in the first cycle. The catalyst activity is 7,9104performance (first cycle) - 418,2 and 386,1 (after three cycles pod succinic acid (after three cycles) - for 99.5% of theoretical.), Tpl.- 185,2 - of 186.0oC.

Example 3b. The hydrogenation of maleic acid is carried out on the installation type 1.

In the ampoule download 11 ml of water, 3.6 g of maleic acid, 0.06 g of the catalyst prepared according to example 3 and the pre-stored in hydrogen atmosphere (15 al) with constant stirring and the temperature of 90owithin 60 minutes

Hydrogenation under the same conditions (90oand 15 at) completed within 1 hour and 20 min after absorbing 695 ml (NTD) hydrogen (100% of theory.). The activity of the catalyst 6,89104.

After filtration to separate the catalyst and cooling catalyzate to ~ 0oC allocate 3,63 g (99,1% of theory.) succinic acid (Tpl.- 186,5 - 187,2oC) that corresponds to the output of ~ 360 with a consumption rate of 3,47 10-5g of palladium per 1 g Y. K.

Example 4B. Hydrogenation of maleic anhydride is performed on the above described installation of type II.

Charged to the reactor solution 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.

The air from the system, replacing with nitrogen, then it is filled with hydrogen, heating the suspension up to 30-35oC and are selective which the hydrogenation temperature is increased up to 90-97oC. After the reaction (1 hour 25 min) and shutter speed for 15-20 min, the catalyst was separated by hot filtration, the catalysate is cooled in the mould, distinguish and analyze the product of the hydrogenation. The mother liquor and the catalyst returns to reload. The hydrogenation time on the second cycle is 1 hour and 30 minutes on the second to 1 hour 45 minutes

The catalyst activity is ~17,1104(after 1 cycle) and 15,5104(average, in three cycles), performance (after three cycles) - 819,1 (or 1124,0 with a consumption rate of ~0,4310-5g of palladium per 1 g Y. K. (or 0,3110-5g Pd per 1 g disodium salt I. K.)

The total yield disodium salt J. K. after three cycles - 694 g (i.e. almost quantitative). The elemental composition of the hydrogenation product:

Found (wt.%): C-29,70; N-2,45; O-39,46; Na - 28,39

Calculated (wt.%): C-29,65; N-2,48; O - 39,50; Na - 28,37

When the hydrogenation of maleic anhydride is carried out in the above conditions, but without addition of sodium hydroxide and in the presence of a catalyst, recovered as in examples 1 and 2 and the time of the hydrogenation in the first cycle is increased to 140 min, the catalyst activity is 1,04104performance 546,0 at the same consumption rate of the catalyst.

is the generation by giammarino salt of maleic acid is carried out at the installation type I.

In a vial load 10 ml of distilled water, 6 g giammarino salt of maleic acid and 0.12 g of the catalyst prepared according to example 5 A.

Hydrogenation under hydrogen pressure of 5 and at a temperature of 80oends in 3 hours after absorption amount of hydrogen, the corresponding account. The catalyst activity is 7,54 104that corresponds to the output of 505 and the consumption rate of ~1,110 land only5g of palladium per 1 g of giammarino salt J. K.

After partial soft distillation of water and subsequent freezing of catalyzate with the release of the 98.9 % allocate giammarino Sol J. K., Tpl.- 162,4 - to 163.1oC.

Example 6b. Hydrogenation of maleic anhydride is carried out at the installation of type II.

The catalyst prepared according to example 6 and in the amount of 3.2 g, suspended in 500 ml of distilled water and allowed to stand in an atmosphere of hydrogen (10-15 MPa) at 70-80oC and stirring for one hour, then load 160 g of maleic anhydride and hydronaut when the hydrogen pressure of 10-12 MPa. The initial temperature of the hydrogenation - 40oC, increases to the point of complete absorption of hydrogen (over 130 minutes) to 90-95oC. the catalyst Activity is 8,79104-5g of palladium per 1 g Y. K.

After three cycles total allocated 576 g of succinic acid (Tpl.186,6-187,1oC), which is ~99,7% (theory.).

Example 7b. Hydrogenation of maleic anhydride is carried out at the installation type 1.

In a vial load 16 ml of an aqueous solution of ammonia ( =0,91 g/cm3), containing ~ 24 wt.% NH3, 10 g of the catalyst prepared according to example 7 A.

Hydrogenation at a constant hydrogen pressure (15 bars) and a temperature of 80oends in 5 hours theoretical uptake of hydrogen. The catalyst - 7,6104his performance 505,2 with a consumption rate of 0,6510-5g of palladium per 1 g of giammarino salt J. K.

Highlighted with the release of 97.8% salt has Tpl.= 161,8-162,2o.

Example 8b. Hydrogenation of maleic anhydride is carried out at the installation type III using the catalyst obtained in example 8A.

Charged to the reactor 14 liters of distilled water and 28 g of catalyst; the suspension with constant stirring and the temperature of 90oC stand for one hour under hydrogen pressure of 15 MPa. Then charged to the reactor 4.0 kg of maleic anhydride and carry out the hydrogenation at a hydrogen pressure UB> (NTD) corresponds to an estimated. The catalyst - 6,98104this corresponds to the output 367 (100 % output) and consumption rate 0,2910-4g of palladium per 1 g Y. K.

The mother liquor after separation of the precipitated sludge Y. C. and the catalyst returns to the reactor hydrogenation on re-hydrogenation. Then, as described in example 2B, the return of the catalyst and the mother liquor again.

Total performance (three cycles) is 285,7 , the average activity of the catalyst ~5,4104rate of application 0,910-5g Pd per 1 g Y. K.

Highlighted with the release of 99.6% of theoretical. succinic acid has Tpl.- 186,8 - 187,0oC.

The method of obtaining succinic acid or its salts liquid-phase hydrogenation of maleic anhydride or maleic acid, or salts of maleic acid in water in the presence of palladium catalyst on the carrier, characterized in that the catalyst used palladium-Nickel catalyst at a ratio of palladium : Nickel, which is 1 : 0.5 to 5, or palladium-iron catalyst at a ratio of palladium : iron is 1 : 0.1 to 6.

 

Same patents:

The invention relates to a method for obtaining succinic anhydride used in the production of pharmaceuticals, insecticides, as a hardener of epoxy resins, in analytical chemistry

The invention relates to the production of dicarboxylic acids, and in particular to methods of producing succinic acid by oxidation with ozone, which is a plant growth regulator [1,2]

There is a method to produce succinic acid by ozonation 1,5,9-cyclododecatriene at 30-40aboutWith acetic acid [3]

The disadvantages of this method of obtaining are high cost and high toxicity of raw materials (1,5,9-cyclododecatriene) [4]

Also known is a method of obtaining succinic acid by ozonation 3-chlorocyclopentane followed by additional oxidation products of ozone with nitric acid, or hydrogen peroxide, or potassium permanganate [5]

The disadvantages of this method are the scarcity and high cost of raw materials (3 chlorocyclopentane), the complexity of the separation of succinic acid from by-products, not a high yield of succinic acid (81-85%)
The invention relates to a method of catalytic hydroxycarbonylmethyl pentenoic acid to adipic acid

The invention relates to the purification of carboxylic acids and/or their anhydrides, in particular to the removal of impurities iodide from acetic acid and/or acetic anhydride, the resulting liquid-phase carbonyliron appropriate materials selected from the group comprising methanol, diethyl ether, methyl acetate or mixtures thereof

FIELD: industrial organic synthesis.

SUBSTANCE: subject of invention is continuous carbonylation of long-chain aliphatic hydrocarbons to produce alcohols, acids, and other oxygen-containing products such as esters. Process comprises paraffin dehydrogenation, carbonylation, and fraction distillation-mediated end product recovery. Advantageously, mixture of paraffins containing different number of carbon atoms isolated from kerosene fraction is processed. Non-converted paraffins are recycled into dehydrogenation zone. Prior to be fed into carbonylation zone, stream is processed by selectively hydrogenating diolefins. In the carbonylation stage, homogenous catalytic system is used containing palladium/imidazole or palladium/triphenylphosphine complex, aliphatic acid (preferably formic acid), and solvent. Catalytic system further includes promoter selected from group: lithium iodide, zirconium chloride, tin chloride, and lithium bromide.

EFFECT: simplified technology, increased conversion of raw materials and selectivity in formation of desired products.

14 cl, 2 dwg, 1 tbl, 11 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of saturated aliphatic carboxylic acids with stable carbon isotopes (1-13C). Method involves the hydrocarboxylation reaction of α-olefins with carbon monoxide (13CO) and water at temperature 100-170°C and under pressure not exceeding 5 MPa in the presence of a solvent and catalytic system containing palladium compound as complex PdCl2(PPh3)2 and triphenylphosphine PPh3 taken in the ratio from 1:2 to 1:100, respectively. Synthesized carboxylic acids can be used as diagnostic test-preparations in medicine practice and in criminology, scientific investigations and in other fields. Invention provides synthesis of enanthic acid and caprylic acid labeled by stable carbon isotope 13C at position 1 for a single step, to increase yield of acids as measured for isotope raw, to decrease cost price of acids and to obtain derivatives of (1-13C)-caprylic acid - (1-13C0-caprylate sodium and (carboxy-13C)-trioctanoine.

EFFECT: improved methods of synthesis.

9 cl, 6 ex

Catalyst system // 2372989

FIELD: chemistry.

SUBSTANCE: present invention relates to a new catalyst system, a new carbonylation reaction medium and to a method of carbonylation of ethylene-unsaturated compounds using the new catalyst system. The catalyst system, which is capable of catalysing carbonylation of an ethylene-unsaturated compound, can be obtained by combining: a) group VIIIB metal, or its compound, b) bidentate phosphinic or arsinic ligand and c) acid, where the said ligand is present in molar excess of at least 2:1, compared to the said metal or said metal in its compound, and the said acid is present in molar excess ranging from 5:1 to 95:1, compared to the said ligand. In another version the catalyst system, which is capable of catalysing carbonylation of an ethylene-unsaturated compound, can be obtained by combining: a) group VIIIB metal, or its compound, b) bidentate phosphic or arsinic ligand and c) acid, where molar ratio of the said ligand to the said metal or said metal in its compound lies in the range greater than 5:1 to 750:1, and the said acid is present in molar excess of at least 2:1, compared to the said ligand.

EFFECT: invention also relates to a method of carbonylation of an ethylene-unsaturated compound, a reaction medium, use of catalyst a system and a complex, which is capable of catalysing carbonylation of an ethylene-unsaturated compound.

39 cl, 35 ex, 9 tbl, 3 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method for synthesis of 1-13C-caprylic acid which is used as a diagnostic preparation when diagnosing motor-evacuation functions of the stomach. The method involves hydrocarboxylation reaction of 1-heptene with carbon monoxide 13CO and water at temperature 100-170°C and pressure not above 5 MPa, in the presence of a solvent and a catalyst system which contains a complex compound of palladium and triphenylphosphine in ratio ranging from 1:2 to 1:100, where the solvent used is dioxane and/or aromatic hydrodrocarbon.

EFFECT: obtaining 1-13C caprylic acid with high isotope purity, increased cost-effectiveness of the process owing to increased degree of utilisation of isotope material.

5 cl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing oxalic acid, involving feeding carbon dioxide through 1.0-13.0 M aqueous trifluoroacetic acid solution which is saturated with oxygen at temperature of 15-25°C and atmospheric pressure. Oxalic acid is separated by evaporating the obtained product. The invention can be used in chemical industry.

EFFECT: method which enables to produce oxalic acid in a single step at room temperature and atmospheric pressure.

2 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to production of palladium catalysts, which can be used for hydrogenating organic electrolytes with unsaturated C-C bonds in molecules, in particular, for selective hydrogenation of maleic acid into succinic acid in aqueous medium. Catalyst is palladium nanoparticles with size of 1.2-5 nm, applied amount of 0.1-2.5 wt% per powder supports of various chemical nature (Al2O3, SiO2, TiO2, ZrO2, Sibunit), having relatively low specific surface area of 2-455 m2/g, which minimises effect of diffusion of reagents, caused by existence of adsorbed solvate layers and double electric layer on surface of support, on rate of catalytic process. Required dispersed state of palladium nanoparticles is achieved by that hydrolytic precipitation of palladium on a support from solutions of H2PdCl4 is carried out at pH 9-9.5 directly in presence of support with further liquid-phase reduction of catalyst, which enables to achieve higher dispersion of applied metal due to complete hydrolysis of complexes of palladium chloride and reducing ageing time of formed hydro complexes in solution as a result of their fast adsorption on support.

EFFECT: technical result is high activity and selectivity of obtained catalysts for hydrogenation of maleic acid into succinic acid in aqueous medium in mild conditions.

5 cl, 2 dwg, 1 tbl, 15 ex

FIELD: chemistry.

SUBSTANCE: two-stage continuous process of preparing propionic acid is provided; it comprises the step of hydrogenating the carbon dioxide in the synthesis gas in the presence of a catalyst comprising cobalt metal on the support as organometallic framework MIL-53 structure (Al), and a step of hydroxycarbonylation of ethylene with carbon monoxide and water in the presence of hydroxycarbonylation catalyst, which is a metallic rhodium on a carrier in the form of organometallic framework MIL-53 structure (Al), and the process is conducted in a flow 2- tray reactor at a pressure of 40-80 atm by contacting the fixed catalyst bed located on the top shelf and the reactor heated to a temperature of 500°C, with a raw material mixture of H2 and CO2 at a volumetric feed rate of gas feedstock 500-1000 h-1, followed by mixing of the produced gas containing CO-H2-CO-H2O mixture heated to 500-520°C with cold ethylene fed into the inter-bed space and the resulting gas mixture at a ratio of CO:H2O:C2H4 close to 1:1:1 is fed to the lower shelf of the reactor and is contacted at a temperature of 140-200°C with the hydroxycarbonylation catalyst therein. The process is carried out at a volume ratio of H2:CO2 in the gas feedstock of 0.8-1.2, and use catalysts having a size of 2-4 nm metallic particles with a cobalt content of 10 wt % rhodium and 5-15 wt %.

EFFECT: propionic acid increase in the yield and selectivity of its formation, while simplifying the process technology and reducing energy consumption, provides a recycling method of the greenhouse gas.

3 cl, 3 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: synthesis method by 13C-linoleic, 13C-linolenic, 14C-linoleic and 14C-linolenic acids includes the carbon dioxide condensation, marked by 14C or 13C, with the Grignard reagent, produced from 1-bromo-8.11-heptadecandiene (in case of linoleic acid) or from 1-bromo-8.11.14-heptadecanthriene (in the case of linolenic acid), carried out in the following sequence of steps: a - production of the Grignard reagent by the reaction of metallic magnesium with 1-bromo-8.11-heptadecandiene (in case of linoleic acid) or with 1-bromo-8.11.14-heptadecantriene (in case of linolenic acid) in the presence of metallic iodine; b - carboxylation of the Grignard reagent, produced at point a, for 5-15 min at temperature -20°C at constant stirring, carbon dioxide, marked by 14C or 13C, produced by the sulfuric acid of barium carbonate decomposition, marked by 14C and 13C, at the CO2 pressure of not more than 500 mm Hg. (maintaining by the drop metering of sulfuric acid); after stopping the pressure change in the system, the reaction flask is cooled with the liquid nitrogen in order to provide the quantitative transfer of the remaining in the system 14CO2 or 13CO2 in it, close the tap connecting the device to the CO2 source, and the reaction mixture is stirred for 15 minutes at the temperature -20°C with the purpose to fully incorporate the isotopically marked carbon dioxide into the product of the synthesis: linoleic or linolenic acid.

EFFECT: target products manufacture process acceleration, reduction of carbon dioxide losses, increase of its total chemical and radiation yield in comparison with the prototype, and elimination of the isotope-marked atoms distribution along the entire length of the acyl chain, the simplification and cheapening of the target products the linoleic and linolenic acids manufacture process, is ensured by the decrease in the duration, the increase of the radiation and chemical yield of the product along the source of the isotope in comparison with the prototype, the radioactive wastes release into the external environment is almost completely excluded, as its inclusion into the target product is approaching to the quantitative.

10 tbl, 2 ex, 4 dwg

FIELD: new 2,4,6-trimethyl-3-oxypyridine nitrosuccinate and method for production thereof.

SUBSTANCE: claimed compound is useful in medicine as future antiishemic agent with vasodilatation effect and has potent protective action in barotraumatic damages and ballistic wounds due to inhibition of secondary necrosis creation and progress. Compound of present invention is obtained by nitration of malic acid with mixture of sulfuric and nitric acids, separation of nitrohydroxymalic acid and treatment thereof with 2,4,6-trimethyl-3-oxypyridine in alcohol media with subsequent isolation of target product.

EFFECT: new antiishemic agent.

2 cl, 1 ex

FIELD: production of calcium succinate useful in pharmacology, veterinary, medicine as drug or bioactive additive.

SUBSTANCE: calcium succinate in obtained by reaction of calcium chloride solution with reactive mixture of succinic acid and sodium hydroxide in molar ratio of 1:2, respectively at 20-30°C. Calcium chloride solution is added for 2 hours followed by mixture conditioning for 3 hours for crystallization finishing. Precipitate is separated, washed on filter and dried at 100°C for 12 hours. Target product is obtained in form of monohydrate.

EFFECT: accelerated method with reduced energy consumption.

1 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to improved method (variants) for conversion of maleic acid to 1,4-butanediol, gamma-butyrolactone and/or tetrahydrofuran. Method for synthesis for at least one of product chosen from a group comprising gamma-butyrolactone, 1,4-butanediol and tetrahydrofuran involves the following steps: creature of the first hydrogenation zone and the second hydrogenation zone that are bound successively; feeding to the first zone of a raw flow that comprises maleic acid; caring out reaction in the first hydrogenation zone of the parent maleic acid and hydrogen in contact with a catalyst to yield the reaction product comprising succinic acid; feeding to the second zone the hydrogenation product from the first hydrogenation zone; carrying out the hydrogenation reaction of the reaction product obtained in the first hydrogenation zone in the second hydrogenation zone in contact with a catalyst for preparing a product that comprises at least one product from a group comprising gamma-butyrolactone, 1,4-butanediol and tetrahydrofuran. Method involves control over temperature in first hydrogenation zone by manner that maleic acid temperature in the raw flow and temperature in the first hydrogenation zone doesn't exceed 120°C, and the reaction heat liberated in the first hydrogenation zone is used in enhancing the reaction product reaction above 130°C before feeding the reaction product from the first hydrogenation zone to the second hydrogenation zone resulting to minimal corrosion effect of maleic acid and enhancing time for working life of reactor and improving the complete effectiveness of the process.

EFFECT: improved method of synthesis.

13 cl, 1 ex

FIELD: organic synthesis.

SUBSTANCE: invention concerns an improved method for synthesis of manganese(II) succinate tetrahydrate wherein manganese(II) carbonate is portionwise added to succinic acid aqueous solution at molar ratio 1:1:4.5, respectively, under continuous stirring and, while maintaining constant temperature 60-65°C, each subsequent portion being added after complete dissolution of preceding manganese carbonate portion, after which desired product is isolated via recrystallization. Method can be used under industrial-scale conditions.

EFFECT: improved purity of product and minimum reactants used.

3 dwg, 2 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing malonate or manganese (II) succinate, which can be used in different areas of chemical practice, in analytical control and scientific research, through direct reaction of a metal and its dioxide with carboxylic acid in the presence of an organic solvent and stimulating iodine additive in a vertical type bead mill with a high-speed mixer and glass beads as grinding medium, where manganese, its dioxide and carboxylic acid in the initial load are taken in molar ratio 1+x):1:(2+x) so as to obtain (2+x)m moles of salt, where x in the given molar ratio of reagents equals 0.4±0.1 for amber acid and 1.0±0.1 for malonic acid, and m is the number of moles of manganese dioxide in the load; iodine is taken in amount of 0.05 mol/kg of the reaction mixture after loading organic solvent and acid, but before loading manganese dioxide and metal. Total mass of acid, metal and its dioxide lies between 15 and 25% of the mass of the initial load, and ratio of mass of beads to mass of the load is 1:1. The process is started at room temperature and carried out under forced cooling conditions at temperature ranging from room temperature to 40°C while controlling by taking samples until exhaustion of all loaded reagents into the target salt, after which the process is stopped. The suspension of the final reaction mixture is separated from the beads and filtered. The product residue is washed with a liquid phase solvent and taken for purification from trace metal and its dioxide through recrystallisation, and the filtrate and washing solvent are returned to the repeated process.

EFFECT: process takes place at acceptable rates and ends with virtually complete consumption of all loaded reagents.

2 cl, 19 ex

FIELD: medicine.

SUBSTANCE: invention refers to a method of producing succinic acid with using a Yarrowia lipolytica yeast strain, Russian National Collection of Industrial Microorganisms No. Y-3314. Said yeast is modified in such a manner that they have lowered succinate dehydrogenase activity. The method involves a stage of yeast strain incubation in a nutrient medium containing glycerine, and recovery of succinic acid from a culture fluid.

EFFECT: use of the Yarrowia lipolytica strain, Russian National Collection of Industrial Microorganisms No Y-3314 has ensured substantially increased yield of succinic acid in this method.

2 cl, 2 dwg, 5 tbl, 5 ex

FIELD: biotechnologies.

SUBSTANCE: strain Yarrowia lipolytica All-Russian collection of industrial microorganisms Y-3753 is proposed - producent of succinic acid. The strain may be produced on nutrient medium, containing glucose as the consumable carbon source, in absence of substances that stabilise pH, succinic acid in amount of up to 60 g/l of cultural fluid.

EFFECT: improved properties of the strain.

1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to improved method of obtaining ammonium salts of fumaric or succinic acid, which are used for production of biologically active additives or medications, as well as in veterinary and food industry. Method lies in neutralisation of respective acid with neutralising compound in water medium, where as neutralising compound ammonium carbonate or bicarbonate is used, with molar stoichiometric or exceeding stoichiometry by 4-5% ratio of acid and ammonium carbonate or bicarbonate, neutralisation is carried out in saturated water solution of synthesised salt, at temperature not higher than 40°C, with further product separation and its drying at temperature not higher than 70°C. Method can be realised in conditions of industrial production. It is possible to obtain ecologically pure salts with content of main substance not lower than 99.0 wt %, and output not lower than 98%.

EFFECT: method makes it possible to increase output of target products and ensures their stably high quality due to obtaining them mainly in crystalline form.

4 cl, 5 ex

Up!