SU1366197A1 - Method of extracting cobalt,manganese and nickel from ash of dimethylterephthalate production - Google Patents

Description

The invention relates to catalytic chemistry, in particular the extraction

CO, Mn and Νΐ from the ashes of dimethyl terephthalate production. To increase the degree of extraction in the process of treating ash with an aqueous solution of an alkaline agent with water and aqueous CH ^ COOH at elevated temperatures and separating the metal salts from the residual ash, an additional treatment of the latter at 80-100 ° C with 2055% aqueous solutions is used HCOOH and at a mass ratio with metals in the residual ash, equal to (0,941.88): 1. Exit by the proposed method, X: Co 94.8; MP 87.2; Νΐ 92.3 and Her 9.3 against 40.3; 39.5; 43.2 and 42, respectively, by a known method. The activity and selectivity of the catalyst based on these metals is at the level of industrial production.

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The invention relates to methods for extracting cobalt, manganese and nickel from waste products of dimethyl terephthalate.

The aim of the invention is to increase the degree of extraction of cobalt, manganese and nickel due to the additional processing of residual ash in certain conditions. ten

The invention is illustrated by the following examples.

Example 1. In a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 15,500 ml of an aqueous solution containing 5 g of caustic soda and 100 g of ashes from dimethylterephthalate containing may be added. MP 4.20;

Νί 0.23; Ge 0.41; alkaline, alkaline-20 earth and other metals 2.27 (in total) - stirred at 20 ° C for 1 h. Then the aqueous solution is separated and the ash is washed to neutral medium with distilled water. After that, 1000 ml of an aqueous solution are added to the ash, containing 100 g of acetic acid, stirred for 2 hours at the boiling point of the reaction mixture, cooled, filtered, the residual ash is washed with 100 ml of distilled water, which is combined with the previous filtrate, and dried.

Get 1135 ml of a solution of metal acetates containing, g / l: Co 28.04; Mp 1.99; Νί 0.14; Re 0.04 and 31.0 g of residual ash containing, in wt.%: Co 56.47; Mp 6.25; Νϊ 0.22;

Re 1.17. The degree of extraction of Co, Μη, Νί, and Pe from ash is 64.5, 53.8, 69.1, and 11.1%, respectively.

To 31.0 g of residual ash is added 61 ml of a 55% aqueous solution of formic acid (the mass ratio of formic acid and metals in the residual ash is 1.88: 1) and stirred at 80 ° C for 18 hours. 1200 ml are added to the reaction mass. distilled water, stirred at 80 ° C for 1 h, cooled, filtered, unreacted residual ash washed with 50 ml of distilled water, which is combined with the previous filtrate, and dried.

Get 1280 ml of a solution containing, g / l: Co 10,88; Mp 1.12; Νί 0.04; Ge 0.02, - and 6.1 g of unreacted residual ash containing,

wt.%: With 58,78; Mp 8.16; Νί 0.28,

Re 5.55. The degree of extraction of Co, MP,

Νί and Re respectively 79.5, 74.2, ¹ 81.0 and 7.0%.

To 6.1 g of unreacted residual ash is poured 12.0 ml of 55% aqueous solution of formic acid (mass ratio of formic acid and metals 1.88: 1) and stirred at 80 ° C for 18 h.

260 ml of distilled water is poured to the reaction mass, stirred at 80 ° C for 1. h, cooled, filtered, washed with an insoluble residue with 15 ml of distilled water, which is combined with the previous filtrate;

Get 280 ml of a solution containing, g / l: Co 9.57; Mp 1.30; Νί 0.03; Re 0.03. The degree of extraction of Co, Μη, Νί and Re, respectively

75.3, 73.1, 79.5 and 2.2%. '

Total extracted from residual ash,%: Co 94.8; 87ι 87.2; Νί 92.3;

25 p _e 9.3.

Approx 2. 100 g of ash produced in dimethyl terephthalate, containing, in May.%: Co 53.55; Mp 3.28;

Νί 0.16; Re 0.35; alkaline, alkaline30 land and other metals 2.10 (in total) are first treated with an alkaline solution and then with an acetic acid solution, as described in Example 1.

3 ₅ Get 1130 ml of a solution of metal acetates containing, g / l:

Co 33.40; Mp 1.63; Νί 0.10; Fe0.04, and 28.0 g of residual ash containing, May. %: Co 60.04; MP 5.14;

40 Νί 0.17; Re 1.09. The degree of extraction from the ashes of Co, Μη, Реnd Re is respectively 70.5, .56.2, 71.1 and 12.9%.

83 ml of a 20% aqueous solution are added to 28.0 g of residual ash.

45 of formic acid (mass ratio of formic acid and metals in the residual ash of 0.94: 1) and stirred at 100 ° C for 24 h. To the reaction mass is poured 800 ml

50 distilled water, stirred at 100 ° C for 1 h, cooled, filtered, unreacted residual ash washed with 50 ml of distilled water, which is combined with the previous filtrate, and dried.

Get 910 ml of a solution containing, g / l: Co 10.22; Mp 0.81; Νί 0.03; Re 0.02, - and 12.1 g of unreacted residual ash containing 3

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lean, wt.%: Co 62.06; MP 5.81; ' Νί 0.16; Re 2.37. The degree of extraction of Co, Μη, Νί and Re, respectively

55.3, 51.2, 58.1 and 5.9%.

To 12.1 g of unreacted residual ash poured 38 ml of a 20% aqueous solution of formic acid (mass ratio of formic acid and metals 0.94: 1) and stirred at 100 ° C for 24 hours

To the reaction mass is poured 400 ml of distilled water, stirred at 100 ° C for 1 h, cooled, filtered, the unreacted residue is washed with 20 ml of distilled water, which is combined with the previous filtrate, and dried.

Get 450 ml of a solution containing, g / l: Co 9.49; Mp 0.81;

Νί 0.03; Re 0.02, - and 5.4 g of unreacted residue containing, in wt.%: Co 60.24; Mp 6,24; Νί 0.11;

Re 3.72. The degree of extraction of Co, MP,

Νί and Re respectively 56.7, 52.0, 67.9 and 3.0%.

17.0 ml of a 20% aqueous solution of formic acid (the mass ratio of formic acid and metals is 0.94: 1) is poured to 5.4 g of unreacted residue and stirred at 100 ° C for 24 hours. 140 ml of distilled water, stirred at 100 ° C, cooled, filtered, the insoluble residue was washed with 10 ml of distilled water, which was combined with the previous filtrate.

Get 167 ml of a solution containing, g / l: Co 10.42; Mp 1.01; Νί 0.02; Re 0.03. The degree of extraction of Co, Μη, Νί and Fe, respectively, 53.5, 50.0, 52.6 and 2.5%.

Total extracted from residual ash,%: Co 91.0; MP 88.3; Νί 97.7;

Re 10.6.

Example: 100 g of the ash produced by dimethyl terephthalate with the composition specified in Example 1 is treated first with an alkaline solution and then with an acetic acid solution, as in Example 1. '

1140 ml of a solution of metal acetates are obtained, containing, g / l: Co 28.20; Mp 2.02; Νί 0.15; Re 0.04, and 30.5 g of residual ash containing, in wt.%: Co 56.32; Mp 6.36; Νί 0.19;

Re 1.19. Ash removal rate

Co, Μη, Νί, and Pe, respectively, 65.2, 54.8, 70.0, and 11.1%.

80 ml of a 35% aqueous solution of formic acid (the mass ratio of formic acid and metals in the ash is 1.56: 1) are added to 30.5 g of residual ash and stirred at 90 ° C for 24 hours. 1200 ml are added to the reaction mass distilled water, stirred at 90 ° C for 1 h, cooled, filtered, unreacted residual ash washed with 50 ml of distilled water, which is combined with the previous filtrate, and dried.

Get 1310 ml of a solution containing, g / l: Co 9.32 Mp 0.98; Νί 0.03; Re 0.02, - and 8.4 g of unreacted residual ash containing, in wt.%: Co 59.17; Mp 7.81; Νί 0.23;

Re 4.15. The degree of extraction of Co, Mn, Νί and Re, respectively, 71.1, 66.2,

66.1 and 7.2%.

To 8.4 g of unreacted residual ash, 24.5 ml of a 35% aqueous solution of formic acid are poured (the mass ratio of formic acid and metals is 1.56: 1) and stirred at 90 ° C for 24 hours. 300 ml are poured to the reaction mass. distilled water, stirred at 90 ° C for 1 h, cooled, filtered, the unreacted residue is washed with 15 ml of distilled water, which is combined with the previous filtrate.

Get 330 ml of a solution containing, g / l: Co 10.36; Mp 1.23; Νί 0.04; Re 0.02. The degree of extraction of Co, Μη, Νί and Fe is respectively 68.8, 61.9, 65.0 and 1.6%.

Total extracted from residual ash,%: Co 91.0; MP 87.1; Νί 88.1;

Re 9.0. *

И p and me 4 (for comparison).

100 g of ash production of dimethyl terephthalate composition specified in example 4, is treated as in example 1.

Get 1135 ml of a solution of metal acetates containing, g / l: Sat 28,10; Mp 2.00; Νί 0.14; Re 0.04, and 31.0 g of residual ash of the same composition as in example 1. The degree of extraction from the ash Co, Μη, and Re, respectively 64.6, 54.0, 69.1 and 11.1%.

70 ml of a 15% aqueous solution are added to 31.0 g of residual ash.

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formic acid (weight ratio of formic acid and 0.55 metals: 1) and stirred at 100 ° C for 24 hours to the reaction mass is poured 300 ml of distilled ^5-water, stirred at 100 ° C for 1 hour, cooled, filtered. unreacted residual ash is rinsed with 50 ml of distilled water, Rui koto- ₁₀ 'are combined with. the previous filtrate, and dried.

Get 360 ml of a solution containing, g / l: Co 9,70; Mp 0.95; Νΐ 0.04; Re 0.10, - and 24.2 g neproreo- - | _{5 of} residual ash containing, May. %: Co 57.62; Mp 6.56; Νΐ 0.23; Re 1.36, the degree of extraction of Co, Μη, Νΐ and Re, respectively, 20.0, 17.7, 20.6 and 9.9%. ' 20

To 24.2 g of unreacted residual ash, 56 ml of 15% aqueous formic acid are added (the mass ratio of formic acid and metals is 0.55: 1) 25

and stirred at 100 ° C for 24 hours, 200 ml of distilled water was added to the reaction mass, stirred at 100 ° C for 1 hour, cooled, filtered, the unreacted residue was rinsed with 30 ml of distilled water, which was combined with the previous filtrate, and dried.

Get 245 ml of a solution containing, g / l: Co 10,56; Mp 1.04;

• Νΐ 0.04; Re 0.13, - and 19.6 g of unreacted residue, containing wt.%: Co 57.94; Mp 6.81; Νΐ 0.23;

Re 1.52. The degree of extraction of Co, MP,

Νΐ and Re, respectively, 18.6, 16.0, _4θ 18.0 and 9.7%. ,

To 19.6 g of unreacted residue is poured 46 ml of a 15% aqueous solution of formic acid (the mass ratio of formic dd

acids and metals 0.55: 1) and stirred at 100 ° C for 24 hours. 180 ml are added to the reaction mass.

• distilled water, stirred at 100 ° C for 1 h, cooled, filtered, dd the insoluble residue is washed with 30 ml of distilled water, which is combined with the previous filtrate.

Total extracted from residual ash,%: Co 47.9; MP 41.6; Νΐ 49.1;

Re 27.4.

Example 5 (for comparison).

100 g of the ash produced by dimethyl terephthalate with the composition specified in example 2 are first treated with an alkaline solution, then with an acetic acid solution, as in example 2.

Get 1130 ml of a solution of metal acetates containing, g / l: Co 33.10; Mp 1.60; Νΐ 0.10; Re 0.04, - and

28.4 g of residual ash containing, in wt.%: Co 56.86; Mp 5.18; Νΐ 0.10;

Re 1.07, The degree of extraction from the ash Co, Μη, Νΐ and Re respectively 69.8, 55, 1, 70.6 and 12.9%.

48 ml of a 65% aqueous solution of formic acid (mass ratio of formic acid and metals 2: 1) is added to 28.4 g of residual ash and stirred at 70 ° C for 8 h (further processing of residual ash was stopped due to the strong thickening of the mixture ). 600 ml of distilled water is added to the reaction mixture, stirred at 70 ° C for 1 h, cooled, filtered, the unreacted residual ash is washed with 50 ml of distilled water, which is combined with the previous filtrate, and dried.

Get 675 ml of a solution containing, g / l: Co 9.65; Mp 0.86; Νΐ 0.03; Re 0,19, - and 16.6 g of unreacted residue containing, in wt.%:

Co 58.05; Mp 5.37; Νΐ 0.16; Re 1.06. The degree of extraction With, Μη, Νΐ and Re, respectively, 40.3, 39.5, 43.2 and

42.0%. .

To 16.6 g of unreacted residue is poured 28.6 ml of a 65% aqueous solution of formic acid (mass ratio of formic acid and metals 2: 1) and stirred at 70 ° C for 8 hours. To the reaction mass is poured 300 ml of distilled water , stirred at 70 ° C for 1 h, cooled, filtered, the insoluble residue was washed with 30 ml of distilled water, which was combined with the previous filtrate.

Get 248 ml of a solution containing, g / l: Co 9,14; Mp 0.83; Νΐ 0.04; Re 0.13. The degree of extraction of Co, Μη, Νΐ and Fe, respectively, 20.0, 15.4, 21.9 and 10.8%.

Get 350 ml of a solution containing, g / l: Co 10.85; Mp 0.96; Νΐ 0.03; Re 0.19. The degree of extraction of Co, Μη, Νΐ and Re, respectively

39.4, 37.1, .38.9, and 37.7%.

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Total extracted from residual ash,%: With 63.9; MP 62.0; Νί 65.5;

Re 63.9.

Example 6. In a glass reactor of bubbling type, equipped with a water separator and a reflux condenser, 20 g of methyl p-toluylate, 0.5 g of p-toluic acid are placed and 0.35 ml of an aqueous solution of the catalyst obtained in Example 1 from the residual ash (total concentration of cobalt, manganese, and nickel in methyl p-toluylate 0.02 May.%), Oxidation is carried out at 16O ° C, oxygen is passed through at a rate of 7 l / h for 3 hours. After oxidation, the oxidate has acid number is 107 and contains 31.0% monomethyl terephthalate. The amount of precipitated carbon dioxide is 20-lehr It takes 2.32% of the monomethyl terephthalate formed.

Example7. 0.5 g of p-toluic acid and 0.4 ml of the aqueous solution of the catalyst prepared in example 2 from residual ash (total concentration of cobalt, manganese and nickel in methyl p-toluylate 0.02 wt.%), And oxidized in the same 30 conditions as in example 6. After 5 hours, the oxidate has an acid number of 104 and contains 30.2% of monomethyl terephthalate. The amount of released carbon dioxide 2.35% of the resulting ₃₅ monomethyl terephthalate.

PRI me R 8 (for comparison). 0.36 ml of industrial catalyst is added to 20 g of methyl p-toluylate! prepared from cobalt acetates, to manganese and nickel qualifications "h” and containing cobalt, manganese and nickel in the same amounts as in the solution ^ obtained from the residual

the ashes in example 1, and oxidized in the same conditions. After 3 hours of oxidation, the oxidate has an acid number of 109 and contains 31.7% monomethyl terephthalate. The amount of carbon dioxide released is 2.3% of the monomethyl terephthalate formed.

From the above examples, it follows that the treatment of residual ash at 80-100 ° C 20-55% solutions

formic acid with a mass ratio of formic acid and metals in the residual ash (0.94-1.88): 1 provides a high degree of extraction and purity of the catalyst, the activity and selectivity of which are at the level of industrial catalyst.

Thus, the proposed method allows to increase the degree of extraction of cobalt, manganese and nickel from the ashes of dimethyl terephthalate production.

Claims (1)

Claim The method of extraction of cobalt, manganese and nickel from dimethyl terephthalate production ashes, including treating the ash with an aqueous solution of an alkaline agent, then with water and an aqueous solution of acetic acid at elevated temperature, separating the solution of metal salts from the residual ash, cobalt, 'manganese and nickel, residual ash is additionally treated at 80-100 ° C with 20-55% aqueous solutions of formic acid with a mass ratio of formic acid and metals in the residual ash (0.94-1.88): 1.