US3301905A - Process for oxidizing olefins to aldehydes and ketones - Google Patents

Process for oxidizing olefins to aldehydes and ketones Download PDF

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US3301905A
US3301905A US84968A US8496861A US3301905A US 3301905 A US3301905 A US 3301905A US 84968 A US84968 A US 84968A US 8496861 A US8496861 A US 8496861A US 3301905 A US3301905 A US 3301905A
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oxygen
reaction
catalyst
olefin
acid
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Riemenschneider Wilhelm
Dialer Kurt
Probst Otto
Bander Otto-Erich
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Hoechst AG
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Hoechst AG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds

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  • the present invention relates to a process for oxidizing olefins to aldehydes, ketones and acids.
  • carbonyl compounds is used in its broad sense, i.e. it covers not only aldehydes and ketones, but also carboxylic acids such as acetic acid.
  • the reactants may be diluted by gases inert towards the reaction, for example by nitrogen, carbon dioxide, methane, ethane, propane, butane, isobutane and other saturated aliphatic compounds and furthermore by other compounds such as cyclohexane, benzene or toluene.
  • gases inert towards the reaction for example by nitrogen, carbon dioxide, methane, ethane, propane, butane, isobutane and other saturated aliphatic compounds and furthermore by other compounds such as cyclohexane, benzene or toluene.
  • the olefins may not only be diluted by one or more of the aforementioned gases, but surprisingly likewise by carbon monoxide and/ or hydrogen. It has unexpectedly been found that the presence of these gases does not affect the course of the reaction. If such gas mixture contains CO, oxygen should be present at least in an amount as is necessary to convert the olefin to aldehyde and carbon monoxide to carbon dioxide.
  • olefin-noble metal complex compounds are formed as intermediary products which then react with water to yield carbonyl compounds. It is, however, known from the literature that carbon monoxide expels from these coordination compounds all olefins, including ethylene. For these reasons a mixture of olefins with carbon monoxide was expected to bring about no or only a very small conversion of the olefin to carbonyl compounds. It is therefore surprising that a mixture of carbon monoxide and olefin, if desired in admixture with one or more other gases inert towards the reaction, such as those mentioned above, practically yields the same amounts of carbonyl compounds as if no carbon monoxide were present. In this reaction the carbon monoxide is partiaily converted to carbon dioxide.
  • the carbonyl compounds can be obtained in the same manner without a reduction in conversion occuring by using a mixture of carbon monoxide and hydrogen with an olefin or a gas containing an olefin; in this case, it
  • the reacted gases may-advantageously after they have been freed from the reaction productsbe recirculated, or, if no or small amounts of olefins are present, may be used for other purposes.
  • the process of this invention may be carried out wit-h catalysts and under the conditions broadly described in applications Ser. No. 747,116, 750,150, 747,115 and 760,539 and referred to above.
  • redox systems for example, those that contain compounds of metals which under the reaction conditions employed may appear in various oxidation stages, for example compounds of copper, mercury, cerium, thallium, tin, lead, titanium, vanadium, antimony, chromium, molybdenum, uranium, manganese iron, cobalt, nickel, or osmium, and also inorganic redox systems other than specified above, such as sulfite/sulfate, arsenite/arsenate or iodide/ iodine systems and/ or organic redox systems, for example azobenzene/hydrazobenzene, or quinones or hydroquinones of the benzene, anthraceneor phenanthrene series.
  • compounds of the noble metals of group VIII of the peirodic table there may be used in the process according to the present invention, for example, compounds of palladium, iridium, ruthenium, rihodium or platinum.
  • Compounds of this series of metals are believed to be capable of forming addition compounds or complex compounds with ethylene.
  • the reaction may likewise be carried out in the presence of a noble metal.
  • oxidizing agent there may be used, for example, oxygen, if desired in admixture with an inert gas.
  • the oxygen may be employed, for example, in the form of air, which is the cheapest oxidizing agent or in the form of air enriched with oxygen.
  • air is, however, confined to certain limits, if the unreacted gases are circulated, inasmuch as nitrogen concentrates as ballast material.
  • the reaction may be supported or carried out by addition of an active oxidizer, such as ozone, peroxidic compounds, especially hydrogen peroxide or sodium peroxide, potassium peroxide, potassium persulfate, ammonium persulfate, alkali percarbonate, alkali perborate, peracetic acid, diacety-l peroxide, benzoyl peroxide, toluyl peroxide, oxygen compounds of nitrogen, such as nitrogen dioxide and nitrogen pentoxide or mixtures of nitrogen oxides containing the same, nitryl halides such as nitryl chloride, free halogen such as chlorine, bromine, or bromotrichloride, halogen-oxygen compounds such as chlorine dioxide, hypochlorous acid, chloric acid, perchloric acid, bromic acid, iodic acid, periodic acid, or compounds of the higher valene stages of metals, such as manganese, cerium, chromium, selenium, lead, vanad um, silver,
  • an active oxidizer
  • molybdenum, cobalt, or osmium for instance potassium permanganate, sodium bichromate, lead tetraacetate, vanadium pentoxide, silver difiuoride, selenium dioxide, cerium-(IVlsulfate, osmium tetroxide.
  • an active oxidizer facilitates the re-formation of the higher oxidation stage of the active catalyst component which is necessary for carrying out the reaction.
  • These oxidizing agents may also be produced during the reaction. If desired, an oxidizing catalyst may be added.
  • a compound yielding anions under the reaction conditions applied for example an inorganic acid, preferably a mineral acid such as sulfuric acid, nitric acid or a volatile acid, such as hydrochloric acid or hydrochromic acid, or a salt such as ammonium chloride, ammonium bromide, zinc chloride, aluminum chloride, iron chloride, chromic chloride, titanium tetrachloride, sodium hydrosulfate, a halogen or a halogen-oxygen compound, for example those mentioned above, or thionyl or sulfuryl chloride, or also an organic substance, preferably a saturated aliphatic halogen compound of low molecular weight such as ethyl chloride, propyl chloride, butyl chloride, acetyl chloride, benzoyl chloride, propionyl chloride, phosgene.
  • an inorganic acid preferably a mineral acid such as sulfuric acid, nitric acid or a volatile acid, such as hydrochlor
  • suitable contact supports are, for example, silica gel, kieselguhr, pumice, silicates, TiO A1 0 active carbon, acid ion exchangers, such as Amberlite IRC 50, Dowex types 50, Permutites, phenol-aldehyde-resins which are substituted by sulfonic acid groups, polystyrene-resins which are substituted by sulfonic acid groups and crosslinked by divinyl-benzene etc., or mixtures of such carriers.
  • carriers are, for example, silica gel, kieselguhr, pumice, silicates, TiO A1 0 active carbon, acid ion exchangers, such as Amberlite IRC 50, Dowex types 50, Permutites, phenol-aldehyde-resins which are substituted by sulfonic acid groups, polystyrene-resins which are substituted by sulfonic acid groups and crosslinked by divinyl-benzene etc
  • liquid catalysts are applied, preferably a pure aqueous solution is used, but the reaction may likewise be carried out in aqueous solutions in which the water is diluted With a hydrophilic solvent such as acetic acid, acetone, methylethyl ketone or other ketones, ethylene glycol, propylene glycol, glycerol, dioxane or mixtures thereof.
  • a hydrophilic solvent such as acetic acid, acetone, methylethyl ketone or other ketones, ethylene glycol, propylene glycol, glycerol, dioxane or mixtures thereof.
  • the present process can be carried out with special advantage at temperatures within the range between 50 and C., preferably 50 and 100 C. if it is carried out in the liquid phase, it is necessary to operate under a raised pressure provided that the temperature used is above 100 C. If desired, the process may also be carried out at temperatures outside the ranges indicated above, for example at C. to C., or for example at 40 C., or within a range of, for example, 80 C. to 120 C. It is furthermore of importance to carry out the process in an acid to neutral medium.
  • the preferred pH-val-ues are within the range between 0.8 and 3; higher pH-values between, for example, 0.8 and 5 or 2 and 6, or lower pH-values, for example, 0.5 may also be used, although such pH-values generally do not involve a special advantage. If solid catalysts are used the solution with which the solid catalyst is impregnated may be adjusted so as to have a pH within the limits indicated above.
  • Difficulties which may appear in working in the liquid phase can be overcome by modifying the ratio of olefin to oxygen. Such difficulties may reside in the precipitation of cuprous chloride or other compounds formed which cause cloggings and undesired disturbances in operation. In view of the fact that these precipitated salts are no longer available for the reaction, the yield decreases more or less rapidly. The moment at which the olefin to oxygen ratio must be modified, can be readily determined by continuously measuring the pH.
  • the pH decreases, it is easily possible to readjust the optimum pH-range by adding either more oxygen or less olefin, or by combining these two steps. If the pH increases, the optimum pH-range can be readjusted inversely.
  • This method of controlling the reaction may also be combined with the above described addition of com pounds yielding anions, for example hydrohalic acid or organic compounds splitting off hydrohalic acid under the reaction conditions, or acid salts. It is especially advantageous to adjust the reaction medium to a certain pH at the onset of the reaction, for example by means of hydrochloric acid, and to regulate the olefin-oxygen ratio during the reaction.
  • the pH may of course also be modified during reaction by addition of an acid.
  • the pH is measured by using a device of known type.
  • the pH may be measured continuously with electrodes arranged in the reactor, or discontinuously by measuring the pH of samples withdrawn in certain intervals of time.
  • the pH-measuring device has an automatic connection to the dosing device for the supply of ethylene and oxygen. In this case the pH is once adjusted to the optimum value and the reaction can then be controlled automatically.
  • a salt such as sodium chloride or potassium chloride may prove advantageous.
  • these salts like that of hydrochloric acid itself or of other alkali metal or alkaline earth metal halides such as LiCl, CaCl MgCl or other salts such as FeCl ZnCl or CuCl -the solubility of CuCl, which may be formed in the course of the reaction and which is only very sparingly soluble in water (0.11% at 80 C.) is improved.
  • the reactivity of CuCl may for instance be improved by'the presence of such salts.
  • the present process can be carried out at atmospheric pressure, under a raised pressure or under reduced pressure, that is, under a pressure of up to 100, preferably of up to 50 atmospheres gauge.
  • the process may be carried out under pressure regardless of whether the temperatures used are above or below 100 C.
  • the reaction may be supported by increasing the ethylene and/or oxygen concentration in the reaction space. This can be achieved, for example, by increasing the pres sure and/or-especially, when the reaction is carried out in the liquid phaseby the presence of a solvent.
  • the ethylene concentration in the reaction solution may be considerably increased, for example, by using higher concentrations of metal salts binding ethylene, for instance copper-, ir0n-, mercuryor iridium compounds, especially halides, or the sulfates, the latter especially when mercury is concerned, or by using organic solvents which are preferably miscible with water, for example acetic acid, methylethylketone or other ketones, monoor polyhydric alcohols, acyclic ethers or dimethyl formamide.
  • the gases may be circulated, if desired, for example as gas containing a few percent of unreacted oxygen.
  • acetic acid may be formed in a small amount in addition to acetaldehyde.
  • the oxidation of acetaldehyde to acetic acid which is known in the art, may be combined with the reaction described above in order to omit partially or totally the aldehyde stage, or acetaldehyde may be oxidized in a second stage to acetic acid.
  • reaction proceeds substantially in a manner analogous to that described and it can be carried out under the same action conditions, for example diolefins.
  • olefins or gases containing olefins or other unsaturated compounds may be reacted in the same manner, provided they are capable of reacting under the re-
  • the reaction of olefins containing 2 to 3 carbon atoms is however preferred. Under circumstances, the reaction conditions must be adapted to the compounds used and to their physcial properties. The higher boiling points of the reaction products may also require a corresponding modification of the reaction conditions.
  • Diacetyl may be obtained, for example from butadiene.
  • the molar ratio of olefinic bond to oxygen must be 2:1 in the complete oxidation of olefins to the corresponding aldehydes or ketones.
  • an oxygen deficiency for example in the range of 2.5:1 to 4:1.
  • work outside the range of explosivity for example with a content of oxygen of 8-20%, or 814% under pressure, and to circulate unreacted gas which consists substantially of non-converted olefin, hydrogen and/ or carbon monoxide, and, if desired containing other inert gases such as nitrogen, and may furthermore contain some oxygen.
  • oxygen and the olefin, such as ethylene are restored as they are consumed.
  • the present process may be carried out for example by contacting the olefin which is diluted with hydrogen and/ or carbon monoxide and oxygen or air simultaneously with the catalytic substances.
  • the olefin which is diluted with hydrogen and/ or carbon monoxide and oxygen or air simultaneously with the catalytic substances.
  • This mode of operating has the advantage that the composition of the gas mixture need not be controlled carefully and that even in recirculating the olefinic reactant, such as an ethylene containing gas, air may be used as oxidizing medium without disadvantages being involved.
  • This variant may be performed by contacting the olefinic gas mixture and the oxidizing agent in periodic alternation with the circulating catalyst liquid in a vessel; in a continuous operation there may be used to this end a reciprocally reversible double apparatus, or the olefinic gasmixture and oxidizing agent are contacted with the circulating catalyst liquid in several reaction vessels.
  • the olefinic gas mixture may still contain oxygen, the oxygen content being outside the range of explosivity, i.e. for example, between 1% and 10%, preferably between 3% and 10% of oxygen, calculated upon the amount of olefin used.
  • the explosive limit of .an ethylene-oxygen gas mixture is at atmospheric pressure at 20.1% of oxygen.
  • the reaction is preferably carried out in such a manner that the oxygen is almost or completely consumed in the reaction vessel and the catalyst is then regenerated in the regeneration vessel.
  • the contact medium is contacted in a further separated stage with the oxidizing medium in an amount sufficient to bring about regeneration, for example oxygen or air.
  • Regeneration is brought about under known con ditions, for example at 50-150 C. and may be carried out under pressures and at temperatures being different from those of the first stage in which the catalyst is contacted with the olefin.
  • the olefin dissolved in the catalyst medium is also oxidized and the dissolved reaction product is removed 'by stripping.
  • regeneration may also be brought about using mixtures of oxygen or air with steam.
  • the use of an olefinic gas mixture containing a small amount of oxidizing agent in one stage and of additional oxidizing agent in the second stage offers the further advantage that an occasional separation of undesired solid products is avoided at the place where an oxygen containing, olefinic gas mixture enters into the reactor, which contains oxygen in an amount smaller than corresponds to the stoichiometric composition as regards the conversion to the carbonyl compound, and the composition of which gas mixture is outside the inflammability limit.
  • a separation of solid substances would cause reduction of the catalytically active substance in the contact liquid and accordingly a reduction of the contact activity; on the other hand, such separation would involve cloggings in conduits, cocks or nozzles.
  • Such separation of solid substances does not appear if the olefin gas mixture contains a minor amount of oxygen or air and such mixture is contacted in the first stage with the contact solution, and if the con-tact solution is regenerated in a second stage :by addition of a further amount of oxidizing agent.
  • the olefinic gas mixture and the oxidizing agent, or an olefinic gas mixture containing a small amount of oxygen and the oxidizing medium, for example oxygen are contacted separately in the manner described above with the catalyst, it may be advantageous to free the olefin-treated contact solution before it is being contacted in a second phase with the oxidizing gases, from residual unreacted olefin and residual reaction product, for example by stronger heating or stripping with an inert gas, such as nitrogen or steam.
  • an inert gas such as nitrogen or steam.
  • the head of the regeneration tower may readily be provided with a safety device of known type to prevent explosion, such as lbursting disks, a breakdown security device (gravel pots) or the like.
  • a safety device of known type to prevent explosion, such as lbursting disks, a breakdown security device (gravel pots) or the like.
  • the danger of explosion is however extremely low in view of the acetaldehyde-oxygen-mixture being saturated with water vapor and in view of the relatively low content of oxygen, which is smaller than the oxygen content of the air.
  • the present process may, e.g. be carried out in an apparatus shown in the appended drawing.
  • a current of an olefinic gas mixture is introduced through a compressor 1 into reactor 2 or 2a in concurrent or countercurrent to the catalyst liquid, and the gas is finely distributed in the catalyst solution by means of a suitable device, for example a frit, a mixing nozzle, an oscillatory sieve, a vibrator, a rapid agitator or the like.
  • the olefin is converted in this solution to a carbonylcontaining reaction product leaving the reactor together with unre-acted olefin and diluting gas, if desired via a cyclone 3.
  • the reaction product is separated in a separating device 4 from the remainder of the olefinic gas mixture, which latter substance may then be recirculated together with a fresh amount of olefin into the reactor via compressor 1 if it still contains substantial amounts of olefin, or may be used for other purposes.
  • the reaction liquid is then conducted to a stripper 5, where it is treated with steam to be directly or indirectly freed from olefin and residues of reaction product.
  • the gases obtained by stripping are conducted, if desired, to separating device 4.
  • the stripped reaction solution is then introduced into regenerator 7 by means of a pump 6 or a static incline.
  • the stripping stage may, however, be omitted, and the reaction solution is then directly introduced into regenerator '7.
  • the solution is intimately contacted in generator 7 with oxygen or gases containing oxygen.
  • the regenerator may be designed so that the contact liquid flows in a countercurrent to the oxygencontaining gases, which leave the regenerator through cyclone 8, and may be returned into the cycle by means of a compressor.
  • the contact liquid is then communicated in the regenerated state to reactor 2 or 2a by means of pump 9. All partial operations may be carried out individually or together at a raised pressure, at a reduced pressure, or at atmospheric pressure.
  • the aforesaid two-stage embodiments have the mutual advantage, that explosive gas mixes are not liable to occur even when operating under a raised pressure, and that each gas current can be circulated separately and replenished by fresh gas to the necessary extent. It is also possible to use air as oxidizing agent in view of the fact that a concentration of nitrogen has here no detrimental effect.
  • a mixture of olefin with hydrogen and/ or carbon monoxide is contacted with gaseous oxygen if desired in the form of air in the presence of water vapor at a solid acid to neutral catalyst comprising a carrier, a compound of a noble metal of group VIII of the periodic system and a redox system containing one or more compounds of one or more metals having an atomic number in the range from 25 to 27, i.e. iron, manganese and/or cobalt.
  • the compounds of iron, manganese or cobalt are added to the catalyst in the usual manner. It is possible, for example, to impregnate the catalyst with the soluble salts of these elements and to convert these salts by heating, preferably with air, to the firmly adhering oxides. There may also be used a mixture comprising the aforesaid compounds.
  • the acid formed can be readily separated from the corresponding aldehyde. It is preferred to concentrate the acid, which has always a boiling point higher than the aldehyde, in a first separator, and to concentrate the aldehyde which has a boiling point lower than the acid, in a second separator. Both separators are connected in series.
  • the simultaneous production of carboxylic acids and aldehydes at solid catalysts containing an iron-, manganeseand/or cobalt salt is preferably carried out in the presence of further redox systems, such as copper compounds.
  • the desired reaction product for example acetaldehyde, and, if desired, acetic acid
  • the residual gas which may still contain hydrogen and/ or carbon monoxide and furthermore inert gas and may be free from oxygen, but may likewise contain oxygen
  • the reactor is reintroduced into the reactor, suitably into its lower part and an amount of olefin and if desired oxygen corresponding to that consumed during the reaction is introduced into the reactor through one or more inlets which may be arranged one above the other or one behind the other, or the olefin and/ or the oxygen are added to the recirculated gas.
  • the resulting gas mixture which may be free from oxygen or in which the ratio of olefin and oxygen is, for example 95 to 99 percent or to percent of olefin (for example ethylene) to 5 to 1 percent or 10 to 5 percent, respectively of oxygen, is then introduced into the reactor.
  • the oxidizing agent i.e. preferably oxygen
  • inert gases such as present in air, is preferably introduced through separate inlets, especially when about stoichiometric amounts of the reactants are applied.
  • the oxidizing agent is introduced below the inlet for the residual gas or, if a circulating cataylst is used, into the circulation conduit of the catalyst.
  • the amount of oxygen introduced may be so modified that even in the catalyst solution the explosivity limit is nowhere surpassed, Such modification is generally not necessary; it is rather sufficient to add the oxygen to the residual gas which escapes from the contact solution, in an amount to keep the composition of this residual gas outside the explosive limits.
  • olefinic gas mixture or oxidizing agent preferably oxygen, or olefinic gas mixture and oxygen
  • oxygen preferably oxygen
  • olefinic gas mixture and oxygen into the reaction vessel, for example a reaction tower, at various places arranged one above the other or one behind the other.
  • the inlets for each reactant are locally separated from the other inlets for the same reactant. It is likewise possible that the amount of oxygen introduced is measured so as to kee at all places of the reaction vessel below the lower limits of the explosive range.
  • a dispersant for example an alkylphenyl sulfonate or a product obtained by the reaction of ethylene oxide, propylene oxide, or
  • the reaction proceeds likewise smoothly if the catalysts used contain only a small amount of compounds of the noble metals belonging to group VIII of the periodic table.
  • a cataylst in which the ratio of the sum of the redox metals, especially the sum of copper and iron to the noble metal, especially palladium, is at least 15:1, preferably 25-500I1. It is, however, preferred to use a catalyst containing copper salts, in which the ratio of copper to palladium is above 10:1, for example above :1 and preferably 50:1 to 500:1, or even above these ranges.
  • This method of operating is more economic in view of the fact that the expensive palladium salt need only be used in a minor amount; it can be used for converting ethylene and olefins other than ethylene, and may be combined as desired with variants hereinbefore or hereinafter described. This embodiment may also be carried out under elevated pressure.
  • the halogen content of the liquid catalysts used in the present reaction may become depleted in the course of time, a fact which possibly causes a reduction in the rate of conversion.
  • the loss of halogen may be counteracted by addition of halogen or hydrohalic acid or organic substances splitting off halogen or hydrohalic acid under the reaction conditions as already stated.
  • halogenated lay-products for example methyl chloride or ethylchloride, which together with the carbonyl compounds produced entrain the halogen from the catalyst more or less rapidly.
  • carboxylic acid corresponding to the olefin is produced during the reaction, for example acetic acid; such acid concentrates in the liquid and increases the solubility of the reaction products. This favors the formation of halogen-containing volatile by-products and promotes the depeltion of halogen.
  • carboxylic acids which have concentrated, especially acetic acid react with the copper ions, which is unfavorable because the copper salts formed, such as copper acetate, are relatively inert towards the olefin oxidation.
  • This may be done by suitable continuous or discontinuous measures, for example by distillation, extraction or precipitation.
  • a preferred variant in operating under atmospheric pressure consists, for example, in that the car- 'boxylic acids formed are allowed to distill over together with the evaporating water; the water consumed is then replaced by a corresponding amount of fresh water.
  • the amount of carboxylic acid removed in this manner is dependent on the surface of the reactor, the temperature used and the amount of gas flowing through, and may be modified by varying these factors. According to another variant the entire contact solution is worked up, carboxylic acid contained in the catalyst is removed, and the contact solution is recirculated into the apparatus.
  • part of the contact liquid may be withdrawn periodically or continuously and freed from carboxylic acid, partially or substantially, for example by distillation, and the liquid obtained may be added again to the contact medium.
  • the reaction of the present invention is favorably influenced by irradiation with rays rich in energy, preferably ultraviolet light, especially in the case where oxygen is used as oxidizing medium.
  • rays rich in energy preferably ultraviolet light
  • Such radiation which may also comprise X-rays activates especially the oxygen, increases its oxidizing activity, and promotes both the reaction With the olefin and a possible oxidative destruction of -by-products, for example oxalic acid.
  • a mercury quartz lamp as source of radiation arranged in the catalyst so that the light energy is fairly substantially utilized.
  • the reaction is carried out with an apparatus into which oxygen or an oxygen-containing gas is introduced separately from the olefinic gas mixture or even a mixture of the said reactants, it is preferred to arrange the source of radiation in the vicinity of the oxygen inlet, so that that part which is rich in oxygen is especially well irradiated.
  • the oxygen is thereby activated as long as it has a high partial pressure.
  • the source of radiation at the lower end of the conductline or, if the reactant is carried out in several stages, at the lower end of the regeneration vessel, immediately above the oxygen inlet. Activation may also be brought about by adding a compound of a radio-active element to the catalyst solution.
  • the process of this invention may be carried out for example in vertically arranged tubes provided with frits or oscillatory agitators.
  • the process may also be carried out in usual reaction towers, for example wash towers, suitably filled with filling material.
  • the gases may be atomized, for example through a frit, or in another suitable manner, and too voluminous gas bubbles may be divided into smaller ones, for example by means of an agitator.
  • a vibro-mixer or a turbo-mixer for all these variants enable the reaction to be carried out continously.
  • the conversion and the space/time/yield depend for example, on the residence time in the apparatus, and the composition of the catalyst, the temperature and the pressure used, and, if liquid catalysts are used, furthermore on the fine distribution of the gas.
  • the most suitable residence time can readily be determined by a simple test.
  • the reaction of the present invention may be carried out in a manner known per se, for example by passing the gases through a tube which is filled with the catalyst, or with the use of a fluidized bed catalyst. Condensates which separate from the reacted gas, especially aqueous condensates, may also be recirculated. If solid catalysts are used, they are of course vaporized to again participate in the reaction, for example as such or after separation of higher and/ or lower boiling reaction products.
  • the catalysts used are made of fine chemicals; they may likewise be produced from suitable metals of commercial purity.
  • Metals such as copper and iron may be readily dissolved even by nonoxidizing acids, such as hydrochloric acid and acetic acid, if desired by addition of an oxidizing agent, especially if copper is used, or by passing through during the dis solving process as gaseous oxidizing medium such as oxygen or air enriched with oxygen.
  • gaseous oxidizing medium such as oxygen or air enriched with oxygen.
  • the contaminations contained in commercially pure metals do not affeet the reaction if the solutions obtained are used as catalysts or are Worked up to the solid bed catalysts for the olefin oxidation. More especially, the catalytic activity remains practically unaffected by small amounts of foreign metals which may appear in copper or iron of commercial purity.
  • the anion forming agents contained in metals such as sulfur, phosphorus, carbon, silicon etc. are converted upon being dissolved to either hydrogen compounds, for example H 8, which escape together with the reaction gases, or oxidized to acids of a higher valence stage, for example H 50 which do not affect the reaction, or converted partially into insoluble compounds, for example CuS, which appear only in minor amounts and, if necessary, can readily be separated from the catalyst, for example by filtration, before the catalyst is used or the catalyst solution is applied to a carrier.
  • hydrogen compounds for example H 8
  • acids of a higher valence stage for example H 50 which do not affect the reaction
  • insoluble compounds for example CuS
  • the solutions so obtained are then admixed with the noble metal compound which is added in substance or in the dissolved state, if desired diluted with water, and the concentration of hydrogen ions is adjusted to the degree desired; the solution so prepared may then directly be used as a catalyst for the olefin oxidation in the liquid phase or they may be concentrated and be applied to a carrier, for instance, to those mentioned above.
  • Solvents suitable for dissolving the metals are chiefly hydrochloric acid and acetic acid in view of the fact that the presence of these acids proves especially advantageous in oxidizing olefins to aldehydes, ketones and acids. Acids other than those indicated above may, however, also be used, for example nitric acid. In this case, it is preferred to remove the acid in excess in order to adjust the solution to the pH desired and to use the solution so treated as a catalyst or for impregnating the carrier. If desired the salt of the metals may also partially be converted into the corresponding chlorides and/ or acetates.
  • Palladium chloride or other noble metal chlorides need not be used, since there may also be employed the metals themselves, e.g. metallic palladium, suitably in a finely divided and finely distributed state, which reacts, for example, with copper chloride, and is converted to palladium chloride or a compound other than palladium chloride.
  • the metals themselves, e.g. metallic palladium, suitably in a finely divided and finely distributed state, which reacts, for example, with copper chloride, and is converted to palladium chloride or a compound other than palladium chloride.
  • the catalyst may contain as anion chlorine ions or halogen ions other than chlorine, such as fluorine or bromine ions, nitrates or chlorateor per chlorate radicals or mixtures of these anions, for example, with sulfate or acetate radicals.
  • anion chlorine ions or halogen ions other than chlorine such as fluorine or bromine ions, nitrates or chlorateor per chlorate radicals or mixtures of these anions, for example, with sulfate or acetate radicals.
  • the catalysts have generally a good activity even after a prolonged time of reaction, especially when anions are added during the reaction, it may be advantageous to regenerate the catalyst from time to time. Such regeneration methods are described hereinafter. Some further variants of regeneration methods have been described in the above-cited applications.
  • a possibility to recover palladium metal from liquid catalysts consists in subjecting the catalyst in known manner and in a strong acid medium to the action of acetylene.
  • a palladium-acetylene compound precipitates which can be readily separated and freed from cations and anions by means of a water wash.
  • the palladiumacetylene compound so obtained may be then converted in the air or in the presence of ammonium nitrate to palladium oxide which in turn is capable of being converted directly to the chloride by means of hydrochloric acid.
  • acetylene can act on the palladium compound in the presence of hydrogen.
  • a solid bed catalyst may be regenerated by arresting the olefin supply for a short while and treating the catalyst simultaneously with oxygen or oxygen-containing gases and steam and an acid in vapor form or gas form, preferably hydrogen chloride or hydrogen bromide.
  • a variant of such regeneration consists, for example, in passing oxygen or an oxygen-containing gas partially or completely and prior to contacting the catalyst through aqueous hydrochloric acid, preferably at a raised temperature. Accurately dosing the hydrochloric acid is especially simple, if a 20 percent hydrochloric acid is used.
  • the catalyst which prior to this treatment has possibly a metallic lustre turns again brown and regains its initial activity, possibly after an induction period of several hours.
  • the apparatus used in the process of this invention should be made of a material which is not corroded by the catalyst and preferably especially if solid catalysts are used, has a sufiicient thermal conductivity. Since the catalysts used contain noble metal compounds, for example palladium compounds, it is less suitable to use the usual metals and alloys as construction material, since there is the risk that these less noble metals, in the presence of water and at the indicated temperatures, precipitate the noble metal salt used in the catalyst, and that they themselves are converted into salt form.
  • noble metal compounds for example palladium compounds
  • an apparatus lined with titanium or titanium alloys containing at least 30 percent of titanium, or with tantalum There may also be used glass vessels or enamelled or rubber-lined vessels.
  • the reaction may also be carried out in brick-lined vessels or, under suitable reaction conditions, in vessels the insides of which are lined with plastic material, for example polyolefins, polytetrafiuorethylene or hardenable unsaturated polyesters, or phenol-, cresolor xylenol-formaldehyde resins.
  • brick lining there may be used, for example, ceramic material, carbon Ibricks impregnate-d with hardenable artificial resins and similar known materials.
  • Example 1 50 cc. of a catalyst solution containing, per liter of water, 1 gram of PdCl 100 grams of CuCl -2H O, and 5 cc. of concentrated hydrochloric acid, are heated to 80 C., and 1.5 liters of :gas are passed through per hour.
  • the gas used consists of 50% of ethylene and 50% of carbon monoxide and is mixed with half its volume of oxygen prior to the reaction.
  • the formed acetaldehyde is separated from the reaction mixture by Washing.
  • Example 2 A gas consisting of 10% of hydrogen, 20% of methane, 35% of ethane and 35% of ethylene, to which half its volume of oxygen has been admixed prior to the reaction, is introduced under the conditions described in Example 1 into the catalyst solution.
  • the conversion to acetaldehyde calculated upon the ethylene used is at about 5
  • Example 3 A gas consisting of 10% of hydrogen, 10% of carbon monoxide, 30% of methane, and 50% of ethylene, to which half its volume of oxygen has been admixed prior to the reaction, is introduced into the catalyst solution under the same conditions as described'in Example 1.
  • the conversion to acetaldehyde calculated upon the ethylene used is above 40%.
  • Example 4 100 cc. of an aqueous catalyst solution containing 0.2 gram PdCl and grams CuCl -2H O were introduced into a vertically arranged tube and maintained at 90 C. by jacket heating. 5 liter/h. of a mixture consisting of 70% by volume propylene, 20% by volume CO and 10% by volume propane and 2.5 liter/h. oxygen were then introduced into the tube through a frit and passed through the above catalyst solution.
  • the reaction was maintained by adding at intervals of about 2 hours 1 cc. 0.5 N-hydrochloric acid.
  • the conversion rate per passage through the catalyst solution was about 32%, calculated on propylene.
  • a catalyst of (a) a salt of a noble metal selected from the group consisting of palladium, iridium, ruthenium, rhodium and platinum and (b), as a redox system, an inorganic salt of a metal showing several valence states under the reaction conditions applied, the improvement of contacting said olefinic hydrocarbon, oxygen, and said catalyst in the presence of a diluent gas selected from the group consisting of carbon monoxide and hydrogen.
  • a noble metal selected from the group consisting of palladium, iridium, ruthenium, rhodium and platinum

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US84968A 1957-09-28 1961-01-26 Process for oxidizing olefins to aldehydes and ketones Expired - Lifetime US3301905A (en)

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3947521A (en) * 1974-04-08 1976-03-30 Diamond Shamrock Corporation Oxidation of allylacetone to 2,5-hexanedione
US3965185A (en) * 1972-07-03 1976-06-22 Union Oil Company Of California Oxidation of olefins to ketones and aldehydes
US3972942A (en) * 1974-04-08 1976-08-03 Diamond Shamrock Corporation Oxidation of allylacetone to 2,5-hexanedione in a water-carbon tetrachloride solvent system
US4034047A (en) * 1974-11-18 1977-07-05 Suntech, Inc. Process for catalytic oxidation of olefins to form hydroperoxides
US4271320A (en) * 1978-09-05 1981-06-02 Kuraray Co., Ltd. Process for producing a higher carbonyl compound
US4571290A (en) * 1984-08-22 1986-02-18 The Standard Oil Company (Ohio) Process for the selective oxidation of olefins with photochemical illumination of semiconductor powder suspensions
US5907056A (en) * 1997-09-17 1999-05-25 Saudi Basic Industries Corp. Catalysts for the oxidation of ethane to acetic acid, processes of making same and processes of using same
US6017846A (en) * 1999-01-11 2000-01-25 Saudi Basic Industries Corporation Highly active and selective catalysts for the production of unsaturated nitriles, methods of making and using the same
US6028221A (en) * 1998-06-29 2000-02-22 Saudi Basic Industries Corporation Catalyst systems for the one step gas phase production of acetic acid from ethylene and methods of making and using the same
US6030920A (en) * 1997-12-24 2000-02-29 Saudi Basic Industries Corporation Catalysts for producing acetic acid from ethane oxidation, processes of making same and method of using same
US6037304A (en) * 1999-01-11 2000-03-14 Saudi Basic Industries Corporation Highly active and selective catalysts for the production of unsaturated nitriles, methods of making and using the same
US6087297A (en) * 1998-06-29 2000-07-11 Saudi Basic Industries Corporation Catalysts for gas phase production of acetic acid from ethane, processes of making the same and methods of using same
US6130356A (en) * 1998-12-23 2000-10-10 Saudi Basic Industries Corporation Catalysts for the oxidation of ethane to acetic acid, methods of making and using the same
US6486091B1 (en) 2000-03-14 2002-11-26 Saudi Basic Industries Corporation Process for making highly active and selective catalysts for the production of unsaturated nitriles
US10035964B2 (en) * 2014-07-04 2018-07-31 Tubitak Circulating fluidized bed gasification or combustion system

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB638754A (en) * 1947-05-16 1950-06-14 Du Pont Improvements in and relating to the synthesis of primary alcohols
FR1210009A (fr) * 1957-10-25 1960-03-04 Hoechst Ag Procédé d'oxydation d'oléfines en aldéhydes, cétones et acides
US3027411A (en) * 1959-06-22 1962-03-27 Gulf Research Development Co Process for oxidizing a normally gaseous hydrocarbon
US3076032A (en) * 1957-10-31 1963-01-29 Hoechst Ag Process for oxidizing olefins to aldehydes and ketones
US3119875A (en) * 1957-10-31 1964-01-28 Hoechst Ag Process for oxidizing olefins to aldehydes and ketones

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE540896C (de) * 1922-05-27 1931-12-28 I G Farbenindustrie Akt Ges Verfahren zur Gewinnung von Kohlenwasserstoffen der AEthylenreihe aus kohlenoxydhaltigen technischen Gasgemischen
DE622965C (de) * 1929-06-04 1935-12-10 Bataafsche Petroleum Verfahren zur Herstellung von Absorptionsprodukten des AEthylens in starken Saeuren

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB638754A (en) * 1947-05-16 1950-06-14 Du Pont Improvements in and relating to the synthesis of primary alcohols
FR1210009A (fr) * 1957-10-25 1960-03-04 Hoechst Ag Procédé d'oxydation d'oléfines en aldéhydes, cétones et acides
US3076032A (en) * 1957-10-31 1963-01-29 Hoechst Ag Process for oxidizing olefins to aldehydes and ketones
US3119875A (en) * 1957-10-31 1964-01-28 Hoechst Ag Process for oxidizing olefins to aldehydes and ketones
US3027411A (en) * 1959-06-22 1962-03-27 Gulf Research Development Co Process for oxidizing a normally gaseous hydrocarbon

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3965185A (en) * 1972-07-03 1976-06-22 Union Oil Company Of California Oxidation of olefins to ketones and aldehydes
US3947521A (en) * 1974-04-08 1976-03-30 Diamond Shamrock Corporation Oxidation of allylacetone to 2,5-hexanedione
US3972942A (en) * 1974-04-08 1976-08-03 Diamond Shamrock Corporation Oxidation of allylacetone to 2,5-hexanedione in a water-carbon tetrachloride solvent system
US4034047A (en) * 1974-11-18 1977-07-05 Suntech, Inc. Process for catalytic oxidation of olefins to form hydroperoxides
US4271320A (en) * 1978-09-05 1981-06-02 Kuraray Co., Ltd. Process for producing a higher carbonyl compound
US4571290A (en) * 1984-08-22 1986-02-18 The Standard Oil Company (Ohio) Process for the selective oxidation of olefins with photochemical illumination of semiconductor powder suspensions
US5907056A (en) * 1997-09-17 1999-05-25 Saudi Basic Industries Corp. Catalysts for the oxidation of ethane to acetic acid, processes of making same and processes of using same
US6013597A (en) * 1997-09-17 2000-01-11 Saudi Basic Industries Corporation Catalysts for the oxidation of ethane to acetic acid processes of making same and, processes of using same
US6030920A (en) * 1997-12-24 2000-02-29 Saudi Basic Industries Corporation Catalysts for producing acetic acid from ethane oxidation, processes of making same and method of using same
US6310241B1 (en) 1997-12-24 2001-10-30 Saudi Basic Industries Corporation Catalysts methods for producing acetic acid from ethane oxidation using MO, V, PD and NB based catalysts, processes of making same and methods of using same
US6383977B1 (en) 1997-12-24 2002-05-07 Saudi Basic Industries Corporation Catalysts for producing acetic acid from ethane oxidation, processes of making the same and methods of using same
US6087297A (en) * 1998-06-29 2000-07-11 Saudi Basic Industries Corporation Catalysts for gas phase production of acetic acid from ethane, processes of making the same and methods of using same
US6028221A (en) * 1998-06-29 2000-02-22 Saudi Basic Industries Corporation Catalyst systems for the one step gas phase production of acetic acid from ethylene and methods of making and using the same
US6156928A (en) * 1998-06-29 2000-12-05 Saudi Basic Industries Corporation Method for gas phase production of acetic acid from ethane
US6274764B1 (en) 1998-06-29 2001-08-14 Saudi Basic Industries Corporation Process for one step gas phase production of acetic acid from ethylene
US6130356A (en) * 1998-12-23 2000-10-10 Saudi Basic Industries Corporation Catalysts for the oxidation of ethane to acetic acid, methods of making and using the same
US6087525A (en) * 1999-01-11 2000-07-11 Saudia Basic Industries Corporation Highly active and selective catalysts for the production of unsaturated nitriles, methods of making and using the same
US6124233A (en) * 1999-01-11 2000-09-26 Saudi Basic Industries Corporation Highly active and selective catalysts for the production of unsaturated nitriles, methods of making and using the same
US6037304A (en) * 1999-01-11 2000-03-14 Saudi Basic Industries Corporation Highly active and selective catalysts for the production of unsaturated nitriles, methods of making and using the same
US6017846A (en) * 1999-01-11 2000-01-25 Saudi Basic Industries Corporation Highly active and selective catalysts for the production of unsaturated nitriles, methods of making and using the same
US6486091B1 (en) 2000-03-14 2002-11-26 Saudi Basic Industries Corporation Process for making highly active and selective catalysts for the production of unsaturated nitriles
US10035964B2 (en) * 2014-07-04 2018-07-31 Tubitak Circulating fluidized bed gasification or combustion system

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