DE1443799C - Process for the production of aide hyden and alcohols - Google Patents

Description

The main patent relates to a process for the production of aldehydes and alcohols by the oxo synthesis with addition of carbon oxide and hydrogen to olefinic hydrocarbon compounds in the presence of cobalt carbonyl compounds as a catalyst, in which the catalyst is made from the hydroformulation product by means of aqueous salt solutions at elevated temperature with binding of the cobalt as a complex extracted and the extracted cobalt compound is reused as a catalyst, the hydroformylation product being treated in the presence of water, carbon oxide and hydrogen at elevated temperature and pressure with a compound of an element of group Ia or Ha of the periodic table with complex formation for the extraction of the catalyst, whereupon the separated water-soluble complex with the aqueous phase and the cobalt carbonyl is set free with acid. The metal compound used can be an oxide or a salt, and "elemental metal" can also be used if it does not react with water. J

The cobalt / carbonyl hydrogen released by the acid treatment is removed from the volatilization column with the aid of a gas such as nitrogen, CO, H ₂ or CO ₂ . The carrier gas entraining the cobalt carbonyl hydrogen is either fed to a further column or the cobalt carbonyl hydrogen is absorbed with the aid of the olefin used for the hydroformylation.

The invention has set itself the task of converting the cobalt carbonyl into the To simplify the cycle and the difficulties associated with handling a carrier gas z. B. with regard to the sealing of the transfer line to avoid.

According to the invention, this is achieved in that the liberated cobalt carbonyl is recycled is dissolved in the circuit in an organic solvent. The obtained solution of Cobalt carbonyl hydrogen can easily be recycled into the reaction zone, as can the added solvent It is particularly useful when the olefin used in the oxo synthesis has difficulties with respect to the solution of cobalt carbonyl hydrogen, e.g. B. if it is under the conditions among which the cobalt carbonyl hydrogen is extracted from the acidic aqueous solution is supposed to be gaseous. Upon transfer of the free cobalt carbonyl hydrogen in the solvent According to the invention, it can be advantageous to carry out the oxo reaction directly in the presence of the acidic aqueous Solution to perform.

Preferably in the method of the invention the organic solvent is an aromatic or saturated aliphatic hydrocarbon, an alcohol, a still residue or other product the oxo synthesis or a mixture of these compounds. On the other hand, the organic solvent can also to be the olefinic hydrocarbon compound used in oxo synthesis.

In one embodiment, the cobalt carbonyl compound set free in the aqueous phase is driven over with an inert carrier gas into the f> 5 organic solvent. According to a In another embodiment, the cobalt carbonyl compound released in the aqueous phase is through intimate contact of the aqueous phase with the organic solvent converted into this.

The conditions under which the process described in the main patent is preferably carried out are as follows: The temperature in the catalyst extraction is between 40 and 16O ⁰ C and the thereby applied pressure between 10 and 150 atmospheres.

It has now been found that the reaction conditions for the oxo synthesis according to the invention can be largely varied from those specified in the main patent, and that completely satisfactory results are obtained with regard to the decobalting. For example, temperatures between 20 and 250 ° C. and pressures between 1 and 500 atmospheres can be used in the catalyst extraction, so that the scope of this possibility of catalyst recovery is considerably expanded This adsorption can take place at a temperature between 10 and 30 ^° C. under a pressure between 1 and 20 atm. This is a considerable advantage, especially when high temperatures and pressures are used in the catalyst extraction.

In addition to the oxo process described here for the production of aldehydes and alcohols can this process for the recovery of cobalt carbonyl compounds, especially of cobalt carbonyl hydrogen, can also be used in any other organic synthesis in which this compound is used is used directly or indirectly as a catalyst.

More precisely, the process according to the invention for the recovery of a cobalt carbonyl compound consists contained in an organic liquid insoluble in water, mainly in that this organic liquid and an aqueous medium, which is a solution or a Suspension of at least one oxide, hydroxide or salt of elements of groups la or Ha des Contains periodic table, is brought into intimate contact with each other, preferably alkali and Alkaline earth metals are used to form an ionic, water-soluble cobalt compound, and the entire cobalt present is brought into solution anionically in the aqueous medium, after which one separates this aqueous medium from the organic liquid, adding a strong acid to the aqueous medium is added to form an acidic aqueous solution containing the cobalt carbonyl compound, and the latter Connection removed from it. This is done, for example, by passing over an inert gas containing the cobalt carbonyl hydrogen entrains and allows recovery of the gaseous compound. Favorably brings according to the invention, the gas containing the cobalt carbonyl compound is in contact with a organic solvent, which absorbs this, so that a solution of the cobalt carbonyl compound that can be returned to the cycle.

According to another embodiment of the method for recovering cobalt according to the invention the acidic aqueous mixture containing the cobalt carbonyl compound is brought directly with an olefinic one Compound or an organic solvent in contact, shakes them out of the aqueous Phase and separates it from the olefinic or

organic phase when the latter has taken up the cobalt carbonyl compound.

example

700 g heptenes containing 1.6 g of cobalt in the form of Dikobaltoktacarbonyl contained were, on in a 2-1 autoclave not oxidizable steel under magnetic contact and at a constant pressure \ '160 kg / cm ² and at a temperature of between ^λ 125 and 160 "C hydroformylated.

The egg cobaltation was carried out in the same autoclave without the hydroformylation product to remove by means of a lock chamber 175 ml of water, which contains the cobalt removal agent contained, introduced and the oxo product> 5 with vigorous stirring for 30 minutes each the 'pressure and temperature conditions treated.

After cooling the autoclave and cleaning the gas, the reaction products were transferred to a separatory funnel transferred, where after separation of the aqueous layer the organic product 3 times with 175 ml Water was washed.

The following quantities were then determined according to the mixing ratio:

the amount of cobalt present in the oxo product after the cobalt removal treatment as well as after three Washes with water remained;

the total amount of cobalt and the amount of cobalt that was in the form of the tetracarbonyl anion [Co (CO) ₄ ] "in the aqueous extract that came from the cobalt removal and to which the water from the first wash of the oxo product had been added,

the ^Kob:; Uii.ci! Gc m learn water from the other two washes.

In carrying out this embodiment, the entire amount of the reaction product was not attempted win so that the yield was determined based on the amount of cobalt, which was contained in the extracted products and accounted for about 70% of the total amount. But there all attempts under similar product recovery conditions were carried out: are the results of Table 2 below, obtained by varying the temperatures, pressures and cobalt removal agents are comparable.

Table 1 shows the various reaction conditions that were used in the experiments compiled.

Table 1

35

attempt Cobalt removal agent temperature pressure I. sodium 150 160 II the same 150 240 HI the same 206 160 IV the same 60 160 V the same 150 10 VI the same 60 10 VII Disodium phosphate 150 160 VIII Sodium oxalate 150 160 IX Sodium sulfate 150 160

Table 2 shows the process conditions and the analytical results of the respective new ones Cobalt removal attempts.

table

Process conditions and analytical results from cobalt removal tests with oxo products

the hydroformylation of 700 g of heptenes

formula

Amount (g)

Stoichiometric
Excess compared to the used
Cobalt (%).

Procedural conditions
Temperature ("C) ..
Pressure (kg / cm ² ) ...

Analyzes

Cobalt in the oxo product (mg) ...

Cobalt in the oxo product after the
Cobalt clearing
and three washes (mg) ..

1.75

150
160

1640

III

Cobalt removal agent

IV

Na ₂ CO ₃

Vl

1.75 1.74 U 1.75 14th 15th 16 15th 150 206 60 150 240 160 160 10 1661 1672 1627 1636 15th 55 .163 17th

1.7

13th

60
10

1670

524

VII

Na ₂ HPO ₄
12th

150

150
160

1590

VIII

Na ₂ (COO) ₂

2.2

21

150
160

1599

84

IX

Na ₂ SO ₄
5.0

156

150
160

1629

344

continuation

Entkohaltierungsmittcl

III

IV

VI

VII

VIII

IX

formula

Cobalt in water
extract

+ Washing water
the 1st washing

Cobalt in the last wash water
both washes

Total amount of
recovered
Cobalts

Cobalt in water
Extract in form
of [

1153 N a ₂ CO ₃ 902 1240 14th 1094 not
definitely 90 3 1182 23 not
definitely 1009 1261 1153 1172 - 819 1188 771 not
definitely

781

69

1374

619

Na ₂ HPO ₄

1100

1145

1082

Na ₂ (COO) ₂

863

988

850

Na ₂ SO ₄

782

139

1265.

450

Thus, one can determine on the basis of the analytical results shown in Table 2 that it is possible to perform the catalyst circulation in an optimum manner if the alkaline Dekobaltierung at relatively high temperatures and pressures performs (Experiment I and II with sodium carbonate at a temperature of 150 ⁰ C. and pressures of 160 and 240 kg / cm ² ).

On the other hand, the Entkobaltierungseffekt remains satisfactory, when the alkaline Entkobaltierung at a relatively high pressure and at a temperature of about 200 ° C (Experiment III, Temperature 206 ⁰ C, pressure 160 kg / cm ²⁾ by stirring, but the circuit yield tends cobalt to a decrease due to the formation of cobalt formate. For this reason, under the conditions mentioned in Experiment III, 30% cobalt is found in the aqueous extract in the form of the formate and thus leaves the catalyst circuit.

At lower pressure and a relatively high temperature (test V, temperature 150 C and pressure 10 kg / cm ² ) the cobalt removal is satisfactory, but the conversion of the cobalt into carbonyl anions is less complete than in the examples in which, due to the formation of a cobalt precipitate higher pressures can be used.

Finally, the cobalt removal tests with chemical agents other than sodium carbonate yield clearly equivalent results, especially in the case of the disodium phosphate, which is in a stoichiometric Excess was applied. It is obvious that the person skilled in the art will find the appropriate Compound for cobalt removal can be selected from the substances that are the subject of the present invention Invention and the main patent are, depending on the special requirements of the chemicals required, Economy etc.

Claims (5)

Patent claims: 1. Process for the production of aldehydes and alcohols by the oxo synthesis with addition of carbon monoxide and hydrogen to olefinic hydrocarbon compounds in the presence of cobalt carbonyl compounds as a catalyst in which from the hydroformulation product the catalyst by means of aqueous salt solutions at elevated temperature with binding of the cobalt extracted as a complex and the extracted cobalt compound is reused as a catalyst is, the hydroformylation product in the presence for the extraction of the catalyst of water, carbon dioxide and hydrogen at elevated temperature and pressure a compound of an element of group I a or Ha of the periodic table with complex formation is treated, whereupon the water-soluble complex is separated with the aqueous phase and the cobalt carbonyl is set free with acid, according to patent 1 206 419, characterized in that, that the liberated cobalt carbonyl dissolved in an organic solvent for recycling will. 2. The method according to claim 1, characterized in that that the organic solvent is an aromatic or saturated aliphatic hydrocarbon, an alcohol, a still residue or other product of the oxo synthesis or is a mixture of these compounds. 3. The method according to claim 1, characterized in that the organic solvent is the in is an olefinic hydrocarbon compound related to oxo synthesis. 4. The method according to claim 1 to 3, characterized in that the in the aqueous phase in Freed cobalt carbonyl compound with an inert carrier gas in the organic solvent is overdriven. 5. The method according to claim 1 to 3, characterized in that the in the aqueous phase released cobalt carbonyl compound by intimate contact of the aqueous phase with the organic Solvent is transferred into this.