Method of removing carbonyl compounds of cobalt or rhodium from an aqueous solution of 3-hydroxypropane

 

The invention relates to the production of 1,3-propane diol by hydroformylation of ethylene oxide through the intermediate solution of 3-hydroxypropane from which to remove residual carbon dioxide and insoluble catalytic compounds of cobalt or rhodium. The process includes the following stages: (a) contacting the solution of 3-hydroxypropane with oxygen in acidic conditions at a temperature in the range from about 5 to about 45oWith obtaining a mixture of oxidation products containing an aqueous solution of 3-hydroxypropane, one or more water-soluble compounds of cobalt or rhodium and by-product carbon monoxide; (b) removing by-product of carbon monoxide from a mixture of oxidation products, and (C) the removal of soluble metal compounds from a mixture of oxidation products by contact with acidic ion exchange resin at a temperature of less than 45oC. Technical result: the effective removal of catalytic amounts of cobalt and rhodium from the reaction products of hydroformylation. 6 C.p. f-crystals, 5 PL.

The invention relates to the selective removal of the metal component from the aqueous stream containing the heat-sensitive component in the solution. Gammu cobalt, the process of obtaining 1,3-propane diol, where cobalt is effectively removed from the intermediate water stream.

1,3-Propandiol is an important industrial chemical, which can be obtained in the two-stage process, where the ethylene oxide in the beginning hydroformylation in organic solution in the presence of a metal catalyst such as cobalt carbonyl or rhodium, which gives it 3-hydroxypropyl. The intermediate compound 3-hydroxypropyl extracted with water under pressure and cobalt catalyst is returned to the cycle in response hydroformylation in the organic phase. Water 3-hydroxypropyl then hydronaut to 1,3-propane diol. 3-Hydroxypropyl can be routed directly to the hydrogenation reactor. However, carbon monoxide dissolved in the water is poison for most of heterogeneous hydrogenation catalysts, when a small amount of metal catalyst is transferred to the aqueous phase during the extraction of 3-hydroxypropane. For acceptable yields of product, the catalyst must be removed from the aqueous 3-hydroxypropane in conditions in which there is no decomposition of 3-hydroxypropane.

Therefore, the object of the invention is to provide a method to effectively remove connections one of the embodiments of the invention additional objective is to provide water flow 3-hydroxypropane for hydrogenation, which essentially does not contain carbon monoxide and residual metal compounds.

According to the invention carbonyl compounds of cobalt or rhodium is removed from the aqueous solution of 3-hydroxypropane method containing the steps: (a) contacting the solution of 3-hydroxypropane with oxygen in acidic conditions at a temperature in the range from 5 to 45oWith obtaining a mixture of oxidation products containing an aqueous solution of 3-hydroxypropane, one or more water-soluble compounds of cobalt or rhodium and by-product carbon monoxide; (b) removing the formed by-product of carbon monoxide from a mixture of oxidation products, and (c) passing the mixture of oxidation products in contact with acidic ion-exchange resin, the temperature of which is supported by at least 45oWith, and removing at least part of the soluble metal compounds from a mixture of oxidation products.

This method is useful, for example, in the production of 1,3-propane diol of ethylene oxide through the intermediate solution of 3-hydroxypropane containing residual carbon monoxide and insoluble catalytic compounds of cobalt or rhodium.

Detailed description of the invention the Method according to the invention otnosites obtain 1,3-propane diol by hydroformylation of ethylene oxide to 3-hydroxypropane with subsequent hydrogenation of 3-hydroxypropane to 1,3-propane diol.

Separate or combined streams of EO (ethylene oxide), and N2(synthesis gas) is fed into the tank hydroformylation, which may be a reactor pressure vessels, such as ozonation column or tank with agitation operating intermittently or continuously. The feed streams are contacted in the presence of a catalyst of hydroformylation, usually of metal carbonyl selected from the CARBONYLS of rhodium and cobalt. The catalyst hydroformylation usually present in the reaction mixture in amounts ranging from 0.01 to 1 wt.%, preferably from 0.05 to 0.3 wt.%, by weight of the reaction mixture of hydroformylation. Hydrogen and carbon monoxide should usually be introduced into the reactor in a molar ratio ranging from 1:2 to 8:1, preferably from 1:1 to 6:1.

The reaction hydroformylation carried out under conditions effective to obtain a mixture of the reaction products of hydroformylation, containing most of the 3-hydroxypropane and less of acetaldehyde and 1,3-propane diol, while the content of 3-hydroxypropane support in the reaction mixture is less than 15 wt. %, preferably in the range from 5 to 10 wt.%. (To ensure that solvents having different densities, jelatek, preferably in the range from 0.5 to 1M). Typically catalyzed by cobalt reaction hydroformylation is carried out at an elevated temperature less than 100oC, preferably from 60 to 90oS, most preferably from 75 to 85oWith, in the case of catalyzed reactions of rhodium hydroformylation respectively approximately 10oWith the above. The reaction hydroformylation usually carried out at a pressure in the range from 0.69 to 34,47 MPa (7,0307-351,535 kg/cm2), preferably (for efficiency of the process) 6,89-24,13 MPa (70,307-246,074 kg/cm2), a higher pressure is preferred for greater selectivity.

The reaction hydroformylation carried out in a liquid solvent, inert to the reagents. By "inert" it is meant that the solvent is not consumed during the reaction. Typically, the ideal solvents for the process of hydroformylating should solubilisate carbon monoxide, must be essentially not miscible with water and must be polarity from low to moderate, as the intermediate product 3-hydroxypropyl should be solubilisation to the desired concentration of at least about 5 wt.% in terms of hydroformylation, while the usesto is not miscible with water" means, the solvent has a solubility in water at 25oWith less than 25 wt. % so forms a separate enriched hydrocarbon phase by extraction with water 3-hydroxypropyl from the reaction mixture of hydroformylation. The preferred class of solvents are alcohols and ethers, which can be described by the formula R2-O-R1(1) where R1means hydrogen or C1-20linear, branched, cyclic or aromatic hydrocarbon or mono - or polyalkylene, and R2means C1-20linear, branched, cyclic or aromatic hydrocarbon, alkoxy or mono - or polyalkylated. The most preferred solvents hydroformylation are ethers such as methyl tert-butyl ether, ethyl tert-butyl ether, diethyl ether, phenyl-isobutyl ether, ethoxyethyl ether, diphenyl ether and diisopropyl ether. The mixture of solvents, such as tetrahydrofuran/toluene, tetrahydrofuran/heptane and tributyl alcohol/hexane can also be used to achieve the desired properties of the solvent. Currently, the preferred solvent due to the high outputs 3-hydroxypropyl, which can be the Oia outputs at moderate reaction conditions, the reaction mixture hydroformylation preferably will contain a promoter and a catalyst, in order to accelerate the reaction rate. Preferred promoters contain a lipophilic salt of phosphonium and lipophilic amines, which accelerate the speed of hydroformylation without imparting hydrophilicity (water solubility) to the active catalyst. As used here, "lipophilic" means that the promoter has a tendency to remain in the organic phase after extraction 3-hydroxypropyl water. The promoter will generally be present in an amount ranging from 0.01 to 1.0 mol per mole of cobalt. The currently favored lipophilic promoters are acetate tetrabutylphosphonium and dimethyldodecylamine.

At low concentrations of water serves as a promoter of education particles of the desired carbonyl catalyst. The optimum water content for hydroformylation in simple solvent methyl tert-butyl ether is in the range from 1 to 2.5 wt.%. Excessive amounts of water, however, reduce the selectivity (3-hydroxypropyl + 1,3-propandiol) below acceptable levels and can cause the formation of a second liquid phase.

After the reaction hydroformylation mixture of reaction products of hydroformylation containing 3-hydroxypropyl, the solvent of the reaction, 1,3-propuskajut in the tank extraction, where an aqueous liquid, usually water and an optional improving the Miscibility of the solvent added for extraction and concentration of 3-hydroxypropane for the next stage of hydrogenation.

Liquid-liquid extraction 3-hydroxypropane in water can be carried out by any appropriate means, such as mixer-settlers, extraction columns with a nozzle or plates or contact devices with rotating disks. The amount of water added to the mixture of reaction products of hydroformylation, as a rule, should be such as to ensure against water-mixture in the range from 1:1 to 1:20, preferably from 1:5 to 1: 15. The extraction with water is preferably carried out at a temperature ranging from 25 to 55oWith, preferably a lower temperature. Extraction with water at 0,34-to 1.38 MPa (3,5154-14,0614 kg/cm2) of carbon monoxide at 25-55oWith leads to the maximum extraction of the catalyst in the organic phase.

The organic phase containing the reaction solvent and most of the cobalt catalyst can be recycled with optional cleaning heavy end fraction from the extraction vessel into the reaction zone of hydroformylation. Water a resin to remove residual cobalt or rhodium catalyst. A large part of the residual synthesis gas is removed from an aqueous solution of a single equilibrium by distillation. Found, however, that even very small amounts of carbon monoxide remaining in the solution can affect the performance characteristics of the catalyst for hydrogenation, and the preferred embodiment of the method of this invention removes the specified residual carbon monoxide, as described below, before passing an aqueous solution of 3-hydroxypropane on hydrogenation.

An aqueous solution of 3-hydroxypropane processed by the method according to the invention typically will contain from 4 to 60 wt.% 3-hydroxypropyl, usually from 20 to 40 wt.% 3-hydroxypropyl, and from 10 to 400 m D. water-soluble and not water soluble compounds of cobalt or rhodium, such as Co[Co(CO)4]2, CO2(CO)8and Rh6(CO)16.

In the method according to the invention the acid containing cobalt aqueous solution of 3-hydroxypropane brought into contact with oxygen under conditions effective for the oxidation of insoluble compounds of cobalt to the water-soluble compounds of cobalt. An aqueous solution of 3-hydroxypropane can be made sufficiently acidic by the addition of the crystals from 3 to 6, preferably from 3 to 4. Suitable acids include C1-4organic acids. Alternative water acid can be obtained as a by-product of hydroformylation of ethylene oxide under conditions favorable for the formation of 3-hydroxypropionic acid.

Oxidation can usually be carried out by introducing oxygen-containing gas, such as air, in an aqueous solution of 3-hydroxypropane. The preferred technology for the oxidation involves bubbling air up through the disc column, when a solution of 3-hydroxypropane, which should be treated flows in a downward direction through the column. The process is carried out at a temperature in the range from 5 to 45oC and at atmospheric pressure. The length of stay depends on other variables, but are typically in the range from 1 to 15 minutes.

The technique ozonation for the oxidation of insoluble metal compounds creates an additional effect displacement of carbon monoxide from an aqueous solution, especially if the composition of the oxidizing gas injected inert gas, such as nitrogen or carbon dioxide, to prevent the formation of flammable mixtures.

Some types is, for example sodium salts of sulfonated polystyrene), alkali metal salts weak acid resins and acid forms as strongly-and weakly acidic resins. Best results in commercial processes reach, when the resin selected for the removal of cobalt or rhodium has a low potential decomposition of 3-hydroxypropane, can be regenerated with the one-stage process and strongly adsorbs particles of the target metal. These requirements will best meet the acid form strongly acidic resin, which strongly adsorb oxidized particles of cobalt and easily regenerated with sulfuric acid in one stage. The use of such resins in the layer with a short contact time at the present time, it is preferable to remove metal. Suitable resins for the removal of metal commercially available as resin IR120, A or a-15 from Rohm & Haas and resin M-31 from Dow Chemical.

In order to minimize the decomposition of 3-hydroxypropane, the temperature of the ion exchange resin should be maintained below about 45oWith and residence time should be kept to a minimum, for example, through the use of shorter layers of ion exchange resin. Such layers are designed to sharpen the profile of the zone of absorption/ion exchange to the point where the transmission channel is not sufficient to operate the About in the water flow. In accordance with one aspect of the invention, contacting the resin with acid, such as 10% sulfuric acid, cleans the resin and restores a stable ion. The acid is preferably at an elevated temperature in the range from 70 to 110oC. the processing Duration from 0.5 to 2 hours is usually sufficient. The efficiency of the method is desirable for removing the concentrated cobalt or rhodium from the resin to turn again in catalytic carbonyl form.

The treated water stream 3-hydroxypropyl missing in the zone and subjected to hydrogenation reaction with hydrogen in the presence of a hydrogenation catalyst to obtain a mixture of products of hydrogenation containing 1,3-propandiol. Catalytic hydrogenation preferably is a Nickel catalyst on a carrier in a stationary layer, such as commercially available as Calsicat E-475SR and R-3142 from W. R. Grace.

The method of hydrogenation of the present invention can be carried out in one stage or in two or more successive temperature stages. In the preferred embodiment, the hydrogenation is carried out, as described above, at a temperature in the range from 50 to 130oWith the subsequent second stage, conducted at temperature a temperature higher than 120oFor the inverse transformation of heavy leaf fractions in 1,3-propandiol. In this process, the hydrogenation zone contains a series of two or more separate reactors.

Residual solvent and water extractant can be extracted by distillation in the column and recycled to the process water extraction by additional distillation to separate and eliminate light end fractions. The flow of product containing 1,3-propandiol, may be placed in a distillation column to extract 1,3-propane diol from the heavy end fraction.

Example 1 cobalt Poisoning of the Nickel catalyst for hydrogenation.

Aqueous solutions of intermediate compound 3-hydroxypropyl (3-hydroxypropyl) with added cobalt or without hydronaut to 1,3-propane diol on the Nickel catalyst on a carrier (50% Nickel on silica - alumina, 814 mesh). In each experiment using 28 g of fresh catalyst is held in an annular basket for catalyst placed in a 500 ml reactor with mixing with exhaust tube impeller for re-dispersion of hydrogen from the upper space in the liquid. Charged to the reactor 320-340 g water ex gaseous hydrogen. Then the reactor is heated to the desired reaction temperature, 1-2 ml samples periodically taken for the analysis of components by gas chromatography.

In experiments 1 and 2, an aqueous solution of 3-hydroxypropyl oxidized by air, containing oxygen, by ozonation through a submerged tube in tanks with subsequent ion exchange with a strongly acidic resin (sulfonated polystyrene). Gas chromatography shows that 3-hydroxypropyl quickly hereroense to 1,3-propane diol.

In experiment 3 an aqueous solution of 3-hydroxypropane not bubbled air and do not handle in contact with ion exchange resins. As a result, 92 M. D. cobalt and residual carbon monoxide remain in the solution. The rate of hydrogenation of 3-hydroxypropane to 1,3-propane diol significantly reduced compared with the speed in experiments 1 and 2.

In experiment 4 an aqueous solution of 3-hydroxypropane first oxidized by ozonation air with subsequent ion exchange treatment to remove residual cobalt. Cobalt then re-add in the form of cobalt acetate to obtain a solution of 3-hydroxypropane containing 533 M. D. cobalt. The rate of hydrogenation of this solution is also significantly lower than for solutions 3-hydroxyp, the cobalt are poisons for the catalyst hydrogenation and that oxidative deformirovanie solution of 3-hydroxypropane (removal of carbon monoxide) is insufficient to prevent poisoning of the catalyst in the hydrogenation of residual cobalt.

Example 2 Influence of oxidation on the removal of cobalt cation exchange resin For subsequent experiments aqueous solutions of 3-hydroxypropane get in a pilot plant continuous operation with a small capacity, consisting of two series-connected 2 l reactors hydroformylation operating at 80oAnd 10,34 MPa (108,976 kg/cm2a 4:1 N2/CO (synthesis gas), through which circulation of the solvent MTBE at 80-100 ml/min and the reagent SW served on the first stage of the reaction when the feeding speed of 1.8-3.0 ml/min Soluble catalyst hydroformylation diaballickall served at 1200-2000 m D. Unreacted EO, the intermediate compound 3-hydroxypropyl and catalyst output from the second stage reactor and dispersed at the bottom of the extraction column with a diameter of 5.08 cm (2 inches), containing 7 lattice plates, placed at intervals of 5.08 cm (2 inches). Water (45o(C) served at 4.5-7 ml/min as AC,27-9,65 MPa (84,368-98,430 kg/cm2). Water flow 3-hydroxypropyl coming from the bottom of the specified column usually contains 25-35 wt.% 3-hydroxypropyl, 0.2-0.4 wt.% SW and 30-200 m D. cobalt.

The specified water flow 3-hydroxypropyl directed to a sight glass with a diameter of 5.08 cm (2 inches) and a height of 20.32 cm (8 inches), typically operating at 1/2 full marks (200 ml), where the instantaneous evaporation of the liquid by reducing the pressure to approximately atmospheric. A significant part of the synthesis gas dissolved in a solution of 3-hydroxypropyl, freed thus from the solution. The aqueous solution extracted from the bottom of the vessel at the control level, contains a small amount of residual synthesis gas.

For experiments 5 and 6 from the specified degassed water intermediate flow 3-hydroxypropyl containing 69 M. D. cobalt, select two samples in a flask under nitrogen atmosphere. Each vial contains 1 part by volume of strong acid (cationic) ion-exchange resin based on sulfonated polystyrene and 3 parts by volume of the liquid sample. In experiment 6 bottle bubbled with air for 5 minutes, and another flask kept closed to exclude air. Both rotate flask for 3 hours for mixing with subsequent analizata remains unoxidized sample, while the content of cobalt oxidized sample is reduced to 1 M. D.

Example 3
The simultaneous destruction of the synthesis gas and the oxidation of the cobalt
For the study of continuous oxidation and removal of cobalt after stage degassing described in example 2 above, add 10-disc glass distillation Oldershaw column with a diameter of 5.08 cm (2 inches). Water the product flows down on a plate column at 6-12 ml/min with a maximum loading plates of 0.48 cm (3/16 inch) and usually 0,24 cm (3/32 inch). Oxidizing and deformirujuschij gas add upward flow through the column by mixing air and nitrogen in two totaltrax producing a common thread 0,0057-0,028 m3/h under normal conditions when the oxygen concentration of 2-10 mol.%. The dilution of oxygen lower than its concentration in the air, it is desirable to ensure that the work outside the scope of ignition. Depending on the working conditions can be provided by changing the number of plates for the liquid.

The second column of diameter of 5.06 cm (2 inches) with a nozzle height of 15.24 cm (6 inches) or section 60,96 cm (24 inches) of 0.64 cm (1/4 inch) perforated stainless steel exploited instead of plate Oldershaw column for the same experiments, allowing you to explore the influence by keeping okisnoi cation exchange resin is placed downstream from desorbers columns. Incomplete oxidation of cobalt in the material to be applied to this layer, can be determined by the appearance of cobalt at the outlet of the ion exchange layer. Samples of water intermediate material supplied to desorber, and samples taken at the outlet of the ion exchange layer, analyze the cobalt by the colorimetric method described above. Ion-exchange layer fill with fresh resin before the experiments to ensure that breakthrough cobalt layer cannot be attributed to contamination of the resin with ethylene oxide.

The results are shown in table 1. The column describes the number of plates of glass columns loaded by the fluid during the test, or the height of the Packed column inches for experiments conducted in the Packed column. Increasing the height of the Packed zone or increasing the number of plates soaked in the liquid, increases the area available for contact between the liquid and gaseous phases, and increases the contact time between the gas and liquid phases.

Column D indicates whether the free acid. A small amount of organic acid is a byproduct of hydroformylation SW. This acid corresponds to at least 10-fold molar excess relative to the present CC)2. If a mixture of solvents hydroformylation recycle at the reaction temperature without the addition of EO, no acid is not formed. More significant fraction of cobalt is extracted into the water stream in the absence of acid. This case corresponds to the mark "no" acid in column D. Column E shows the dilution gas is mixed with air to provide desorbers ability to perform work outside the scope of Flammability. In most cases the use of nitrogen, although experience 19 is carried out with carbon dioxide. Column F gives the total flow rate of the mixed Stripping gas in m3/h at standard conditions, while column G gives mol.% oxygen consumption desorbers gas. Column H gives their work to describe the flow in m3/h only oxygen. Column I shows the cobalt (M. D. ), emerging from the ion exchange layer. This non-oxidized cobalt, which was not removed by ion exchange. Column J shows the original amount of cobalt in the aqueous intermediate product before processing, oxidation and ion exchange. Column K shows the molar ratio of oxygen to cobalt in the oxidation desorber. In all cases serves excess oxygen.

Experience the 19th ironically by ion exchange. In the experience of 20 essentially all of the cobalt is removed after desorption and oxidation of aqueous intermediate product in the same column under the described conditions. Experiments 9 through 11 show the effect of flow rate of Stripping gas at a fixed molar percentage of oxygen for a glass column trays. The removal of cobalt increases when increasing the intensity of the desorption. A similar result is observed in the absence of acid for experiments 15-17. Experiments 12 and 13 show the effect of mol.% oxygen on the oxidation efficiency: the ability to oxidize the cobalt is increased as the concentration (partial pressure) of oxygen in desorbers gas increases. Comparison of experiments 11 and 14 shows that when the number of plates ("steps") to reduce the oxidation of cobalt is less complete. To such conclusion comes when comparing experiments 20 and 21 in the Packed column 60,96 cm (24 inches) with the characteristics of the column 15.24 cm (6 inches) in experiments 22-24. In the lower column of the cobalt is oxidized completely, despite the increased concentration of oxygen in relation to similar experiences in higher 60,96 cm (24 inches) Packed column.

Experiments 12 and 15 show the effect of acid. In the presence of acid oxidation is complete, then oxygen.

Solid compounds of cobalt are precipitated in the absence of acid, a by-product of hydroformylation. In the experience of 18 CO2used as a dilution gas, forming carbonic acid upon absorption of an aqueous phase intermediate product. Although, it would seem that this should not increase the degree of oxidation, the formation of solid substances is excluded. It is observed that the addition of CO2in a glass column solubilities precipitation of cobalt formed during operation in the absence of acid with N2as a diluent.

The results, summarized in table 1, confirm that and desorption, and oxidation containing cobalt water flow necessary for the conversion of cobalt in the form, remove the ion exchange layer.

Example 4
The influence of acid on the oxidation of cobalt
To study the effect of acid on the oxidation of cobalt conducted a series of experiments in which the product hydroformylation extracted in the presence of sodium acetate, resulting in the extraction of cobalt, mainly as NaCo(CO)4. This allows a higher concentration of cobalt can be extracted in the aqueous intermediate product, so that its concentration is now suppresses the oxygen is and tetracarbonyl cobalt can be monitored by infrared spectroscopy (1890 cm-1). Acetic acid is then added to bring the total equivalents of carboxyl acid particles to equivalents With++and Na+with subsequent oxidation by ozonation air samples of the final fluid.

Table 2 shows the results of oxidation of cobalt at the 35oWith excess carboxylic acid. Oxidation continues essentially to completion. Table 3 shows the results of similar studies in which the initial concentration of the acid was not excessive. The oxidation in this case, apparently, it stops before completion and continues only after the addition of excess acid. These results confirm that organic acid facilitates the oxidation of cobalt.

Example 5
The influence of residual carbon monoxide by oxidation of cobalt carbonyl.

Additional studies of the oxidation is carried out in a 50 ml reactor with stirring, equipped with ZnS (45oC) an infrared crystal for tracking the location of anion tetracarbonyl cobalt. An aqueous solution disproportionating cobalt catalyst for this research is prepared by extraction solutions MTBE Co2(CO)8water at elevated temperatures of the initial solution with the concentration of cobalt 212 M. D. weight without carboxylic acids. In experiment 27 25 ml of the indicated solution is placed in a reactor, which provide a steel tube of 0.08 cm (1/32") for entry of gas, is inserted into the bottom of the reactor. The mixture is heated to 40oWith stirring and bubbling 100 ml/min of nitrogen at ambient pressure. The initial spectrum of this mixture shows the anion tetracarbonyl cobalt in 1908 cm-1and cluster anion in 1979 cm-1.

Oxidation is then carried out by switching bubbling fluidised bed gas at 3% oxygen in nitrogen. The degree of reaction can be measured by changes in the infrared spectrum that occur during oxidation. The spectrum shows the initial addition of the anion tetracarbonyl cobalt due to the expenditure of the cluster anion. Then the spent anion, forming CARBONYLS of cobalt (0) (found and Co2(CO)8and Co(CO)12). These CARBONYLS are then oxidized, forming the "main" cobalt carbonate. Under these conditions, the complete oxidation of cobalt is achieved within 45 minutes.

In the experience of 28 25 ml of the original solution is placed in a 50 ml reactor (without fixtures for ozonation gas). The solution is heated to 40oC in nitrogen atmosphere with thorough mixing. Okelani what oredom, the atmosphere override, relieving pressure and re-creating the pressure in the reactor fresh 2% oxygen in nitrogen at 35 and 50 minutes from the start of the reaction. The changes occurring during this oxidation, the same as in the experience of 27 released carbon monoxide is removed from the reaction mixture, except that the reaction rate is much less. After approximately one hour of oxidation increase, replacing the mixture of 2% oxygen by air under pressure of 0.52 MPa (5,273 kg/cm2). For complete oxidation requires an additional 25 minutes. These results demonstrate that free carbon monoxide, not desorbed from the stream water of intermediate products, including carbon monoxide associated with cobalt, as a ligand, is to suppress the oxidation of cobalt carbonyl.

Example 6
Regeneration of the ion exchange resin
Layer 83 g of strongly acidic resin A-1200 in gel form (Rohm and Haas) used for treatment of 7-12 ml/min aqueous intermediate product, extracted from the product of hydroformylation SW within one month. The aqueous intermediate product containing 22-30 wt.% 3-hydroxypropyl, 0.1 to 0.5. % residual ethylene oxide and 40-120 m., of cobalt, previously subjected to oxidation, Yes what about the carbon monoxide, and oxidizes all of the cobalt to the cationic form. After the breakthrough of cobalt on the output layer of the layer regenerate recirculation 500 ml of 10% sulfuric acid in water at ambient temperature followed by washing for 1 hour with deionized water. The adsorption and regeneration in this case considered a "cycle".

After one month of alternating operations is observed that the layer loses its effectiveness for the removal of cobalt, even after attempts of regeneration. In the final acid regeneration layer does not find that the cobalt is released from the layer with the acid regeneration. Resin is more reddish than brown fresh resin.

A sample of resin is removed from the layer and heated to 95oWith 10% sulfuric acid for 3 hours. Some pink color characteristic of cobalt sulfate was observed in the supernatant, confirming the successful regeneration of the resin. Moreover, the sample resin acquires a brown color characteristic of fresh resin. The treated sample of the resin is thoroughly washed with deionized water and dried with air to a uniform dryness. The part is soaked with 75 parts of NaOH 0.1 N. during the night, followed by reverse titration of the supernatant Hcl 0.1 N. for determining a pressure of about 6,89 kPa (0,0703 kg/cm2)) to determine the water content in the resin used in the experiment soaking over night. From these definitions the equilibrium exchange capacity of the resin is defined as 4.7 mEq./g with respect to theoretical maximum capacity of 4.9-5.1 mEq./g for fresh resin.

Resin, remote from the working layer, but not subjected to regeneration with hot acid, also washed, dried by air and balance 0.1 G. of NaOH to determine the ability. The observed ability of the resin is less than 1 mEq. centers of currency per gram of dry resin. Attempts to regenerate the specified resin at ambient temperatures of 20% sulfuric acid were also made, but essentially no cobalt is released and the resin retains its red color, characteristic of the contaminated resin. Back titration of the resin NaOH 0.1 N. shows essentially no increase in the ability of the resin is less than 1 mEq./g).

This example shows that the strongly acidic cation exchange resin subjected to a water flow of intermediate product from the stage of hydroformylation SW, loses its ability to remove cations such as cobalt, despite the regeneration of sulfuric acid, as usually practiced, when the material is to strengthen the ability of the resin to close to its original capacity. In the absence of regeneration with hot acid resin over time loses its ability to remove cobalt.

Example 7
Sample macroporous strongly acidic (Catino) exchange resin a-15 open access water flow intermediate product from the stage of hydroformylation SW for approximately one month, after which the ability to remove cobalt after regeneration at an ambient temperature of 10% sulfuric acid is reduced essentially to zero.

A sample of the specified resin and sample fresh resin analyze13WITH NMR. Contaminated resin detects new chemical shifts at 70 and 60 M. D., indicative of simple ester bonds-O-CH2-CH2- end-CH2HE, respectively. High temperature (80oC) regeneration of 10% sulfuric acid essentially fixes the peaks of the NMR spectrum. This result suggests that the contamination of the resin is the result of the influence of residual ethylene oxide in the water flow of the intermediate product in contrast to the 3-hydroxypropyl, which would give-O-CH2CH2CH2the corresponding chemical shift for the Central carbon atom due to oligomerization on the pitch.

Example 8
Some see the and 4-20 days at ambient temperature. After such exposure, the resin is thoroughly washed with deionized water, air dried and soaked in NaOH 0.1 N. to determine the ion exchange capacity and evaluation of the content of solids of resin, as described above. The results are shown in table 4.

Comparison of experiments A, D and E shows that the degree of contamination is correlated with the concentration present SW at essentially a fixed concentration of 3-hydroxypropane (25%), with 3-hydroxypropane present in at least 4:1 molar excess. This result confirms the conclusion derived from the13With NMR, pollution and loss of ion exchange capacity, which is the result of adsorption and reaction of EO on the acid centers of the resin, and not 3-hydroxypropane.

Comparison of experiments and shows that the Na-form resin is less prone to contamination than strongly acidic resin. Analysis13With NMR shows-O-CH2-CH2or derived from EO pollution to the Na-form resin and weakly acidic resin, although at lower values than observed for strongly acidic resin. "The share on the ability of fresh resin" in table 4 also shows a lower share of capacity (more extensive contamination), remaining strongly acidic resin in seegenerally contaminated SW resin.

The degree of regeneration of the resins examined as a function of temperature for contaminated strongly acidic resin by soaking samples of resin in 10% sulfuric acid for varying intervals of time and at varying temperatures. Samples of the resin, thus treated, is removed from the heating bath and is separated from the acid supernatant in the filter funnel with a thorough rinsing with deionized water to remove residual supernatant. The sample is then air dried and soaked in NaOH 0.1 N. for the reverse titration to determine the ion exchange capacity, as described above.

When the temperature increases, the degree of regeneration of sulfuric acid, the active ion-exchange capacity increases, indicating that the return of the contaminated resin to a former condition is temperature-dependent kinetic process.

Example 10
Continuous research on acid and Na-form strongly acidic resin is conducted to explore the characteristics in industrial environments. Test conditions continuous flow described in example 1. In early studies using 200 ml layer of about 87 g dry resin. In more recent studies use 12-13 g dry resin, on the tube, to ensure operation at a controlled temperature above ambient in order to investigate the effect of temperature on the degree of regeneration, which is determined by the amount of cobalt that can be removed in the following ion-exchange cycle.

The results are shown in table 5. Column F shows the time on stream for a given cycle of adsorption, G is the total time of all cycles. Column N gives the number of processed feed material per unit mass of resin for this cycle, where "I" gives the total amount of feed material processed for all cycles, for this type of resin. The adsorption cycle is defined as the time flow in the layer until then, until a breakout occurs when cobalt 4 wt.m.D. in the exhaust from the layer flow. Column J shows wt.% cobalt has been replaced by the layer at the time of breakthrough, while It gives the ratio of the number of remote cobalt to the number, which presumably fresh resin could be removed, if they were in equilibrium with the amount of cobalt in the feed material (CA.70 wt.m.D.).

The acid form of the resin during regeneration when the ambient temperature is 10% sulfuric acid (series a) detects contamination of the resin, so that after the sixth cycle resin stanovich, that supported the removal of cobalt can be achieved through high temperature (95o(C) acid regeneration of the acid form of the resin. Reach the configuration of a steady state in which the ability of the removal of cobalt stabilize at approximately 30% from the quantity that you would expect in the absence of contamination of the resin. (Independent study periodic process to determine the adsorption isotherms for the removal of cobalt fresh resin is used to determine the equilibrium ability of a fresh (uncontaminated) resin for a given concentration of cobalt in the water supplied to the intermediate product).

The third study (series C) considers the sodium form strong acid resin. This resin requires two agents regeneration: 10% sulphuric acid, which removes all of the cobalt and the greater part of the exchange of the sodium on the resin, and 4% NaOH, which makes the resin again from the acid form to the sodium form after regeneration with acid. Requirements for agents of regeneration, therefore, is significantly higher than for the regeneration of the acid form of the resin, and the regeneration can be carried out in two stages. However, the resin retains its essentially equilibrium sposobnosti cycles.

Final examination (series D) considers the acid form weak acid resin with a water flow of intermediate product with pH is brought to 5.5 by the addition of alkali, in order to improve characteristics of the resin. You need more layer of specified resin because of its weaker adsorption (more linear adsorption isotherm). Breakthrough cobalt with 0-2 memorial plaques happens early, before gradually increasing to a significant "breakthrough", which is taken as cobalt, washed out of the layer when more than 4 M. D. layer Specified regenerate 10% sulfuric acid at ambient temperature. As is evident from columns J and K, the layer substantially maintains its ability to remove cobalt for 9 cycles.


Claims

1. Method of removing carbonyl compounds of cobalt or rhodium from an aqueous solution of 3-hydroxypropane, comprising (a) contacting an aqueous solution of 3-hydroxypropane with oxygen in acidic conditions at a temperature in the range from 5 to 45oWith, effective for the oxidation of insoluble compounds of cobalt and rhodium to water-soluble compounds with a mixture of oxidation products containing an aqueous solution of 3-hydroxypropane, at least, odnogo product of carbon monoxide from a mixture of oxidation products, when it is formed, and (C) passing the mixture of oxidation products for making contact with ion exchange resins in the acid form at a temperature of less than 45oWith, and removing at least part of the above mentioned water-soluble compounds from a mixture of oxidation products on the specified ion-exchange resin.

2. The method according to p. 1, characterized in that the pH of the solution 3-hydroxypropane is in the range from 3 to 6.

3. The method according to p. 1, characterized in that an aqueous solution of 3-hydroxypropane contains 3-hydroxypropionic acid.

4. The method according to p. 1, wherein stage (a) is conducted at a temperature in the range from 5 to 45oAnd atmospheric pressure.

5. The method according to p. 1, wherein stage (b) is carried out by ozonation of air upward through the mixture of oxidation products.

6. The method according to p. 1, characterized in that an aqueous solution of 3-hydroxypropane contains from 10 to 400 M. D. cobalt.

7. The method according to p. 6, characterized in that the pH of the aqueous solution of 3-hydroxypropane is in the range from 3 to 4.

 

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29 cl, 7 dwg, 26 tbl, 17 ex

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3 cl, 2 tbl, 6 ex

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7 cl, 1 tbl, 2 ex

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15 cl, 1 dwg, 1 tbl, 2 ex

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