Method for regenerating catalyst for liquid-phase oxidation of olefins to aldehydes and ketones

 

(57) Abstract:

The invention relates to the petrochemical industry, and more specifically to processes for acetaldehyde, acetone and methyl ethyl ketone, in particular to methods for regenerating catalyst of liquid-phase oxidation of olefins to aldehydes and ketones, which is an aqueous solution of palladium chloride, copper and acetic acid, by the action of carbon monoxide, or olefin, or hydrogen with obtaining the recovered solid residue which is treated with oxygen or gas containing oxygen, with the addition of hydrochloric acid and water, and obtained after recovery of the mixture of salts precipitate and the mother liquor add a solution of hydrate of sodium oxide or sodium carbonate concentration of 0.08 and 0.12 wt. % in a volume ratio to the catalyst solution of 0.8-1.2: 1, the mother liquor separated from the crystals, which, after leaching of cations of sodium and potassium oxidize. The technical result - the regeneration of poisoned cations of sodium and potassium and other poisons the catalyst solution is almost full utilization of copper ions and palladium. 1 Il., table 2.

The invention relates to the petrochemical industry, and more specifically to about the Oia acetic acid, acetic anhydride, ethyl acetate, pentaerythritol, etc.

Lower ketones (acetone, methyl ethyl ketone are widely used as solvents in industry varnishes and paints, as well as intermediates in the synthesis of various monomers.

These compounds get direct oxidation of olefins in the presence of a catalyst is an aqueous solution of salts of palladium and copper (Chem. Eng., 168, N 10, 66, 1961, Smidt; Ang. Chem, 74, N 3, 93, 1962).

Such catalysts lose activity over a long period of time, assuming a constant input of chlorine ions in the form of hydrochloric acid, the concentration of which is reduced due to the formation of organochlorine compounds derived from the catalyst solution by separation of the reaction products. In the catalyst solution is periodically added to replace losses chlorides of palladium and copper.

Also in the catalyst solution is continuously introduced khimochistka water for partial compensation of evaporated water together with the reaction products. In addition, water is introduced into the system due to the need for salt flushing devices and seal upon absorption of vapors of acetaldehyde (ketones) from the reaction gases. In addition to the treated water passes when condensables in the catalyst solution. Although khimochistka water contains small amounts of salts of sodium and potassium, in the long run production cations potassium and sodium accumulate in the catalyst solution. In the catalyst solution for 5 to 10 year period of operation up to 20 g/l of cations potassium and sodium, which neutralize contained in the catalyst solution of chlorine ions. Acidity decreases that leads to the precipitation of palladium and basic salts of copper chloride.

To increase the acidity of the solution it is necessary to increase the concentration of chlorine ions by the additional consumption of hydrochloric acid. If a conventional catalyst ratio between copper ions and chlorine ions is taken in the range of 1: 1.4 to 1:2, (PP 50, 51) patent formula, patent, Belgium N 569036, class C 07 B, page 41) in the catalyst solution containing a higher concentration of potassium and sodium ions, the ratio between copper ions and chlorine ions have to maintain in the range of 1:2.8 to 1:3,4. Due to the high concentration of chlorine ions, the catalyst has a low activity. To restore the activity of the catalyst solution should be clear from potassium and sodium ions.

According to the author svidetelstvuet-copper-palladium catalyst solution is treated with a solution of alkali at a pH of 10-11, obtained after separation of the precipitate washed with water until neutral and dissolved in hydrochloric acid.

This method has the following disadvantages.

To turn duhalista copper hydrate of copper oxide requires a lot of alkali. In addition, the spent alkali to neutralize the acetic acid contained in the catalyst solution.

The resulting precipitate of hydrate of copper oxide, palladium consists of very small crystals, it is difficult separated from the mother liquor. The separated precipitate requires a lot of water for washing from sodium ions. To implement this method in industry failed, because together with the sediment in the catalyst solution were sodium ions, which leads to its complete poisoning.

The prototype of the present invention is a patent Belgium N 569036, class C 07 B, according to which the catalyst is recovered, acting carbon monoxide, or olefin, or hydrogen. After cessation of olefin process layer of the solid catalyst with oxygen or gas containing oxygen with the addition of hydrochloric acid and water.

When this regeneration cannot be fully translated into the sludge produced during recovery of the catalyst, chloride adnovate.

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Chlorides of monovalent copper in acidic solution form complexes CumCly-mand so on, which are soluble in the mother liquor (O. N. Temkin and other Acetylene chemistry, reaction mechanisms, technology, Ed. "Chemistry", M., 1991, page 94).

Our research has shown that about 70% of salts of monovalent copper is deposited, the rest is in solution.

The aim of the invention is the regeneration of poisoned cations of sodium and potassium and other poisons the catalyst solution is almost full utilization of copper ions and palladium.

It was found that the goal in accordance with the present invention is solved by the method of regeneration of the catalyst of liquid-phase oxidation of olefins to aldehydes and ketones is a solution of the chlorides of palladium, copper and acetic acid by the action of carbon monoxide, or olefin, or hydrogen with subsequent treatment of the obtained solid residue, oxygen or gas containing oxygen, with the addition of hydrochloric acid and water, characterized in that it is obtained after recovery of the mixture of the precipitate and the mother liquor add a solution of 0.08 and 0.12 wt.% hydrate of sodium oxide or sodium carbonate (soda ash) in a volume ratio to the katariah and potassium oxidize.

Example 1-7. In a glass reactor with jacket, heated water from a thermostat, with a diameter of 4 cm and a height of 25 cm was placed an aqueous solution of an industrial catalyst containing palladium chloride, chlorine copper, acetic acid, hydrochloric acid and the cations potassium and sodium. Through the filter SCHOTT miss 5 liters of a reducing gas. After cessation of gas flow in the reactor was added a solution of hydrate of sodium oxide.

Then served for 0.5 h gas-reducing agent for mixing and after the termination of gas supply the suspension settles within 2 hours. Then the mother liquor is removed, the crystals washed with water. After washing to the precipitate add a solution of hydrochloric acid and distilled water and air-tight. The results of the experiments are presented in table. 1.

For a better understanding of the invention and Fig. 1 shows a diagram of the regeneration of the catalyst.

In the activator 1 serves catalyst solution, heated to 100-110oC, on regeneration.

To prevent cooling of the catalyst solution during the restoration of the olefin it warm up in the activator with water vapor coming into the built-in activator coil.

ESWL olefin. The reaction gases containing unreacted olefin, aldehyde (ketone), water vapor, proceed through the tank 4 into the reactor oxidation of the olefin plant producing acetaldehyde (ketone). When using carbon monoxide or hydrogen to recover unreacted gases are disposed of by other known methods.

After recovery of the catalyst solution for 4-6 hours and receive data analysis the recovered catalyst solution in the absence of divalent copper solution is cooled to a temperature of 50-60oC water supply to the coil.

After cooling activator download solution of hydrate of sodium oxide or sodium carbonate and the mixture is stirred with ethylene. Then, supply of ethylene was stopped, and sucks is formed of metallic palladium and crystals odnoklasniki copper. After settling the mother liquor is extracted from the activator of nitrogen through the filter 2 in the container 3 for further purification in a known manner.

In the activator serves himochishchennuju water (steam condensate) for washing the crystals and serves ethylene for sparging. After washing, stop filing ethylene and is sucks. Then wash solution is extracted with sodium or sodium carbonate. If necessary, the precipitate may again be washed with demineralized water (steam condensate).

After washing activator blown off with nitrogen, and then upload the calculated amount of hydrochloric acid and water in the form of steam condensate and the activator serves the air. The oxidation is carried out 4 to 6 hours at a temperature of 50-110oC. a purified solution of the activator squeeze nitrogen into the container 4 and serves to install the oxidation of olefins.

Example 8-10. Catalyst solution with a temperature of 110oC into the activator 1 at 10 m3. After purging the system in the activator serves ethylene and raise the pressure up to 14 kg/cm2. The consumption of ethylene was set to 250 kg/h of the Reaction gases containing ethylene, acetaldehyde, and so on, dropping into the reactor for the synthesis of acetaldehyde. After recovery of ethylene for 6 hours in the activator download 10 m3solution of sodium carbonate concentration of 0.1 wt. %. The mixture is stirred with ethylene for 1 hour. Then, supply of ethylene was stopped and the resulting crystals assert within 2 hours. The mother liquor is extracted with nitrogen through the filter 2 in the container 3 for processing.

Then upload 10 m3steam condensate and hours and wash solution is extruded nitrogen into the container 3 through the filter 2. After purging with nitrogen in the activator serves the calculated amount of hydrochloric acid and water in the form of steam condensate and served in the air in quantities of 600 nm3/H. the Oxidation of lead for 6 hours at a temperature of 90oC. the resulting catalyst is regenerated solution is poured into the container 4 and used in site of synthesis plant producing acetaldehyde.

The results of the experiments are presented in table. 2.

Method for regenerating catalyst for liquid-phase oxidation of olefins to aldehydes and ketones, which is an aqueous solution of palladium chloride, copper and acetic acid, by the action of carbon monoxide, or olefin, or hydrogen with obtaining the recovered solid residue which is treated with oxygen or gas containing oxygen, with the addition of hydrochloric acid and water, characterized in that it is obtained after recovery of the mixture of salts precipitate and the mother liquor add a solution of hydrate of sodium oxide or sodium carbonate concentration of 0.08 and 0.12 wt.% in a volume ratio to the catalyst solution of 0.8 - 1.2 : 1, the mother liquor separated from the crystals, which, after leaching of cations of sodium and potassium oxidize.

 

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