BE498380A - - Google Patents

Description

       

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  SYNTHESIS DIALCOOLS.



   The present invention relates to the preparation of oxygenated organic compounds by the reaction of olefinic carbon compounds with hydrogen and carbon dioxide in the presence of a carbonylation catalyst. More specifically, the present invention relates to an improved process for increasing the selectivity of the process over useful alcohols.



   It is well known in this art that the synthesis of oxygenated organic compounds can be carried out from organic olefin compounds, by the reaction of the latter with carbon monoxide and hydrogen in the presence. of a catalyst containing cobalt or iron or other carbonylation catalyst, in a generally three-phase process. In the first phase, the keyfinic material, the catalyst and the synthesis gases are reacted under pressure to obtain a product consisting mainly of aldehydes containing one more carbon atom than the olefinic material, as well as a product. certain amount of side reaction products, polymerized material, etc.



  This oxygenated organic mixture, which contains compounds of the catalyst metal in solution, can be treated in a second phase by heat, in order to cause the decomposition of the soluble catalytic material and the elimination of the latter from the catalyst. organic mixture.

   The material freed from the catalyst can then be hydrogenated in a hydrogenation phase to obtain the corresponding alcohol, or it can be oxidized to form the corresponding carboxylic acid.
This carbonylation reaction provides a particularly interesting method for the preparation of valuable primary alcohols which find large clogs, particularly as intermediates for plasticizers, detergents and solvents.

   Suitable substances for this type of reaction are not only the short or long chain olefinic hydrocarbons, but also most of the other species of organic compounds containing at least one olefin double bond.

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 EMI2.1
 that ,, such as acids, esters, alcohols, ketones, etc. not saturated.



   The catalyst for the first phase of the reaction, in which the olefinic material is converted to aldehydes, is usually added.
 EMI2.2
 in the form of salts of the catalytically active metal of high molecular weight organic acids, such as oleic stearic acid, naphthenic etc.



  Examples of such salts or catalytic soaps are oleates, stearates, naphthenates of cobalt or iron. These salts are soluble in
 EMI2.3
 olefinic liquid feed or parainic olein and they can be played, in the first phase. in solution in the feed, or in the form of a solution in a hydrocarbon.



   As the consumption of the two synthesis gases takes place in equivalent or equimolar quantities, the gaseous components of the synthesis are
 EMI2.4
 Usually added in equimolar doses of H2 and COp although it has been suggested to use an excess of hydrogen and an excess of CO. The conditions for the reaction of olefinic compounds with hydrogen and carbon monoxide vary somewhat depending on the nature of the olefinic feed, but the reaction is usually carried out at pressures of about 3,000 English pounds per square inch. and at temperatures of between 250 and 400 F approximately.

   The ratio of syngas feed to olefin can. vary. between wide limits; In general, 1,000 to 15,000 cubic feet of H2 + CO are employed per barrel of olefinic feed.



   At the end of the first phase, when the desired transformation of the olefins into oxygenates has been carried out, the products and the material
 EMI2.5
 After not reacting, are generally transferred to a catalyst removal zone, where the dissolved catalyst is removed from the mixture.



     One of the main problems with the synthesis reaction of aldehydes is that the catalytic metal and other metals which can form carbonyls such as cobalt, iron, etc., react, although they are added to the reaction zone as organic salts, with carbon monoxide under the conditions of the synthesis to form metal carbonyls. There is a reason to believe that carbonyl
 EMI2.6
 or metallic 1-hydrocarbonyl is the active form of the catalyst.

   The carbonyl remaining dissolved in the reaction product from the first carbonylation phase must therefore be removed in an intermediate phase of catalyst removal and this is usually done by heating the primary reaction product. in a suitable chamber or tower, with or without stacking, at atmospheric pressures or above atmospheric pressure and generally in the presence of a slow stream of inert scrub gas, such as hydrogen, in order to remove from above carbon o- xide, resulting from the decomposition of metallic carbonyl., to protect nickel or cobalt or another metal which can form carbo-
 EMI2.7
 nyls, used in the next high pressure hydrogenation phase,

   if such a metal is used. This process is satisfactory, as far as it involves the removal of carbonyl from cobalt, since it effects the decomposition of the latter into metallic cobalt and carbon monoxide, although this process leaves small amounts remaining. of metallic carbonyls, in particular of iron carbonyl. The iron carbonyl can be obtained from a variety of sources, such as the reaction of carbon monoxide, at high pressure, with the iron-containing impurities existing in the feed. oxides of carbon with the walls of the reaction apparatus and transfer lines, 1 stacking of the reaction apparatus and the like
 EMI2.8
 lookouts.

   Iron carbonyl is considerably more stable than its cobalt analogue and, therefore, when the latter is decomposed under the appropriate conditions in the catalyst removal zone, iron carbonyl can only be partially decomposed. .



   In addition it has been found that other cobalt compounds, particularly cobalt formate, are not specifically added as a catalyst,
 EMI2.9
 can be present in amounts up to 0.5% in the cobalt carbonyl decomposition zone outlet stream. These compounds are not

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 not readily decomposed by heat in the presence of an inert gas such as
 EMI3.1
 19hyd: rogen.

   The presence of the soluble metal in the product which leaves the catalyst removal zone is highly undesirable because of the tendency of the metal compound to decompose under the increased conditions prevailing in the hydrogenation zone and in the heating coils which. precede it, which results in the obstruction of the pipes and also
 EMI3.2
 deactivation of the hydrogenation catalyst. Therefore, it is highly desirable to keep the total cobalt concentration low.
 EMI3.3
 less than about $ 0.005 in the catalyst removal zone outlet stream.



   It was found that the residual cobalt content in the stream
 EMI3.4
 The output of the cobalt stripper, which will hereinafter be referred to as the "beater", is a function of the water content of the decobalt feed from the primary carbonylation reaction apparatus and is narrow. - ment associated with said water content.

   It has also been found that when the water content of the decobalteur feed, which water can come from
 EMI3.5
 side reactions, such as the formation of acetals and aldols, is greater than about 1% the soluble cobalt content of the output stream of the decobaltor becomes excessive after the heat treatment, at temperatures-
 EMI3.6
 peratures reaching about 350 to 400QF in the presence of hydrogen and that, subsequently, these cobalt compounds decompose in the furnace coils and in the high pressure hydrogenation apparatus which follows them.

   The for-
 EMI3.7
 Cobalt miate in particular appears to form during the cobalt removal phase when excess water is present and this compound is much more heat stable than cobalt carbonyl.



   To prevent the. formation of these heat-stable cobalt salts, it has been suggested to treat the feed from the primary reaction apparatus, and introduced into the decobaltor, by suitable dehydration means in order to reduce the water content to less than about 1%
 EMI3.8
 and preferably about 0.15%. The suitable means are ordinary dehydrating agents placed in towers, water separators inserted in the feed line of the decobalteur, etc. As a result of this treatment, the formation of cobalt formate is almost completely. inhibited..
 EMI3.9
 



  As desirable as it is to prevent the formation of these undesirable compounds and to ensure that the feed to the decobaltor is waterless, it has been found that the hydrogenation of the decobaltor output stream, containing less About 1% water, in order to form alcohols, was not a fully satisfactory process. It has been found that nota-
 EMI3.10
 The d901fins were corresponding, in terms of the number of carbon atoms, to the hydrogenated aldehydes, probably resulting from the dehydration of the alcohol formed during the hydrogenation phase. It was thus found that when a C7 olefin was subjected to the synthesis reaction
 EMI3.11
 of alcohol a substantial amount of C8 hydrocarbons was formed of which up to 60% were olefinic.

   Further, it was found that an excessive part of bottoms resulted from the distillation of alcohol from the hydrogenation reaction of these bottoms, about 20% were acetals or related compounds.



   The formation of these undesirable by-products is particular-
 EMI3.12
 This is sensitive to the use of an 'isulfacti ±' <catalyst on a support, such as molybdenum sulfide carried by activated carbon. This type of catalyst requires higher temperatures than more common hydrogenation catalysts, such as nickel or drunk chromite, to achieve relatively complete hydrogenation. At higher temperatures reg-
 EMI3.13
 In 19 dghyd ogenat.n9 oven the formation of the undesirable by-products listed above is strongly favored.

   The use of these "sulfactîj's2l d. \) Bydrogenation catalysts is, however, exceptionally interesting, since not only are they not poisoned by the sulfur contained in the feed, but, moreover, they are not affected by the sulfur. 'carbon monoxide which could be entrained in the output stream of the decobaltor. On the other hand, they have an exceptionally rough structure and long life.

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 long and they are very economical and easily regenerated.



   The object of the present invention is to provide an improved means, intended to increase the selectivity of the process with regard to the formation of alcohols, during the hydrogenation of the output stream originating from the decomposition zone of the catalyst, in a carbonylation process.



   It is also an object of the present invention to inhibit the formation of the overhead and bottoms of the distillation during the hydrogenation of the output stream of the decobaltor, the feed to the decobaltor having previously been treated to remove water therefrom.



   Other subjects of the invention will appear below.



   According to the present invention, the water which has been removed from the charge of the decobaltor is replaced, when the outlet stream of the decobaltor is subjected to the hydrogenation reaction, to convert the decobaltor product into alcohols. . It has thus been found that following the addition of water to the "decobalted" product sent to the hydrogenation oven, in doses of up to about 7%, the selectivity of the process over to the desired alcohols increases to 6 mole% or more for a given level of hydrogenation temperature. The decrease in acetal formation and dehydration of alcohols in the hydrogenation step may be water dependent.



   Water can be added by separate injection into the hydrogenation oven or by injection into the feed stream of this apparatus.



   The injection of water not only increases the selectivity of the process with respect to alcohols, but also allows the reactions of the hydrogenation zone to operate at higher temperature levels, without the product decomposing, causing thereby increasing the level of activity at which a "sulfactive" catalyst can be employed.



   The general nature of the invention having been explained above, the latter will be better understood by virtue of the more detailed description below, with reference to the appended drawing which schematically represents an embodiment of the invention.



   A clefinic hydrocarbon, having one carbon atom less than the number of carbon atoms of the resulting alcohol desired, and containing in solution a catalyst which promotes the reaction of olefinic compounds with carbon monoxide and hydrogen, a reaction which gives oxygenated organic compounds, is introduced into the lower part of a primary reaction apparatus 1 through the feed line 2, as shown in the figure. Any common catalyst, such as cobalt stearate, cobalt naphthenate, cobalt oleate, iron linoleate, etc., can be employed. The make-up catalyst, dissolved in the olefin feed, can be discharged into the main olefin feed line 2 through line 3.

   The concentrations of the catalyst and the ratios of the feed containing catalyst to the feed which does not contain it are such that the concentration of the catalyst in the total olefin feed varies between 0.1 to 5.0% by weight and , preferably between 1 and 3% by weight of the catalyst salt relative to the olefin Simultaneously, a gas mixture containing hydrogen and carbon monoxide in the approximate ratio of 0.5 At 2.0 volumes of hydrogen per volume of carbon monoxide, is introduced through line 4 into the primary reaction apparatus 1. The reaction apparatus 1 is preferably maintained at an effective pressure of about. 3000 English pounds per square inch.

   The reaction apparatus may not contain a stack, or it may contain a stack of solid, catalytically inert materials, such as ceramic rings, pumice, and the like.



   Reaction apparatus 1 is preferably maintained at a temperature of about 250 to 400 F, depending on the nature of the olefin feed and other reaction conditions. The flow of synthesis gas and oil

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 fines through the reaction apparatus 1 is adjusted so as to obtain the desired degree of transformation of the olefinic material.



   A mixture of liquid oxygenated reaction products, containing in solution unreacted olefins, dissolved catalyst, unreacted syngas and side reaction products, is removed from the top of the reaction apparatus 1 and transferred through line 8, cooler 10 and line 12, to high pressure separator 14, where unreacted gases are removed from above through line 16, washed in scrubber 18 to rid them of the entrained liquid and used in any desired manner.

   They can be switched back to line 4 through line 20, in order to adjust the desired partial pressure of H2 and to adjust the H / CO ratio in the feed to the reaction apparatus 1. If one if desired, only a part of the gases from separator 14 can be used in this way. The remainder can be removed from the system through line 22,
A liquid mixture stream, comprising the primary reaction product !, unconverted olefins and side reaction products, and containing relatively high concentrations of cobalt carbonyl as well as other compounds and complexes of the cobalt. cobalt, and which may contain 3% water or more, is withdrawn from separator 14 through line 24.

   A portion of this removed mixture stream can be returned to the circuit if desired, in the reaction apparatus 1, through line 26, to aid in cooling and maintaining temperature control of the carbonylation phase. primary. The remainder of the primary reaction product can be removed through line 28 and led into water separator 30, which can be provided with a reheat coil (not shown) if desired. .

   The flow rate of the primary reaction product is sufficiently reduced to allow the formation of a lower water layer which can be removed continuously or intermittently through line 32, while the upper layer, now containing less than 1% of water, may be removed through line 34 and fed into deco-baler 380 Under certain circumstances, for example where the load contains a considerable amount of water, it may be desirable to employ , in combination with the water separator 30, an ordinary drying tower (not shown), packed with dehydrating materials, inert to the aldehydes present in the feed.



   The outlet stream from separator 30, which contains less than about 1% water, and preferably no more than about 0.5%, is conducted through line 34 to the catalyst and decobalt removal zone. on "38, where the dissolved cobalt carbonyl is decomposed by a suitable heat treatment at temperatures of about 300 to 400 F, and liberates the metallic cobalt. A gas stream comprising hydrogen may be admitted to zone 38 through line 40 to help separate and remove CO resulting from the decomposition of metallic carbonyl.

   Zone 38 can work at high pressure, although preferably the effective pressure is between 15 to 200 pounds per square inch. The gas stream, including H2 and CO, can be removed from zone 38. via line 42 and be employed in any desired manner, such as sending to the catalytic reduction zone where CO is reduced to CH4, and the mixture can then be used for the subsequent hydrogenation or as a purge gas.



   As a result of the dehydration phase, followed by the "decobaltation" process, not only is the cobalt carbonyl virtually completely transformed into metallic cobalt and carbon monoxide, but cobalt salts, such as cobalt formate, which are not decomposed by the heat treatment, are also almost completely removed from solution and are suspended or precipitated in the decobaltor. The liquid product exiting the decobaltor, which may suspend finely divided precipitated metallic cobalt and the above-mentioned salts, is withdrawn from the decobaltor 38 through line 44 and may pass through filter 46 to remove suspended solids.

   The sludge can be removed from the decobalteur via line 41.

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   The liquid product of the carbonylation reaction, now substantially free of dissolved and suspended catalyst, is withdrawn from filter 46 through line 48 and introduced into the lower portion of hydrogen generator 50. At the same time, hydrogen is removed. introduced into the reaction apparatus 50 via line 52 in a proportion sufficient to convert the organic carbonyl compounds contained in the oxygenated feed into the corresponding alcohols. Although any ordinary catalyst can be employed the highest yields are achieved according to the present invention when a mass of hydrogenation catalyst containing molybdenum sulfide carried on activated carbon is used.

   The hydrogenator 50 can operate at effective pressures of between 2,500 and 4,500 pounds per square inch and temperatures of between 300 and 600 F, depending on the nature of the product comprising the aldehyde being treated.



  Reaction apparatus 50, however, is preferably operated at temperatures between about 400 and 500 F and effective pressures between about 2000 and 3500 pounds per square inch and more preferably between 2800 and 3200. pounds per square inch with a liquid feed rate of 0.25 to 2 Vol / Vol / hr. and a H2 feed rate of 5,000 to 20,000 normal cubic feet per barrel of load.



   According to the present invention, water is injected into the hydrogenator 50 through line 53 and pump 55. The dose of water added can be up to 50%, although it is preferably 1 to 10% of the load introduced into the apparatus 50, depending on the temperatures and pressures. It is desirable to add the water in such an amount that it is substantially completely in the vapor state under the conditions prevailing in the hydrogenation zone. The addition of water can be continuous or intermittent. The rate of addition is determined to some extent by the feed rate to the decobaltor and can be 0.0025 to 0.2 Vol / Vol / h. about.



  If desired, the injected water can be preheated to the temperature of the hydrogenation cabinet.



   The products of the hydrogenation reaction can be withdrawn from the top through line 54 and passed through cooler 56 to high pressure separator 58, where unreacted hydrogen can be withdrawn from above through line. 60 for subsequent use in the system, if desired. The liquid products are withdrawn from the gas separator 58 through line 62 and introduced into a settling tank 61, from where water can be removed through line 63, the upper layer, containing the alcohols, passing into the hydrocarbon still. 64, where the low boiling point products, mostly hydrocarbons with a lower boiling point than the alcohols produced, are distilled and removed at the top.

   Thus, when the feed to the carbonylation apparatus consists of C7 olefins, the product having a boiling point of 340 F or less is generally removed as a top product in the still. still 64. This material can be removed from the top, through line 66, and can be used to shut off gasoline. The bottoms of this first distillation are withdrawn from still 64 and sent through line 68 to alcohol still 70 where the alcohols produced, whose boiling points lie between desired limits, can be withdrawn from above through line 72, by distillation at atmospheric or reduced pressure, depending on their molecular weights.

   The bottoms of this distillation, discharged through line 74, can be subsequently processed or, if desired, be used as fuel.



   The system illustrated by the drawing and by the description above leaves the possibility of making various modifications, without departing from the scope of the invention. Thus, it may be desirable in certain circumstances to add water to the hydrogenator feed line at the same time as the aldehyde feed, instead of injecting it separately.



  Likewise, although the invention permits operation with an "sulfactive" catalyst at higher temperatures (ie, at higher activity levels) than those possible without the addition of water. , the invention can also be applied to other types of hydrogenation catalyst. The addi-

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 water should not be reserved, in all cases, for the charges of the hydrogenation oven, containing 1% or less water.



   The invention can be further illustrated by the following examples, which clearly show the advantages obtained by the operation according to the present invention.
EXAMPLE I
To illustrate the need to remove water from the charge of the decobaltor, it was found, in semi-industrial operation, that when the charge of the decobaltor was not dehydrated and the charge contained more than 1% water, the amount of soluble cobalt in the output stream of the decobaltor ranged from 0.014 to 0.049%, increasing with the time that the decobaltor remained connected to the circuit.

     However, when the decobalteur charge was dehydrated, the unwanted soluble cobalt content fell to 0.002% when 1.1% water was left in the decobaltor charge, and to 0.0001% when the water content. , remaining in the decobalteur charge, was 0934%. This indicates how desirable dehydration of the decobaltor feed is, as long as it is to free soluble cobalt from the decobaltor output stream.



   It was, however, observed that the selectivity of the process with respect to alcohols fell, in a semi-industrial installation (100 "barrels" per day), from an average value of 80 mole%, during a period of 3 months, before the dewatering treatment of the decobaltor charge was introduced, at about 73% during the 5 months, after this dehydration of the decobaltor charge became part of the process. At the same time, acetal formation increased from an average of about 10% to 17%.



   It is therefore evident that although the dehydration of the decobalt feeder markedly reduces the amount of cobalt dissolved in the aldehyde product leaving the decobaltor, the selectivity of the process is somewhat adversely affected.



   EXAMPLE II
To illustrate the excellent selectivities of the process with respect to alcohols which can be obtained by injecting water into the hydrogenation oven, a product containing C8 aldehydes, from a semi-industrial carbonylator, was treated as described above, to prepare a decobaltor outlet stream containing 0.39% water. This relatively anhydrous material was hydrogenated in a hydrogenator at the rate of 1/8 barrel per day, using a 10% molybdenum sulphide catalyst carried by activated carbon. Small amounts of water were injected directly into the hydrogenation oven by means of a Hille-MoCanna pump coupled to a Vickers transmission.

   The operating conditions were a feed rate (liquid) of 0.6 Vol / Vol / hr, and an effective pressure of 3,000 pounds per square inch of hydrogen between temperature limits of 475 to 525 F. ..

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  Effect of water on the hydrogenation of the product leaving the decobaltor and con-
 EMI8.1
 holding aldehydes in CP9 with MoS2 charcoal catalyst 3,000 pounds per effective square inch of hydrogen, 0.6 Liquid Vol / Vol / hr .:, per 1,000 cubic feet per barrel.
 EMI8.2
 
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  On <SEP> E <SEP> E <SEP> F <SEP> H <SEP> I <SEP> J <SEP> J <SEP> K <SEP> L <SEP> L
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<tb> Hours <SEP> of <SEP> on <SEP> 7-12 <SEP> 13-18 <SEP> 7-12 <SEP> 1-12 <SEP> 1-12 <SEP> 1-6 <SEP > 7-12 <SEP> 7-12 <SEP> 13-18 <SEP> 19-24
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<tb> Average temp <SEP> F <SEP> 479 <SEP> 479 <SEP> 477 <SEP> 502 <SEP> 500 <SEP> 512 <SEP> 524 <SEP> 521 <SEP> 521 <SEP> 521
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<tb>
<tb> H2O <SEP> total <SEP> in <SEP>% <SEP> in
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 EMI8.3
 load weight 0.39 0339 4.46 7.77 4t28 4.33 4.43 8.00 0.39 0939
 EMI8.4
 
<tb> <SEP> analysis of <SEP> prod.
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 EMI8.5
 No. of hydroxyl 288 291 293 295 298 295 288 292 275 273 Il of carbonyl L, 4 1.99 2.0 1.3 097 0.7 0.7 z 0.6 0.5
 EMI8.6
 
<tb> Selectivity <SEP> by
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<tb> report <SEP> to <SEP> hy-
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<tb> Drocarbons
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 EMI8.7
 in C8, moles% 3y .3, .3290 2.7 l,

  0 49 7.9 5.2 9.4 9eO C8 alcohols 74.6 75.4 z6 79e2 77.1 76.6 75.8 77.7 71.9 L-f prod. tail 21.2 20.8 19.7 17.3 18.1 17.6 15.4 15.6 18.7 1799
These data indicate the following:
A. The addition of water had no particular effect on the activity of the catalyst, and the carbonyl number of the alcoholic product fell to a value of 2.Cl, when the hydrogenation was carried out to 477. F, to a value of 0.5-0.6, when the reduction was carried out to 521 F. These results were obtained with or without the addition of water.



   B. There was a marked increase in selectivity to alcohols. For a water concentration of 4.3 to 4.5%, an increase in overall selectivity of 3-4 mole% was achieved, while an addition of 7.7 to 8.0% water increased. the selectivity of about 6 mole%. With the addition of a larger quantity of water, the selectivity to alcohols at 520 F is about 3% higher than at 480 F, without the addition of water; furthermore, there is the marked advantage of a more complete hydrogenation at higher temperature.



   C. Without the addition of water, the selectivity to C8 hydrocarbons becomes critical at an average temperature of about 520 F. That is to say, that the hydrogenation, at or above this temperature
 EMI8.8
 nière, produces high losses by olefins in C8. The addition of., 3 to, 4.5% of water, however, decreased the selectivity to hydrocarbons in cg by 1.5 to 2%. while a concentration of 7.7 to 0.0 H 2 O decreases the selectivity to hydrocarbons by 2 to 2.5%. The addition of water therefore makes it possible to use a hydrogenation temperature of 520 F, with
 EMI8.9
 active tallow catalysts? and Higher inactivity of the catalyst at this temperature can be achieved. Catalyst life can also be extended in this way.



   Do The selectivity of the process with respect to tail products
 EMI8.10
 is decreased from 1 to 2% by the addition of 4.3 to 4.5% water, and from 2 to 255 by the addition of 7.7 to 8.0% water.
 EMI8.11
 Therefore, by injecting water into the hydrogenation zone, increased yields and higher selectivity to alcohols are achieved accompanied by decreased formation of hydrocarbons and bottoms of the still.



   Although in the foregoing emphasis has been placed on the addition of water to the hydrogenation zone, to compensate for the water removed during or before the decobaltation operation, it is understood that in certain circumstances it may be It is desirable to add water in an amount greater or less than the amount removed before the decobaltation operation.

   Furthermore, under certain operating conditions, such as for example in the case where only small amounts of water are produced in the primary reaction zone.

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   may, however, be desirable to add water, in
 EMI9.1
 ques above, in the -hydrogenation zone without necessarily passing the decobalteur feedstock through a water delimiting device,
Other modifications, which are obvious to those skilled in the art, are within the scope of the invention.



   CLAIMS
 EMI9.2
 The carbonylation process in which olefinic compounds of carbon monoxide and hydrogen are contacted with a cobalt-containing carbonylation catalyst, in an initial reaction zone, under the conditions necessary to form an aldehyde product containing per molecule one more carbon atom than said olefinic compound, and in which a liquid product, containing dissolved aldehydes and cobalt carbonyl, is introduced into a decomposition zone of the catalyst and said products are subjected under conditions in which the catalyst decomposes, and in which the oxygenated liquid product, withdrawn from said decomposition zone of the catalyst,

   is subjected to hydrogenation in a
 EMI9.3
 hydrogenation zone in the presence of a hydrogenation catalyst under hydrogenation conditions to form alcohols of interest, characterized by
 EMI9.4
 this comprises the addition of water to said hydrogenation zone.



  2. Method according to claim 1 ;, characterized in that said dihydrogenation catalyst is a “sulfactive.11” catalyst.


    

Claims (1)

3. Method according to claim 2, characterized in that said EMI9.5 The sulfactive catalyst is molybdenum sulfide carried by activated carbon. 4. Method according to claim 1, characterized in that the EMI9.6 Water is added to the hydration zone in doses not exceeding 50% of the total feed to said zone. 5. Process for preparing alcohols from olefins in high yield, characterized in that it comprises the introduction of olefinic compounds, carbon monoxide and hydrogen in a carbonylation zone in contact with cobalt-containing carbonylation catalyst at high pressures and temperatures, forming a product comprising aldehydes containing in their structure one more carbon atom than said olefinic compounds contained in said zone, removing said zone of a liquid product comprising aldehydes; , water, side reaction products, and dissolved cobalt compounds and complexes containing cobalt carbonyl, passing said product through a water removal zone whereby the content of water of said product is preferably reduced to less than about 1%., passing said dehydrated product through a catalyst decomposition zone where said product is subjected to heat treatment in the presence of a gas. inert washing whereby the cobalt carbonyl largely decomposes and liberates the metallic cobalt, the removal from said zone of a product substantially devoid of dissolved cobalt, the introduction of said product into a hy- EMI9.7 drogenation where said product is subjected to hydrogenation conditions in the presence of 1 to 10% by weight of water and the removal of a product rich in alcohols from said d-hydrogenation zone. 60 The process of claim 5 characterized in that said hydrogeneration conditions comprise effective pressures of about 2,800 to 3,200 pounds per square inch and temperatures between the limits of about 400 and 550 F. 7. The method of claim 5, characterized in that a catalyst consisting of molybdenum sulfide carried by charcoal ac- EMI9.8 activated in said hydrogenation zone. 80 Process according to claim 5, characterized in that 8% of <Desc / Clms Page number 10> approximately weight of water is injected into said hydrogenation zone. 9. The method of claim 5, characterized in that the water content of the outlet stream of said catalyst removal zone is approximately 0.5%. 10. The method of claim 5, characterized in that the water injected into said hydrogenation zone is substantially completely in the vapor state under the conditions prevailing in said hydrogenation zone. in appendix 1 drawing.