MXPA97005493A - Hydroformilation of a food stream of multiple components - Google Patents

Abstract

A process for the production of aldehydes of 3 to 6 carbon atoms by hydroformylation of a mixture of: (i) olefins of 2 to 5 carbon atoms and mixtures thereof, (ii) alkynes of 2 to 5 carbon atoms and mixtures of the same, and optionally (iii) accumulated dienes, in the presence of a solution of a rhodium organophosphorus complex catalyst, at a rhodium concentration in solution of 1 to 1000 ppm by weight, in particular the olefin is ethylene and the alkyne is acetylene, and the proportion of phosphorus to rhodium is greater than 30. Aldehydes are intermediary useful in the production of different alcohols, polyols and

Description

HYDROFORMILATION OF A POWER SUPPLY OF MULTIPLE COMPONENTS FIELD OF THE INVENTION This invention relates to hydroformylation methods for certain multi-component synthesis gas feed streams containing hydrogen, carbon monoxide, olefins of 2 to 5 carbon atoms, and alkynes of 2 to 5 atoms of carbon. BACKGROUND OF THE INVENTION There is an intense research around the world directed to the use of natural gas as a petrochemical supply. The current use of natural gas is mainly restricted to the production of synthesis gas ("syngas", a mixture of carbon monoxide and hydrogen), and heat. However, it has long been known that methane can be converted into synthesis gas mixtures containing acetylene using short contact time acetylene burners. The co-production of ethylene or ethylene blending with these acetylene-rich feeds could provide a power supply based on economical natural gas. However, the use of these co-produced feeding currents has presented problems in certain processes.

The hydroformylation of mixtures of highly purified olefins and synthesis gas in aldehyde and alcohol products is well known (see B. Cornils "Hydroformylation, Oxo Synthesis, Roelen Reaction" in "New Syntheses with Carbon Monoxide", Ed. J. Falbe, Springer Verlag: New York, 1980. When pure alcohol products are desired, the aldehyde products can be hydrogenated to obtain the corresponding alcohol derivatives.A particularly useful catalyst has been described for the hydroformylation of pure light olefin feeds as a homogenous oil-soluble phosphine-modified Rh catalyst (see, e.g., U.S. Patent Nos. 3,527,809, 3,917,661, 4,148,830), which operates at lower pressures than other homogeneous catalysts, gives high proportions from normal to iso in the hydroformylation of olefins of 3 carbon atoms and higher, and it has been proven to be very effective with these olefin feeds The use of this homogenous soluble oil-soluble Rh catalyst for hydroformylating purified ethylene feeds to obtain propanal has also been described by Evans et al. (J. Chem. Soc. (A) 1968, 3133), as well as Pruett et al. (J. Org. Chem., 1968, 34, 327). However, there is a great need for strict purification of the feed supply, because the activity of the catalyst is strongly inhibited by acetylene and other highly unsaturated hydrocarbons if they are present as impurities in the commercial oxo feeds. These components must be removed essentially before hydroformylation (see B. Cornils "Hydroformilation, Oxo Synthesis, Roelen Reaction" in "New Syntheses with Carbon Monoxide", Ed .: J. Falbe, Springer Verlag: New York, 1980, pages 64 and 73). The highly purified feeds of synthesis gas (mixtures of CO and H2) and olefins are currently made in two separate processes. The light olefins are usually made by steam disintegration, and are purified by cryogenic distillation and selective hydrogenation to remove even traces of acetylenes and dienes. The highly purified olefin feeds currently used contain less than 100 ppm, and typically less than 10 ppm of these impurities. In fact, a large portion of the cost of ethylene currently produced for hydroformylation by steam disintegration is associated with its purification. The synthesis gas component can be made from a hydrocarbon, such as methane or a crude distillate, and oxygen in a partial oxidation reactor (POX), in a way that essentially does not produce dienes or acetylenes. Even when the synthesis gas made in the partial oxidation reactor contains only trace amounts of acetylenes and dienes, it is also carefully purified further before being mixed with the purified olefin feed. The hydroformylation of pure acetylenes and pure dienes with Co or Rh catalysts is also known (see: U.S. Patent Number 5,312,996, 1994; P.N.M. Van Leeuwen and C.F. Roobeek J. Mol. Catal. 1985; U.S. Patent Number 4,507,508, 1985; 31, 345, B. Fell, H. Bahrmann J. Mol. Catal. 1977, 2, 211; B. Fell, M. Beutler Erdól and Kohle -Erdgas - Petrochem. 1976, 29 (4), 149; U.S. Patent Number 3,947,503, 1976; B. Fell, W. Boíl Chem. Zeit. 1975, 99 (11), 452; M. Orchin, W. Rupilius Catal. Rev. 1972, 6 (1), 85; B. Fell, M. Beutler Tetrahedron Letters 1972, No. 33, 3455; C. K. Brown and G. Wilkinson J. Chem. Soc. (A) 1970, 2753; B. Fell,. Rupilius Tetrahedron Letters 1969, No. 32, 2721; F.H. Jardine et al., Chem. And Ind. 1965, 560; H. Greenfield et al., J. Org. Chem. 1957, 22, 542; H. Adkins and J.L.R. Williams, J. Org. Chem. 1952, 71, 980). The hydroformylation of these highly unsaturated compounds with cobalt catalysts is slow, even at high temperatures and pressures 145-175 ° C, 20-30 MPa). In addition, the reaction often produces side products, and results in uncontrolled reactions with sudden surges of temperature and pressure. The hydroformylation of olefins is severely inhibited by acetylenes, since these compounds form very stable adducts with cobalt carbonyl. The stoichiometric amounts of acetylenes can effectively transform the cobalt catalyst into these catalytically inactive acetylenic adducts (H. Greenfield et al., J. Org. Chem. 1957, 22, 542). With conventional Rh catalysts, reported reaction conditions and reaction rates are far from practical for any commercial use. Fell typically used pressures of 17-23 MPa using PPh3 / Rh catalyst, and yet high conversions required reaction times of 2 to 5 hours. Wilkinson achieved a high conversion in the hydroformylation of hexin-1 at a pressure of 4.8 MPa, but only with a reaction time of 12 hours. Van Leeuwen and Roobeek applied conditions of 1.2 MPa, 95-120 ° C, and P / Rh ratios of 10 or less in the hydroformylation of butadiene, but observed low activities (orders of magnitude lower than for olefins). In U.S. Patent Number 3,947,503 a two-step process for hydroformylating 1,3-butadiene is described. In the first step a PPh3 / Rh catalyst is used in the presence of alcohols or diols to make the acetals of the unsaturated carbon atom aldehyde. In the second step, this intermediate is hydroformylated using Co catalysts. The process described in U.S. Patent No. 4,507,508 also claims the conversion of conjugated dienes with P / Rh catalyst promoted by ester or organic acid in the presence of alcohols. U.S. Patent No. 5,312,996 discloses a polyphosphite ligand-modified Rh catalyst for the conversion of 1,3-butadiene. When a two-step process is used for the hydroformylation of 1,3-butadiene with the described catalyst, more severe conditions are recommended in the second stage to ensure acceptable conversions. This latter patent also describes 1,3-butadiene as a strong inhibitor in the conversion of alpha-olefins. In the co-conversion of alpha-oleas with 1, 3-butadiene oxo-aldehyde, products of both alpha-olefins and 1,3-butadiene were produced. As mentioned, acetylenes and dienes act as strong inhibitors / poisons of the catalysts in the hydroformylation of alpha-olefins, and their removal from the oxo feeds is required. European Patent Application No. 0225143 A2 describes a method for the production and use of synthesis gas mixtures containing acetylene and ethylene. One of the described schemes of use is to produce propanal by hydroformylation, but first the acetylene must be removed from the feed by selective hydrogenation in ethylene on a heterogeneous metal oxide or sulphide catalyst. The Patent of the United States of North America Number 4, 287,370 also teaches that inhibitors, such as 1,3-butadiene, should be removed from the olefin feed supplies of 4 carbon atoms by selective hydrogenation before hydroformylation using HRh (CO) (PPh3) 3 as a catalyst. German Patent Number DE 2638798 teaches that the removal of acetylenes and dienes is needed in order to ensure an acceptable life of the catalyst in the hydroformylation of olefins with a rhodium catalyst modified with phosphine. In one of the most frequently cited sources (B. Cornils "Hydroformylation", Oxo Synthesis, Roelen Reaction "in" New Syntheses with Carbon Monoxide ", Ed.: J. Falbe, Springer Verlag: New York, 1980, page 73), acetylenes and dienes are referred to as "classical catalyst poisons" for oxo catalysts of phosphine-modified Rh ox. It is also reported that acetylenes and dienes are strong poisons in the hydroformylation of olefins with cobalt catalysts (V. M. Polievka Rau Roe 1976, 18 (1), 18; Patent of the United States of America No. 2,752,395. Known catalytic processes that convert synthesis gas mixtures containing acetylene and ethylene, produce products other than propanal, or the conditions employed and / or the reaction rates achieved are far from practical. Accordingly, for example, European Patent Application Number 0,233,759 (1987) teaches the conversion of synthesis gas containing acetylene and ethylene (a mixture of acetylene, ethylene, CO, and H 2 at a ratio of 6: 3: 30: 61, respectively) in a mixture of acrylate and propionate esters in the presence of an alcohol using an Rh catalyst. When an Rh oxo catalyst modified with PPh3 is used to convert the same feed to a P / Rh ratio of 10.6 under otherwise identical conditions, the catalyst essentially dead (change frequency 1.5x10"4 moles product / mol of Rh / second, and a total change of 13 in 24 hours) described in European Patent Application Number 0,233,759 (1987) produces some propanal and acetone in a molar ratio of 90 to 1, with traces of methyl ethyl ketone and methylene propionate T. Mise et al. (Chem. Lett, 1982, (3), 401) have reported that synthesis gas mixtures containing acetylene and ethylene produce β-unsaturated ethyl ketones in the presence of an Rh catalyst; , there is no phosphine present in the catalyst The observed catalyst activities are very low, of the order of 5 rotations / hour, or of 1.39x10"3 moles of product / mol of RH / second, even when the concentration of ethylene in the feeding of gas is high, 41.7 percent by volume. The total turnover reported by Mise is only 30 in 6 hours. Accordingly, it would be desirable that methods could be found to make possible the processing of oxo / hydroformylation feed streams, using rhodium-based catalysts containing olefins and alkynes, particularly ethylene and acetylene. The present invention meets these needs. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 describes a hydrotreatment protection bed for reducing the level of multiple unsaturates in a multi-component synthesis gas, using a rhodium complex as a reagent in a protection bed of the scrubber. Figure 2 describes a two-stage oxo process for the hydroformylation of multi-component synthesis gas mixtures. Figure 3 describes an integrated process for the separation of the aldehyde product and the recovery of alkylolefin with alkylene-olefin recycle. SUMMARY OF THE INVENTION The present invention provides methods for using mixed unsaturated hydrocarbon feeds containing multi-component synthesis gas, having both an olefin (particularly ethylene) and more highly unsaturated hydrocarbons, particularly alkynes (in particular acetylene), accumulated dienes (especially aleño), and mixtures thereof, instead of single-type feed streams, in hydroformylation reactions carried out in the presence of certain rhodium complexes as catalysts. As a benefit, the invention allows the co-conversion of acetylene and ethylene using rhodium-based catalyst technologies, and provides a new feed supply and processing options, and simplified production schemes for the synthesis of the corresponding aldehyde product, particularly propanal Accordingly, the present invention provides a process for the production of aldehydes of 3 to 6 carbon atoms, which comprises hydroformylating a mixture containing: - (a) olefins of 2 to 5 carbon atoms and mixtures thereof, and - (b) (i) alkynes of 2 to 5 carbon atoms and mixtures thereof, or (ii) accumulated dienes of 3 to 5 carbon atoms and mixtures thereof, or (iii) mixtures of (i) ) and (ü), with CO, H2 and a solution of a rhodium complex catalyst produced by complexing with Rh and an organophosphorus compound in a concentration of Rh in solution of 1 to 1,000 ppm by weight. The present invention also provides a process for the production of aldehydes of 3 to 6 carbon atoms, which comprises hydroformylating a mixture containing: - (a) olefins of 2 to 5 carbon atoms and mixtures thereof, and - - (b) (i) alkynes of 2 to 5 carbon atoms and mixtures thereof, or (ii) accumulated dienes of 3 to 5 carbon atoms and mixtures thereof, or (iii) mixtures of (i) and (ii), with CO, H2 and a solution of a rhodium complex catalyst produced by the complex formation with Rh and an organophosphorus compound, wherein the catalyst solution has an atomic ratio of P / Rh of at least 30. The present invention also provides a process for the production of aldehydes of 3 to 6 carbon atoms, which comprises hydroformylating a mixture containing: - (a) olefins of 2 to 5 carbon atoms and mixtures thereof, and - (b) (i) alkynes of 2 to 5 carbon atoms and mixtures thereof, or (ii) accumulated dienes of 3 to 5 carbon atoms and mixtures thereof, or (iii) mixtures of (i) and (ü), with CO, H2 and a solution of a rhodium complex catalyst produced by the complex formation with Rh and an organophosphorus compound, wherein the catalyst solution has an atomic ratio of P / Rh greater than the RL value where: P (? S / R) where RB is the ratio of P / Rh sufficient for a catalytically active Rh complex, pKaTPP is the pKa value for triphenylphosphine, pKaL is the pKa value for the triorganophosphorus compound, R is the gas constant, and ΔSB is 35 (N-1) cal / mol ° K, where N is the number of P-Rh bonds per molecule of the ligand. The hydroformylation, as described above, yields the aldehydes of 3 to 6 corresponding carbon atoms. Typically, the atomic ratio of P / Rh, RB for the catalytically active Rh complex, is between 1 and 3. Typically, the rhodium complex catalyst is an oil-soluble rhodium complex catalyst produced by the complex formation in solution of a low valence Rh, and an oil soluble triorganophosphorous compound. Typically, the catalyst solution can be prepared with an oily solvent, such as aliphatic or aromatic hydrocarbons, esters, ethers, aldehydes, the condensation by-products of the oxo-aldehyde product, etc. The present invention also provides the production of the corresponding derivatives of the aldehydes produced as provided above, including alcohols, acids, aldol dimers, and different hydrogenation and oxidation products produced from the aldol dimers. We have discovered that the presence of acetylene stabilizes the hydroformylation catalyst. The present invention may suitably comprise, consist, or consist essentially of the elements described herein, and may be practiced in the absence of any step not specifically described as required. DETAILED DESCRIPTION OF THE INVENTION The headings herein are for convenience only, and are not intended to limit the invention in any way. In addition, exclusively for convenience, the numbering in the Figures and throughout the text is as follows: the process streams (for example, reagent and product) are numbered in ci in nts, and the elements to perform a process or operation (for example, units or devices) are numbered in tens. The first digit of each identifies the figure to which it corresponds. The present invention pertains to processes that use multi-component synthesis gas. A mixture of multi-component synthesis gas (SMC) is defined as mixtures of gas containing carbon monoxide, hydrogen, olefins (with a general formula of CnH2n and with a functional group of C = C) having 2 to 5 carbon atoms, and more highly unsaturated hydrocarbons, such as alkynes (with a general formula of CnH2n_2 / y with a functional group of C = C) having 2 to 5 carbon atoms, or dienes accumulated (with a general formula of CnH2n_2 and with a functional group of C = C = C). The multi-component synthesis gas mixtures may optionally contain other unsaturated hydrocarbons, such as conjugated dienes (with a general formula of CnH2n_2 and with a functional group of C = CC = C) having from 3 to 5 carbon atoms, (with a general formula of CnH2n_4 and with a functional group of C = CC = C and diinos (with a general formula of CnH2n_4 and a functional group of C = CC = C) having from 4 to 5 carbon atoms. Multi-component synthesis gas can also contain inert components, for example, nitrogen, carbon dioxide, functionally inert hydrocarbons, such as alkanes and aromatic hydrocarbons, and water vapor.As used herein, the term "olefin" includes alkenes and excludes dienes, the dienes, when present, are referred separately., "monounsaturated" are understood as a subgroup of synthesis gas components of multiple hydrocarbon components that have an unsaturated functionality that is olefins or alkynes. The "unsaturated of 2 carbon atoms" are ethylene or acetylene individually or combined. The "multi-unsaturated" are a subgroup of the multi-component hydrocarbon synthesis gas components having at least two carbon-carbon multiple bonds, ie, dienes, diinos and eninos as defined herein, taken individually or in any combination. The present invention provides methods for converting certain multi-component synthesis gas feeds by reassembling their major components, hydrogen and carbon monoxide (ie, synthesis gas), alkynes of 2 to 5 carbon atoms, particularly acetylene, and olefins of 2 to 5 carbon atoms, particularly ethylene, by hydroformylation (oxo reaction). One embodiment of the process of the present invention provides a method for using a multi-component synthesis gas feed containing at least carbon monoxide, hydrogen, and monounsaturated hydrocarbon reagents of olefinic hydrocarbons having from 2 to 5 carbon atoms ( ie, ethylene, propylene, butenes and pentenes), and alkynes having from 2 to 5 carbon atoms (such as, e.g., acetylene and methylacetylene), in a low pressure oxo conversion process catalyzed with rhodium. These monounsaturated alkynes and olefins include the alkyne components and the individual 2 to 5 carbon atoms olefin components, as well as mixtures of the alkyne components of 2 to 5 carbon atoms and mixtures of the olefin components of 2 to 5. carbon atoms. In a preferred embodiment, the main monounsaturated hydrocarbon reactants are essentially ethylene and acetylene. These reagents are fed into the process as components of a multi-component synthesis gas, which may also contain, depending on its preparation method, reactive monounsaturates of 3 to 5 carbon atoms and multi-unsaturated of 3 to 5 carbon atoms as minor components , and functionally inert materials in varying amounts, such as carbon dioxide, water vapor, nitrogen and functionally inert hydrocarbons (such as alkanes and aromatics). The multi-component synthesis gas containing substantial amounts of inert (and functionally inert) components can be referred to as a diluted multi-component synthesis gas. The diluted multi-component synthesis gas can incorporate any multi-component synthesis gas feed wherein the reactive components (CO, H2, olefin, alkyne) can be present together with substantial amounts of inert components. It is desirable to use feed streams having substantial diluent levels, because these feed streams may be available at a substantial discount relative to the cost of the highly purified components. For example, the olefin contained in the light ends of the catalytic disintegrator or in the effluent of the steam disintegrator furnace may be available at a substantial discount relative to the purified olefins. In the same way, acetylene and synthesis gas are less expensive if they can be obtained without a complete purification. In addition, partial oxidation (POX) processes can be less expensive if air is used as a feed instead of oxygen. The synthesis gas, or the multi-component synthesis gas from this partial air-blown oxidation, could be characterized as a diluted multi-component synthesis gas, due to the substantial levels of N2 included. Mainly, the amount of inert components present in the diluted multi-component synthesis gas can be any value, reaching even 99 percent of the power supply. Typically, the levels of the inert component in a diluted multi-component synthesis gas are between 1 percent and 80 percent of the stream. Table 2 (Example 1) shows an example of the hydroformylation of a diluted multi-component synthesis gas having 63 percent inert components, including N2, C02, CH4 and C2H6. It is known that certain trace components in the multi-component synthesis gas feed of the overall process referred to herein as "multi-component process feed" are deleterious in the oxo reaction. Some are irreversible catalyst poisons, e.g., sulfur compounds, such as H2S and COS. Others cause a reversible poisoning or an accelerated deactivation of the catalyst. This last group includes components such as halides, cyanides, oxygen and iron carbonyls. The concentration of these detrimental components can be adjusted by a variety of techniques known in the art, to provide a multi-component synthesis gas feed acceptable to the oxo reactor or the unit, referred to herein as "oxo reactor feed". multiple components. " Synthetic gas mixtures of multiple components are available in a variety of different sources. A benefit of the present invention is that any mixture of mixed acetylene-ethylene synthesis gas can be used as a feed supply in the processes of the present invention. There are a variety of methods for making multi-component synthesis gas mixtures useful in the process of the present invention. One is to mix a stream that contains synthesis gas (a mixture of CO and H2) with a stream that I contain! a mixture of acetylene, ethylene, and optionally other unsaturated hydrocarbons. Both streams can be obtained from conventional petrochemical processes. The stream containing synthesis gas (CO and H2) can be produced by conventional partial oxidation (POX). Light monounsaturates (2 to 5 carbon atoms) containing ethylene and acetylene as the main components of unsaturated hydrocarbon can be obtained from petrochemical processes, such as steam disintegration or acetylene manufacture, or by modifying one of the known processes used to make acetylene or synthesis gas. Accordingly, acetylene can be formed using a partial oxidation process that applies a burner to react methane-oxygen mixtures. Acetylene burners fed with a molar ratio of approximately two to one methane and oxygen, can directly produce a mixture of acetylene-rich gas containing ethylene, as well as CO and hydrogen. The suffocation of the reaction with naphtha can further increase the concentration of acetylene and ethylene in the product stream of the acetylene burner. Ethylene or synthesis gas can also be added to the acetylene-rich mixtures to adjust the molar proportions of the components. One side of the above is that it allows the use of an abundant feed supply, such as natural gas, and eliminates the need for elaborate and costly separation and purification of oxo feeds, which often result in significant yield losses. and an additional expense. In order to maintain the partial pressure of the acetylene below the safety limit, a portion of the acetylene can be purified from the multi-component synthesis gas feeds before being compressed to the reaction pressure for the oxo reactor. Alternatively, streams containing acetylene can be diluted with other feed components, eg, ethylene, carbon monoxide, hydrogen or mixtures thereof. Synthetic gas streams of multiple components entering the hydroformylation reactor oxo or to the reaction zone (feeds of the multi-component oxo reactor) in the process of the present invention, contain monounsaturates of 2 to 5 carbon atoms, among which which the ratio of ethylene to acetylene is on a scale of 1: 100 to 100: 1, preferably 1:10 to 10: 1. Typically, the mixture contains an amount of olefins that is at least 40 percent of the total unsaturates. The amount of CO and H2 in the multi-component oxo reactor feed, with respect to the amount of monounsaturates, is preferred to be at levels of at least about that required for the stoichiometric conversion of the monounsaturated hydrocarbons in the oxo reaction. .

A stoichiometric conversion of these species requires that the molar percentage of CO is equal to the sum of the molar percentages of monoinstruments. In a similar way, for the stoichiometric conversion, the molar percentage of acids must be equal to the sum of the molar percentages of olefins of 2 to 5 carbon atoms plus twice the molar percentages of alkynes of 2 to 5 carbon atoms . It is preferred that the CO and the H2 are present in the feed of the multi-component oxo reactor in a range from half to 100 times that required for the stoichiometric conversion. It is more preferred that the concentrations of CO and H2 are in the range of 1 to 10 times that required for a stoichiometric conversion. Subject to these requirements, the proportions of H2 / CO in the multi-component synthesis gas entering the oxo reactor (that is, in the multi-component oxo reactor feed) can be from 1: 1 to 100: 1, preference from 1: 1 to 50: 1, and more preferably from 1: 1 to 10: 1. Although the presence of excessive volumes of H2 is preferred from a chemical perspective, a large H2 excess of more than 10 is undesirable from a material handling perspective, and may result in an unnecessary expense in the operation of the unit. A range of composition values is given in Table 1, as well as a typical composition for the major species present in the multi-component synthesis gas mixtures entering the oxo reactor (ie, in the feeds of the oxo reactor). multiple components) for the process of the present invention are given in Table I. Table I. Oxo multi-component reactor feed compositions for the major components Multi-component synthesis gas mixtures produced by, for example, steam disintegration, or by partial oxidation, may contain a variety of molecular species that are detrimental to the hydroformylation process, or are known to deactivate the oxo catalysts. For example, it is known that rhodium metal complex hydroformylation catalysts are poisoned by certain sulfur-containing molecules (e.g., H2S and C0S) that bind irreversibly to the center of the metal. These poisons can be eliminated through the use of common chemical engineering and chemical engineering techniques, such as the use of protection beds, particularly protection beds containing zinc oxide. The streams used with the present invention may also contain multiunsaturates having from 3 to 5 carbon atoms. Their concentrations are typically less than 5 mole percent of the total unsaturated hydrocarbon fed to the hydroformylation. The catalysts described herein as active for the hydroformylation of olefins and alkynes, will be similarly active for the hydroformylation of olefins and multiinsaturates. Highly unsaturated components, such as these multiinsaturates, can be inhibitors in the oxo conversion of olefins. They can reduce the activity of the oxo catalyst by a very strong association with the metal, and thus decrease the activity of the catalyst towards the hydroformylation of the olefins. Accordingly, the multi-unsaturated amounts are preferably less than 5 percent of the total unsaturated hydrocarbon fed to the hydroformylation. More preferably, the multiunsaturates must be present in the hydroformylation feed in amounts less than 1 mole percent of the total unsaturates. Examples 4 and 8 demonstrate the hydroformylation of multi-component synthesis gas mixtures containing olefins and multiinsaturates (specifically, aleño). An exception to the above preferences over multiunsaturated concentrations is the group of non-conjugated and non-accumulated dienes (diolefins), for which there are no restrictions. Generally speaking, the multi-component oxo reactor feed streams preferably contain monounsaturates. Multi-unsaturated hydrocarbons containing conjugated and accumulated diene and enine type unsaturation are considered less desirable. These multi-unsaturates can be removed from the multi-component process feeds, or their concentrations can be reduced prior to contact with the hydroformylation catalyst. Although multi-component synthesis gas products generally do not require treatment before use in the processes of the present invention, the multi-unsaturated containing feed streams at a higher concentration than the above preferred concentrations are they can treat, segregate or dilute with currents that comprise substantially CO, H2, monounsaturated and inert. ELIMINATION OF MULTI INSATURATES If necessary, the multi-component process feeds can be treated before entering the oxo reactor (ie, hydroformylation beads), if the concentration of the above-specified multiunsaturated inhibitor components is too high. A light selective hydrogenation, for example, using heterogeneous catalysts (e.g., Pd on alumina, or mixed oxide and sulfide catalysts as described in European Patent Application Number 0,225,143), can convert these reactive hydrocarbons to olefins and alkanes. However, these conventional heterogeneous hydrotreating methods have drawbacks. For example, in heterogeneous systems, high concentrations of unsaturated hydrocarbons (ie, olefins, alkynes and multiunsaturated) with high concentrations of hydrogen present a risk of a highly exothermic uncontrolled reaction. The selectivity of the catalyst, and other operational issues of the plant provide additional incentives to look for alternative solutions. Accordingly, another embodiment of the present invention provides a selective process in liquid phase to solve the problems associated with the application of the known heterogeneous catalysts. The liquid phase used in the process can be a homogeneous phase or a paste that contains solids, and that can be pumped. Applicants have discovered that the Rh catalyst used in the hydroformylation process of the present invention is suitable for the selective conversion of the above multiunsaturated hydrocarbon components into olefins, when the complex is used, not as a catalyst, but as a reactant stoichiometric in a separate pre-treatment step. The preferred reagent is the organophosphorus modified rhodium catalyst of the oxo / hydroformylation reactor described in more detail in "Rh 0X0 CATALYZER" below. In a preferred embodiment, a two-step process is used to convert the excess of multi-unsaturates into the multi-component synthesis gas, into olefins and alkanes. In the first step of the process, the Multi-Component Synthesis Gas is contacted with a solution containing the rhodium complex with ligand as a reagent. The strong preferential bond of the multiinsaturates to the rhodium complex serves to extract them from the synthesis gas of multiple components, and into the solution, where they remain as a bound species on the rhodium. This gas / liquid "scrubbing" effectively removes the multi-unsaturated ones from the multi-component synthesis gas feed. The Rh complex functions essentially as a stoichiometric reagent by fixing the multi-unsaturated hydrocarbons of the multi-component synthesis gas during contact. In a separate second step, the multiinsaturates are converted into the corresponding olefins, and the rhodium complex is regenerated by contacting the solution containing complexed multiinsaturates., with a gas with a high hydrogen content and low carbon monoxide content, for a sufficient time to effect the conversion of the multi-unsaturated. If this multi-unsaturated hydrogenation was carried out under conventional hydroformylation conditions, that is, at partial CO pressures of 10-1,000 kPa, the conversion of these strongly bound species, into olefins, would be slow (see Example 4), in such a manner that the required rhodium concentrations would not be economical. However, we have found that the conversion of these multiunsaturates can be accelerated substantially under conditions of higher partial hydrogen pressures, and especially lower partial pressures of CO, than the conventional rhodium hydroformylation. The Rh solution containing complexed multiinsaturates can be regenerated in a separate reactor, with a gas rich in hydrogen, that is, a gas having high concentrations of hydrogen and low concentrations of CO, or pure hydrogen. During this regeneration, the Rh complex is returned to its multi-unsaturated form, while the multi-unsaturated ones are hydrogenated to obtain the corresponding olefins and alkanes. For example, the aleño, for example, is hydrogenated during this process to obtain propylene first, while the butadienes are hydrogenated to obtain butenes. In this regeneration hydrotreating step, some of the olefins formed from multiinsaturates will be hydrogenated further to obtain the corresponding alkanes. The hydrogenation rate in the regeneration step can be adjusted by adjusting the partial pressures of hydrogen and CO. Higher partial pressures of hydrogen will increase the rate of hydrogenation. On the other hand, the increase in partial pressures of CO will reduce the hydrogenation activity of the catalyst. The speed and selectivity can be conveniently controlled by adjusting the partial pressure of CO in the hydrotreating reactor. The benefit of the process described herein is that the composition of the depuration solution used for the stoichiometric elimination of multiunsaturates can be essentially the same as that used for the catalytic oxo passage. Any level of multi-unsaturated elimination can be performed. The multi-unsaturated hydrocarbons (e.g., aleño or vinylacetylene) are preferably removed from the gas phase, because they bind more strongly than the monounsaturates, particularly the olefins. Since the components that are most strongly fixed are the strongest inhibitors in the oxo conversion of monounsaturates, particularly in the oxo conversion of defines, the process removes the strongest inhibitors first, and produces a multi-component synthesis gas deficient in multi-unsaturated, purified, which is preferred as the oxo / hydroformylation reactor feed. An additional advantage of using the rhodium-oxo catalyst solution for the pretreatment of the hydroformylation feed of the multi-component synthesis gas is that it is not necessary to rigorously control the losses of rhodium complex due to the entry into the multi-component synthesis gas phase, because the downstream hydroformylation reactor system has elements to effectively capture this Rh complex. In addition, any Rh compound carried forward by the multi-component synthesis gas stream will not contaminate the catalyst in the oxo reactor, since the compositions are essentially the same. By way of example, Figure 1 shows the Absorbent 11, where the multi-component multi-unsaturated synthesis gas feed (101) is contacted with a depleted multi-unsaturated solution of the oil-soluble rhodium complex (105). . This absorbent is analogous to sacrificial catalyst protection beds that are sometimes used in heterogeneous catalysis. The multi-unsaturated multi-component synthesis gas stream (102) emerges from the absorbent to be sent to the hydroformylation (shown here as two reactors (13 and 14) in series, each with surrounding pumping cooling (107 and 109) and reactor effluents (108 and 110)). Unlike the "protection bed" of the heterogeneous catalysts, the multi-unsaturated "sacrifice" catalyst of this process is a pumpable liquid phase solution of an Rh complex (106) which is recovered at the bottom of the absorbent. The complexed multiinsaturated solution (106) is pumped into a regeneration reactor (12), where it is treated with a hydrogen-containing gas (104). In the regeneration rector, the multi-unsaturated rhodium complex is recovered by hydrogenation of the multiinsaturates complexed in olefins and alkanes. A gas purge stream (103) is used from the regeneration reactor to retain high concentrations of hydrogen. The depleted, multi-unsaturated, regenerated solution of the Rh complex (105) is returned from the regenerator (12) to the absorbent (11). To the extent that the olefin and alkane products of the multi-unsaturated hydrogenation remain undissolved in the catalyst solution, they will be transferred back into the multi-component synthesis gas stream during contact with the catalyst solution in the absorbent ( eleven) . The temperature in the absorbent (11) is maintained on the scale from 0 ° C to 150 ° C, preferably between 20 ° C and 60 ° C. If the temperature exceeds these limits, the Rh complex can decompose in an unacceptably fast manner. Also, at higher temperatures, there is the possibility of high reactivity and exotherms, if the absorbent has locations where both the Rh-containing solution and the multi-component synthesis gas are depleted in inhibitors. This would be true, for example, in the upper part of a counter-current absorber. Lower temperatures are acceptable. However, the equilibrium speed between the Rh complex and the inhibitors will become limiting at some low temperatures. In addition, low temperatures can involve an extra cost of cooling without an additional advantage from a process point of view. The pressure in the absorbent 11 is preferably maintained at less than about 5 MPa, with a partial pressure of acetylene below the safety limit of 0.2 MPa. In a preferred embodiment, the absorbent is placed immediately before the oxo / hydroformylation reactor. The temperature in the regenerator (12) is maintained in the range of 50 ° C to 150 ° C, more preferably between 80 ° C and 125 ° C. The pressure in the regenerator is typically limited by engineering and economic factors. The higher hydrogen pressures accelerate the regeneration of the multi-unsaturated Rh complex, and the hydrogenation of purified and complexed multi-unsaturates, allowing for smaller regeneration vessels and smaller amounts of rhodium complex. Preferably, the pressure in the regenerator is maintained in the range of about 0.1 to 50 MPa, and more preferably in the range of about 1 to 10 MPa. The liquid feed to the regenerator leaves the absorbent (11) without treatment. The gas supply in a gas containing hydrogen, which can be essentially pure hydrogen or a mixture of hydrogen enriched gas and deficient in CO. Other protection beds designed to remove the irreversible poisons of the oxo catalyst from Rh, such as sulfur compounds, halides, cyanides, iron carbonyls and the like, must also be used to pretreat the feed stream of the multi-component synthesis gas. towards the multi-unsaturated absorbent (11). The hydrogen-rich feed gas to the regenerator (12) must also be essentially free of the above irreversible poisons, and other compounds detrimental to the Rh complex. The addition of pure hydrogen, free of sulfur is preferred, in the gas feed to the regenerator. The speed and selectivity of the hydrogenation step towards the production of olefins from multiinsaturates and alkynes can be controlled by adjusting the partial pressure of CO. The partial pressure ratio of H2 / CO in the regenerator should be 10 or higher, preferably 50 or higher. The higher partial pressures of CO lead to a higher selectivity towards olefins, but at a reduced rate of multi-unsaturated conversion. In certain cases, the CO dissolved in the solution containing complexed multiinsaturates (106) can provide a sufficient partial pressure of CO in the regenerator (12). If necessary, CO can be coalified with hydrogen-containing gas to the regenerator, or gas mixtures deficient in CO and enriched in hydrogen can be used. The absence of CO does not have a destabilizing effect on the Rh complex, but it does affect the speed and selectivity of the hydrogenation of the unsaturated hydrocarbons present in the regenerator. Without CO present, all unsaturated hydrocarbons, including olefins, tend to be hydrogenated in alkanes. Accordingly, it is desirable to maintain the concentration of CO in the regenerator at a level sufficient to hydrogenate preferably the polyunsaturated only in olefins, in order to achieve an economic compromise between a more rapid regeneration of the multi-unsaturated Rh complex (and by consequently, a smaller equipment size, and a smaller load of Rh), and the loss of the olefin source of 2 to 5 carbon atoms due to reduced selectivity. The separation of the multiinsaturates from the main stream of the multi-component synthesis gas improves the overall selectivity of the process, since the multi-unsaturates are treated separately, in such a way that the volume of ethylene and acetylene in the synthesis gas is not exposed. multiple components to the appropriate hydrogenation conditions for rapid conversion of the multi-unsaturated. The flow rate of the catalyst solution to the adsorbent is set to meet the concentration limits given for the multi-unsaturated ones of the multi-component oxo reactor feed, as described above. The flow velocity of the rhodium should be set at a sufficient level to be combined stechio-metrically with the Ccintidad of multiinsaturados that are going away to eliminate. Therefore, a treatment ratio can be defined with the ratio of the rhodium flow rate to the absorbent (expressed as moles per unit time), at the flow rate of the multi-unsaturated ones that are to be removed (also as moles). per unit of time). For an ideal absorption system, this treatment ratio can be exactly 1.0 for a perfect removal of only the desired multiunsaturates. The ratios of treatment should be between 0.5 and 50 in the present invention, preferably between 1 and 10. Higher treatment rates would be recommended if a significant fraction of the rhodium complex is inactive, or if it is desired to remove and convert some fraction of the alkyne component of the multi-component synthesis gas in addition to the multi-unsaturated. The conditions (temperature, pressure, residence time, etc.) in the regenerator are established in such a way that the conversion rate of the multi-unsaturated is equal to the speed at which they are being carried towards the regenerator by the catalyst solution. (which, in turn, is equal to the elimination rate of multiinsaturated in the absorbent). Example 4 includes the selected multi-unsaturated conversion rates that can be used by one skilled in the chemical engineering art to specify the operating conditions of the regenerator. The purifying solution can be essentially the same as that of the catalyst solution used in the passage of the oxo reactor, or any paste or soluble catalyst that achieves the same effect under the conditions herein. Preferably, the absorption process uses the spent catalyst solution from the oxo reactor as a purifying solution, before its final disposal, and / or its recycling. An advantage of the use of the above-described treatment, from the aspect of the process of the present invention, is that the multi-unsaturates do not become the oxo reactor and, therefore, do not involve a large amount of active catalyst. They are removed from the main feed stream and converted separately into olefins. The olefins then formed are preferably recycled to the multi-component oxo reactor feed, and hydroformylated in the oxo reactor. An additional advantage of the use of the present absorption-regeneration process for the multi-unsaturated conversion is in the elimination of the risk of uncontrolled hydrogenation reactions associated with the hydrogenation of highly unsaturated hydrocarbons. This risk is eliminated in the practice of the present invention, because the amount of unsaturated species in the reactor is limited to the amount carried fixed to the rhodium or physically dissolved in the solvent. Therefore, each Rh site is limited to a very limited rotation before it leaves the unsaturated species to be hydrogenated. Under this situation, even a rapid increase in the speed of the reaction can only result in the conversion of a limited amount of the unsaturated species, and in this way, the resulting heat release is strictly limited. OXO CATALYST OF Rh. In the process of the present invention, the oxo / hydroformylation catalyst is a rhodium complex catalyst, preferably an oil-soluble rhodium complex catalyst. The oil-soluble catalyst is typically formed by a complexing reaction in solution between a low-valent rhodium, an oil-soluble organophosphorus compound, preferably a triorganophosphorus compound, or a mixture of these compounds, and carbon monoxide. . Under the reaction conditions, the central atom of Rh can complex with other species present in the reaction mixture, such as ethylene, and other olefins (eg propylene), acetylene, and other alkynes (e.g., methylacetylene), dienes, and other highly unsaturated hydrocarbons (eg, butadiene, butadiene, vinylacetylene, etc.), and hydrogen, which may also act as ligands. Preferred triorganophosphorous compounds suitable for the preparation of the complex catalyst Rh for use in the oxo reactor of the present invention belong to the group of triarylphosphines, trialkyl phosphines, alkyldiarylphosphines, aryldialkylphosphines, trialkyl phosphites, triaryl phosphites, soluble in oil, containing at least one phosphorus atom per molecule. These must be able to complex with Rh, by virtue of having a single pair of electrons on phosphorus. Non-limiting examples of these oil-soluble triorganophosphorus compounds for use in the catalyst include triarylphosphines, such as triphenylphosphine or tri-p-tolylphosphine, trialkylphosphines, such as trioctylphosphine or tricyclohexylphosphine, or alkyldiarylphosphines, such as octyldiphenylphosphine. -na or cyclohexyldiphenylphosphine, or aryldialkylphosphines, such as phenyldioctylphosphine or phenyldicyclohexylphosphine, etc. The triorganophosphorus compounds which can serve as a ligand can also be other phosphorus-containing compounds, such as triorganophosphites, for example, trialkylphosphites, such as trioctylphosphite, triarylphosphites, such as tri-p-tolylphosphite. In addition to the monodentate phosphorus ligands, bidentate compounds, such as diphos (bis (diphenylphosphino) ethane) can be used. An exempt list of suitable phosphine ligands is given in Falbe's book, pages 55-57. Preferably, the oil-soluble triorganophosphorus compound is a trialkylphosphine, such as tricyclohexylphosphine and trioctylphosphine, or a triarylphosphine, such as triphenylphosphine. However, other ligands may be used, if desired, such as phenyldicyclohexylphosphory, diphenylcyclohexylphosphine, phenyldiocylphosphine, tri-p-tolylphosphine, trinaphthylphosphine, phenyldinaphylphosphine, diphenylnaphthylphosphine, tri- (p-methoxyphenyl) phosphine, tri- ( p-cyanophenyl) phosphine, tri- (p-nitrophenyl) phosphine, pN, N-dimethylaminophenyl- (diphenyl) phosphine, and the like. Mixtures of triorganophosphorus compounds can also be used. It will be recognized by an expert in this field, that in turn, other ligands used with rhodium for the hydroformylation, in the present invention, can be used for the hydroformylation of multi-component synthesis gas, since the catalyst is used in a Sufficient ratio of the ligand / Rh. Other examples of ligands for hydroformylation include metal bis-phosphite catalysts of transmission (as described in U.S. Patent No. 4,885,401), bidentate organo-phosphorus ligands (as disclosed in U.S. Pat. from North America Number 4,742,178), and transition metal polyphosphite ligands (as described in U.S. Patent No. 4,769,498). It will be further recognized by one skilled in the art, that other reaction means than the oily ones in the present invention can be used for the hydroformylation of multi-component synthesis gas. Typically, the catalyst is made soluble in a reaction medium by the use of ligands suitable for complex formation. Accordingly, the hydroformylation of the multi-component synthesis gas can be carried out in an aqueous medium, by the use of organophosphorus ligands containing at least one substituent on the hydrocarbon radical of the ligand, which imparts to the ligand water solubility. These substituents include, for example, the carboxylic, amino and sulfo functional groups. Examples of these ligands can be found in U.S. Patent Nos. 4,248,802, 4,808,756, 5,312,951 and 5,347,045, which are incorporated herein by reference. The hydroformylation of the multi-component synthesis gas can also be carried out in a fluorinated hydrocarbon medium, as the Rh complex becomes soluble in fluorine, as described in U.S. Patent No. 5,463,082, which is incorporated herein by reference. Rhodium complexes prepared using the aforementioned ligands can also be used in solution in the absorbent / regenerator system for removing multiunsaturates described above. In fact, it could be convenient to use the spent catalyst solution from the hydroformylation reactor before its final disposal and / or its recycling, due to the potential savings in the cost of the reagent in the multi-unsaturation elimination step. It is known that rhodium complex catalysts prepared using the aforementioned ligands, provide good catalytic activity in the hydroformylation of pure olefin feeds, but are inhibited / poisoned by the alkynes, particularly by acetylene. However, applicants have discovered in an unexpected manner that these ligands can be used in the hydroformylation of synthesis gas containing olefin and alkyne feed supplies of 2 to 5 mixed carbon atoms, especially acetylene and ethylene, since phosphorus and rhodium in the catalyst are present in amounts that make the catalyst catalytically active. Preferably, the P / Rh ratio is maintained above a specified minimum value. We have found that, for triphenylphosphine (PPh3), this minimum value should preferably be 30. The preferred ligand concentration can also be expressed in terms of the minimum concentration of the coordinately active phosphorus [P] in the solution, or in terms of of a minimum proportion of [P] / pco in the reaction, where pco is the partial pressure of carbon monoxide in the gas phase. For PPh3, [P] should preferably be greater than 0.01 mol / liter, and the ratio of [P] / pco preferably should be greater than 0.1 millimoles / liter / kPa. The concentration of Rh in the reaction mixture should be in the range from about l × 10"s to about l × 10" 2 moles / liter. This scale of Rh concentrations corresponds to an Rh concentration on the scale of about 1 to about 1,000 ppm (by weight). In a more preferred embodiment, the Rh must be present in the range of 50 to 750 ppm, based on the total weight of the solution. Within the above scales, the choice of catalyst concentration may reflect engineering and economic considerations. The hydroformylation of the feed of the oxo reactor is carried out by contacting the catalyst with the multi-component synthesis gas, in a solution of the catalyst, prepared with a solvent or a mixture of solvents. Oily solvents that can be used for the preparation of a catalyst solution used in the oxo / hydroformylation step are known in the art, and include aliphatic and aromatic hydrocarbons (e.g., heptanes, cyclohexane, toluene, etc.) , esters (eg dioctyl phthalate), ethers and polyethers (eg tetrahydrofuran and tetraglima), aldehydes (eg propanal, butanal, etc.), the aldol condensation products of the oxo- aldehydes, the triorganophosphorus ligand itself (eg, triphenylphosphine), etc. For catalyst compositions outside the specified ranges, particularly for catalysts with P / Rh ratios less than the minimum value for a catalytically active hydroformylation catalyst (which for PPh3 is 30), the catalyst has significantly reduced activity. Preece and Smith (European Patent Number 0,233,759), for example, have investigated the hydroformylation of a multi-component synthesis gas mixture containing acetylene in the presence of an Rh5 (CO) 12 catalyst modified with PPh3. Despite the fact that the feed gas contained high concentrations of the reactants (acetylene, ethylene, CO, and hydrogen, with a ratio of 6: 3: 30: 61, respectively), the catalyst solution contained a high concentration of Rh (0.0108 moles / liter), and PPh3 (0.114 moles / liter), and the total pressure was 0.91 in MPa, the catalyst failed as evidenced by the fact that the total rotation, in the presence of acetylene, was only 13 in 24 hours, giving a very low rotation frequency of 1.5xl0 -4 moles of propanal / mole of Rh / second. Under these reported conditions, the Rh catalyst has a high activity in the hydroformylation of ethylene alone (C.K. Brown and G. Wilkinson, Tetrahedron Letters 1969, 22, 1725). In addition to the expected propanal, the product mixture also contained 1.1 mole percent acetone, not observed in the hydroformylation product of ethylene mixtures. This effect of acetylene on the oxo conversion of ethylene is well documented in the literature, and is the reason why acetylenes are referred to as "classical catalyst poisons" for phosphine-modified Rh catalysts (see B. Cornils, " Hydroformylation, Oxo Synthesis, Roelen Reaction "in New Syntheses with Carbon Monoxide, ed J. Falbe, Springer Verlag, New York, 1980, page 73). However, applicants have discovered that, under appropriate conditions, particularly in specific appropriate P / Rh ratios, the inhibition / poisoning effect of the alkynes can not only be overcome, but in fact the alkyne components themselves can be overcome. convert into the corresponding saturated aldehydes. These proportions are typically high. The catalyst used by applicants here shows a better activity, and is not poisoned by alkynes of 2 to 5 carbon atoms, such as acetylene, but rather co-converts them with olefins into aldehydes of 3 to 6 carbon atoms. corresponding carbon, as evidenced by its high frequency of rotation with feed streams containing acetylene, ethylene, CO, and hydrogen. Applicants have discovered that the catalyst system gives evidence of a changed activity with different concentrations of coordinately active P and P / Rh ratios. The physical evidence of this change comes from experiments conducted with multi-component synthesis gas feeds containing acetylene and ethylene at 100 ° C and 110 ° C, and at total pressures of 0.8 and 2.2 MPa, respectively, with different proportions of PPh3 / Rh (see Examples 1 and 2). When the PPh3 / Rh ratio was 9.3, essentially the same as in the Preece and Smith experiment, despite using a different Rh source, the final catalyst solution had a dark brown color, but it looked orange when the proportion of PPh3 / Rh was higher, v.gr. 300. The brown color of the solution containing the catalyst with a P / Rh ratio of 9.3 showed that the catalyst decomposed. At 110 ° C, and at a total pressure of 2.2 MPa, the total rotation with a PPh3 / Rh ratio of 9.3 was only 4.9 in 2 hours, while under lighter conditions of 100 ° C and a total pressure of 0.8 MPa , the total rotation was 221 in 45 minutes, when the PPh3 / Rh ratio was 300. This last catalytic velocity is on the scale of the hydroformylation rate of propylene under otherwise identical conditions. The catalyst with a PPh3 / Rh ratio of 300 in this manner showed an average rotation frequency of 0.082 mole propanal / mole Rh / second, while the catalyst with a PPh3 / Rh ratio of 9.3 gave a frequency *, average rotation rate of 6.8x10"4 moles propanal / mole Rh / second, ie 120 times slower Initial rotation frequencies as high as 2 mole propanal / mole Rh / second with the process have been reached of the present invention, in the conversion of a multi-component synthesis gas feed containing 15.5 percent by volume of ethylene, and 6.5 percent by volume of acetylene, using a PPh3 / Rh catalyst with a PPh3 / Rh ratio of 660, and higher (see Example 3). Accordingly, one embodiment of the present invention is that, for any organophosphorus compound used to modify the rhodium for use in hydroformylation, there is a sufficiently high P / Rh catalyst ratio to create an active catalyst for the hydroformylation of the synthesis of multiple components. Although catalysts below this P / Rh ratio can provide a minimum level of rotation, as evidenced by the rotation frequency of 6.8x10 ~ 4 moles of oxo / mole of Rh / second achieved with PPh3 at a ratio of P /. Rh of 9.3, a catalyst with utility would preferably be at a sufficiently high P / Rh ratio to provide activity of at least 10-2 moles of oxo / mole / Rh / second. Other experiments performed with multi-component synthesis gas mixtures in the presence of rhodium-PPh3 catalysts, with P / Rh ratios of 100 or higher, showed a high selectivity for propanal of approximately 99.5 percent in a broad range. range of H / CO, and acetylene / ethylene ratios and temperatures, including conversions as high as 99 percent. The only different product detected was ethane. On the other hand, it has been reported (T. Mise et al., Chem. Lett., 1982, (3), 401) that multi-component synthesis gas mixtures containing acetylene and ethylene produce α-β-unsaturated ethyl ketones in the presence of the unmodified Rh catalyst, where the ratio of P / Rh is zero. Applicants have found that, in proportions of PPh3 / Rh of at least 30, and preferably above about 100, significant improvements in speed, conversion and stability are achieved. For example, in proportions of PPh3 / Rh greater than 30, initial velocities of at least 0.04 mol / mol Rh / second have been reached, and conversions of at least 80 percent, with an orange-yellow catalyst color indicating a stable catalyst. In these proportions of PPh3 / Rh, the hydroformylation of multi-component synthesis gas mixtures containing acetylene and ethylene is facilitated, and the catalyst can also be stabilized in a form that catalyzes hydroformylation in preference to the formation of other oxygenates, such as ketones and esters. The aforementioned effect, wherein the hydroformylation of multi-component synthesis gas mixtures containing acetylene and ethylene stabilizes the catalyst, can provide a strong incentive to add alkynes (especially acetylene) to olefins (especially ethylene) for hydroformylation . Under conditions suitable for the hydroformylation of olefins with alkynes and other multiinsaturates, both the ligand and the alkyne have strongly tilted equilibria toward rhodium fixation. This greatly reduces the rhodium deposit which has insufficient ligation, which in turn reduces the formation speed of the rhodium assembly, whose ensemble formation is the main rhodium deactivation path. Accordingly, as shown in Example 7, deactivation of the catalyst can be greatly reduced by the addition of a small amount of alkyne. As such, a preferred embodiment of the present invention is a process for hydroformylating olefins (particularly ethylene), wherein a small amount of alkynes (particularly acetylene) and / or multiunsaturated is added, sufficient to mitigate the deactivation of the catalyst. A preferred level of alkyne addition would be from about 10 ppm to about 10 percent over the total unsaturated, more preferably from about 100 ppm to about 5 percent over the total unsaturated. The addition of alkynes or multiunsaturated can provide sufficient advantage in terms of reduced deactivation, and in terms of the higher severity conditions (eg temperature, olefin conversion, etc.) enabled by the reduced deactivation, that this modality can be used to improve the hydroformylation of olefin (particularly ethylene), where the alkynes or the multiinsaturates are present essentially for the purpose of mitigating deactivation, and wherein the yield of aldehyde from these alkynes or multiunsaturated can be inconsequential or insignificant. For other ligands other than triphenylphosphine, the minimum ligand concentration may be different. When the catalyst is used to convert multicomponent synthesis gas mixtures containing alkynes, an important feature of the ligand is its ability to compete against the alkyne by the rhodium bond. The active rhodium catalyst has a variable amount of linked ligand, but an average can be defined on the active states in terms of a ratio of net bound phosphorus / rhodium, RB. For common hydroformylation catalysts, RB changes over time in the catalytic cycle, but has an average value of about 2. If a ligand has a greater attraction to bind to Rh, it will need to be in solution less binding in order to maintain the Rh in its preferred state (RB). A measure of the level of attraction of the ligand for rhodium can be found in the pKa value of the ligand. (The pKa values for some common ligands are mentioned in B. Cornils, "Hydroformilation, Oxo Synthesis, Roelen Reaction" in New Syntheses with Carbon Monoxide, ed J. Falbe, Springer Verlag, New York, 1980, page 48). pKa is the base-10 logarithm of Ka, which is the equilibrium constant for ligand acid-base interactions. A second measure of the level of attraction of the ligand for rhodium can be derived from the entropy of interaction when multiplied ligands are used. This interaction entropy,? SB, has a value of approximately 35 cal / mol / ° K for each aggregate point of attachment (see, for example, Benson, S.W. Thermochemical Kinetics, Wiley, New York, 1976). This entropy contributes to releasing energy as -T? S, thereby providing a contribution of free energy of about -10 to -15 kcal / mol. The free energy has influence on the equilibrium as exp (-? G / RT), in such a way that the influence of the entropy effect of multidentate ligands is included as exp (? SB / R). Both measures of the binding strength will attenuate the concentration of the unbound ligand that is required in solution 5 in order to maintain an active amount of ligand bound to the rhodium. RL is defined as the overall ratio of rhodium phosphorus to a hydroformylation catalyst with "L" ligand, and includes both the unbound ligand and the rhodium-bonded ligand. The concentration of unbound ligand (expressed as a ratio to the rhodium concentration) is (RL-RB). The following equation defines the effect of binding force parameters on the minimum ligand concentration for other ligands other than PPh3. the? B ?? ? B i? Nü (PKatpp-pKaL) RTPP - «B ß (AS R) Where RL is the minimum ratio of P / Rh sufficient to provide an active hydroformylation catalyst with this ligand. RTPP is the minimum ratio of P / Rh for the ligand PPh3 (Rtpp = 30), RB is the average ratio of P bound with rhodium (approximately 2), pKatpp is the value of pKa for PPh3, pKaL is the value of pKa for the new ligand. • SB is approximately 35 kcal / mol ° K for each additional point of attachment (beyond a junction point of PPh3), and R is the gas constant (1.99 cal / mol / ° K). Therefore, RL, as calculated using this equation, represents the minimum ratio of P / Rh sufficient to provide an active hydroformylation catalyst for any "L" ligand. Rhodium can be introduced into the reactor by methods known in the art, either as a preformed catalyst, for example, a solution of hydrurocarbonyltris (triphenylphosphino) rhodium (I) [HRh (CO) (PPh3) 3], or can form in if you If the catalyst is formed in itself, the Rh can be introduced as a precursor, such as acetylaceto-natodicarbonyl-rhodium (I) [Rh (C0) 2 (acac)], rhodium oxide [Rh203], rhodium carbonyls [ v.gr. Rh4 (CO) 12 and Rh6 (CO) 16], tris (acetylacetonate) rhodium (I) [Rh (acac) 3], or rhodium carbonyls substituted by triarylphosphine. { [Rh (CO) 2 (PAr3)] 2, where Ar is an aryl group} . REACTOR VARIABLES Typically, in the process of the present invention, the hydroformylation of the multi-component synthesis gas feeds is conducted at a temperature in the range of 80 ° C to 180 ° C, and preferably in the 80 ° C scale. ° C to 155 ° C. If the temperature exceeds these limits, the catalyst can be quickly deactivated. Lower temperatures are acceptable, however, the speed of the reaction may be too slow to be economically practical. The reaction is conducted at a total pressure in the reactor in the range of less than about 5 MPa (absolute), preferably from about 0.05 to 5 MPa, with a partial pressure of carbon monoxide not greater than 50 percent of the pressure total. The maximum practical pressure can be limited by production considerations and capital and safety costs. The molar percentage of carbon monoxide, hydrogen, olefins of 2 to 5 carbon atoms, preferably ethylene, and alkynes of 2 to 5 Garbono atoms, preferably acetylene, in the feed of multi-component synthesis gas to the oxo reactor to the above pressures, it should be maintained as follows: CO of about 1 to 50 mole percent, preferably about 1 to 35 mole percent; H2 from about 1 to 98 mole percent, preferably from about 10 to 90 mole percent, - monounsaturated individually and in combination from about 0.1 to 35 mole percent, preferably from about 1 to 35 mole percent . The gas compositions within the oxo reactor in the process of the present invention are then affected by the mode of operation, the composition of the feed and the conversion. The reaction can be conducted either in a batch mode or on a continuous basis. Preferably, the reaction is executed on a continuous basis. In a continuous mode, surface velocities of approximately 1.5 e? about 61 centimeters / second (0.05 to 2 feet / second), preferably from about 3 to about 30 centimeters / second (0.1 to 1 foot / second). Since the oxo catalytic conversion takes place in the liquid phase, and the reactants are gaseous compounds, a contact surface between the gas and liquid phases is very desirable, in order to avoid the limitations of mass transfer. The high contact surface can be provided by any suitable manner, for example, by stirring in a batch reactor operation. In a continuous operation, the reactor feed gas can be contacted with the catalyst solution, for example, in a continuous stirred tank reactor where the gas is introduced and dispersed in the bottom of the vessel. Good contact between the catalyst and the feed gas can also be ensured by the dispersion of the Rh complex catalyst solution on a high surface support by recognized methods in this field. In the process of the present invention, the hydroformylation of feedings of the multi-component oxo reactor can be conducted in a single-stage reactor, or using multiple reactors. The reactors can be configured in any number of parallel trains when operating in a continuous mode. The number of parallel trains is determined by the total capacity desired and the capacity of a single train. The present invention can be practiced using one or more stages per train, and each reaction stage can be designed using any suitable reactor configuration. For example, plug flow or constantly stirred tank reactor contact (RTCA) are two common reactor configurations. The number of stages and reactor types for the stages can be calculated using conventional chemical engineering principles, given the kinetics and objectives of the reaction system. In batch experiments, there is an indication that the olefin and alkyne components of the multi-component synthesis gas feeds react in two well-defined phases. The first phase corresponds to the conversion of the olefins present in the feed of the multi-component synthesis gas oxo reactor. In the second phase, on the other hand, most of the alkyne content is converted. The first phase is essentially the hydroformylation of olefins in the presence of alkynes. The second phase, on the other hand, is in itself a two step conversion, where the alkynes are first hydrogenated to obtain olefins, and then these olefins formed are hydroformylated to obtain the corresponding aldehydes. The step that determines the speed in this second phase of conversion of synthesis gas of multiple components is the hydrogenation of alkynes to obtain olefins. Following this unexpected order and complexity of the oxo conversion of olefin-alkyne mixed feeds, the conditions for the different phases of the oxo reaction are preferably different. Accordingly, a preferred embodiment of the present invention is to divide the total hydroformylation into two steps, each step being operated under conditions suitable for the chemistry that occurs at that stage. Therefore, the conditions of the reaction and the composition of the catalyst in the first reactor should improve the hydroformylation of olefins in the presence of alkynes. The conditions of the reaction and the composition of the catalyst in the second stage, on the other hand, must facilitate the hydrogenation of alkynes, which is the slowest step in its conversion into aldehydes. U.S. Patent No. 4,593,127 discloses a two-step hydroformylation process for the oxo conversion of olefins. The patent gives a common engineering solution for an improvement in the overall conversion of the olefin reactants. However, it is to be understood that the purpose and necessity of an oxo conversion of multiple stages, and in particular of two stages, in the process of the present invention, is different.

The chemical reactions that take place in the different stages of the oxo process of the present invention are different. In the first oxo phase, the main reaction is the hydroformylation of olefins in the presence of alkynes. In the second stage, however, the main reaction is the hydroformylation of alkynes, which in itself is a two-step reaction. The first step in the conversion of alkyne is the hydrogenation of alkynes to obtain the corresponding olefins, which is followed by the hydroformylation of the formalized olefins to obtain the corresponding aldehydes. The chemical reaction in the two stages of the process described in U.S. Patent No. 4,593,127, on the other hand, is the same: hydroformylation of olefins to obtain aldehydes. The need for the two steps in the process of the present invention, therefore, does not arise simply from the need for a better overall conversion, but from the unexpected nature of the chemical process, i.e., that the stronger bonding alkyne components they react much more slowly than the weaker link olefin components. As a result of these characteristics of the oxo conversion of the alkyne-olefin mixtures, the olefins react by first producing the corresponding aldehydes, and therefore, the alkyne reagents will be enriched in the reaction mixture. In addition, since the oxo conversion of alkynes to obtain the final saturated aldehyde products, requires first of the hydrogenation of the alkynes to obtain the corresponding olefins, and since it is this first step that determines the overall speed of this reaction, the conditions in the second stage of the reactor must in fact improve not only the hydroformylation of olefins, but the hydrogenation of alkynes as well. The need for the second reactor stage, therefore, arises from the nature of chemistry, and not simply a common engineering solution to improve the overall conversion of a chemical process. An example of a single-train, two-stage oxo / hydroformylation unit is shown in Figure 2 and is described as follows: The hydroformylation reaction is carried out in two continuously stirred tank reactors (21, 23). Each reactor is cooled and stirred using a surrounding pump cooling cycle (202, 207). The hydroformylation feed (201) enters the first rector. The product from the first reactor (203), which possibly contains some solvent and / or catalyst entrained, can be cooled and separated in an evaporation drum (22) for an intermediate removal of the aldehyde product (204). The remaining (non-converted) multi-component synthesis gas (205) is introduced into the second reactor (23). Additional multi-component synthesis gas components, such as hydrogen (206) can be added to this multi-component synthesis gas feed, in the second reactor. For example, hydrogen addition could be used to provide the highest proportions of H2 / CO that are preferred in the second stage. The product from the second reactor (208) is combined with the intermediate product (204) to give a stream (209) which is introduced to a product separation and catalyst recovery train (combined for simplicity in block 24). This block can use separations based on conventional boiling point (eg distillation) to separate the crude product in a stream of unconverted multi-component synthesis gas (210), a stream of purified aldehyde (211), and a solvent / catalyst stream from the process (212). The solvent stream and process catalyst (212) is recycled back to the individual reactor stages. The conditions in the two-stage oxo unit mode of the process of the present invention are adjusted for the two stages of the conversion of the multi-component synthesis gas feeds., as described above. Accordingly, in the preferred embodiment, the reaction conditions in the first stage of the two-stage oxo unit must be optimized to facilitate the hydroformylation of ethylene in the presence of acetylene. In the second stage of the conversion process, the overall conversion rate is determined essentially by the rate of hydrogenation of alkynes, in the preferred embodiment, acetylene. Therefore, the reaction conditions in the second stage of a two-stage oxo unit should facilitate the hydrogenation of the alkyne reagent, in the preferred embodiment, acetylene. The reaction conditions in the first stage should be maintained as follows: H2 / CO ratio from about 1: 1 to 100: 1, preferably from 1: 1 to 10: 1; the temperature should be from about 80 ° C to 180 ° C, preferably in the range from 80 ° C to 155 ° C, more preferably from about 80 ° C to 130 ° C; the total pressure in the reactor should be about 0.05 to 5 MPa, preferably about 0.1 to 2.5 MPa, with a partial pressure of CO not greater than 50 percent of the total pressure, and the partial pressure of the acetylene reagent not must be greater than 0.2 MPa (safety limit). The reaction conditions in the second stage of a two-stage oxo unit of the process of the present invention should facilitate the hydrogenation of alkynes to obtain olefins, by, for example, maintaining lower partial pressures of H2 and lower CO than in the first stage. Higher temperatures can also be applied in the second stage to increase the reaction rate. In some cases, it may be economically convenient to use a different ligand in the second stage, to improve the heat stability and / or the hydrogenation activity of the catalyst. Therefore, the reaction conditions in the second step should be maintained as follows: H2 / CO ratio from about 1: 1 to 100: 1, preferably from about 2: 1 to 50: 1; the temperature should be maintained between about 80 ° C and 180 ° C, preferably from about 80 ° C to 155 ° C; the total pressure must be maintained between approximately 0.05 and 5 MPa, preferably from approximately 0.1 to 2.5 MPa, with a partial pressure of CO not greater than 35 percent of the total pressure, and with partial pressure of acetylene not greater than 0.2 MPa (security limit). Surface velocities of about 1.5 to about 61 centimeters / second (0.05 to 2 feet / second), preferably from about 3 to about 30 centimeters / second (0.1 to 1 foot / second) in both reactors, should be employed in order to put the catalyst in the reactor. Rhodium complex catalysts are used within the range of compositions described above. The compositions of the catalyst solutions in each stage of a multi-stage oxo unit are preferably the same, but may also be different, within the ranges described for the rhodium complex catalyst, if desired. The overall conversion of the alkyne and olefin content of the multi-component synthesis gas feed to the oxo unit of the process of the present invention can be essentially as high as desired. However, the life of the catalyst is shortened as the 100 percent conversion in a single pass approaches, if higher catalyst concentrations and / or more severe conditions, ie, higher temperatures, are used to reduce the residence time necessary to achieve the desired conversion. Therefore, in general it is desirable to keep the conversion in a single pass lower than the desired overall conversion, and to recycle the reagents after separation of the product. Thus, for example, an overall conversion greater than 99 percent can be achieved, with a reagent conversion of 80 percent per pass in the oxo unit, and a reagent recovery of 96 percent in a recovery unit. recycle described later. Under these conditions, the concentration of reactant in the reactor can be 24 times higher than the resulting concentration of the same level (99 percent) of single pass conversion in the absence of recycle. This higher concentration contributes to a proportionally 24 times higher reaction rate, and in the case of the oxo / hydroformylation process of the present invention, it also contributes to a greater stability of the catalyst complex. RECOVERY AND RECIRCULATION OF THE REAGENT The use of a recycle of the unreacted unsaturated hydrocarbon components is highly desirable in the processes of the present invention, to increase the productivity of the oxo unit and the life of the catalyst., allowing higher concentrations of unsaturated hydrocarbons in the oxo reactors. However, feeds having relatively high concentrations of inerts and non-stoichiometric reagents, such as multi-component synthesis gas feeds, effectively discourage this recycling, due to the rapid accumulation of excessive, ie inert, gaseous materials ( v. nitrogen, water vapor, methane, ethane, propane), and the excess reagents (typically hydrogen) that would occur in the recycling cycle. It would be beneficial if a process could be devised to overcome these problems. Applicants have discovered that unreacted unsaturated hydrocarbon components, especially acetylene, can be conveniently recovered from the gaseous effluent of the oxo reactor, by purifying this "tail gas" with a liquid consisting of the liquid aldehyde product of the oxo reactor. This unsaturated containing liquid can then be separated with the unsaturated synthesis gas, to produce a recycle stream of multi-component synthesis gas that is more concentrated in the unsaturated hydrocarbon than was the tail gas, or Preferably, the unsaturated containing liquid can be recycled directly to the oxo reactor. Applicants have discovered that the solubilities of the unsaturated hydrocarbon components (e.g., ethylene, and in particular acetylene) of the multi-component synthesis gas mixtures in certain oxygenated solvents, more particularly oxygenated solvents of 3 to 6 carbon atoms, especially the aldehyde product of the hydroformylation process, as described herein for the conversion of multi-component synthesis gas mixtures, are exceptionally high. In addition, the solubilities of these unsaturated hydrocarbons are substantially higher than the solubilities of other reagents, such as hydrogen and carbon monoxide, and inert, such as methane and nitrogen (see Tables 6 and 7 in Example 5) present in the multi-component synthesis gas mixtures used in the process of the present invention. Therefore, another embodiment of the present invention provides a process for the separation or preferential removal of unsaturated hydrocarbons, especially acetylene, from the effluents of the oxo reactor containing them, and their recycling to the oxo reactor for further processing. hydroformylation without accumulation of the aforementioned excessive reagents and inerts in the oxo reactor. The process provides a method to concentrate and recover the unsaturated hydrocarbons from the effluent of the oxo reactor to produce a stream that is enriched in alkyne and olefin, and that is deficient in excessive gaseous material, to be recycled to the oxo unit without accumulation of inerts and Excessive components. The concept of recycling and recovery of the present invention comprises the use of the aldehyde product of the hydroformylation as the absorption solvent in a system for concentrating the unconverted unsaturates in the effluent of the oxo reactor. A simple embodiment of this invention would be the use of coupled absorption and separation towers. In this method, the oxo effluent is fed to the bottom of an absorption tower, where it is contacted with cold aldehyde to condense out the liquid aldehyde and dissolve the unsaturated species (particularly acetylene). The oxo glue gas greatly diminished in these components, emerges from the top of the absorption tower. The aldehyde containing unsaturates from the bottom of the absorption tower is fed to the top of a separation tower, where gas free of unsaturates (such as synthesis gas, hydrogen or nitrogen) is used to separate the unsaturated in a concentrated vapor phase suitable for recycling to the oxo. The liquid aldehyde product free of unsaturates from the bottom of the separator is divided between the recycle to the absorbent, and a stream that is the product of oxo aldehyde. By using this scheme, the absorber / separator is made to serve the three purposes: (i) recover the aldehyde product from the effluent of the gas process, (ii) recover the unsaturates to be recycled to the oxo, and (iii) eliminate the unsaturated aldehyde product, where these unsaturated would be unwanted contaminants. A preferred embodiment of the recycle and recovery concept of the present invention accomplishes these same three purposes, but also provides for the recycling of the unsaturated components as solutes in a liquid phase recycle aldehyde stream. Figure 3 shows an example flow chart for this mode. In the oxo reactor (31), which has a surrounding pumping cooling cycle (340), a multi-component synthesis gas feed (331) is introduced. The gaseous or mixed phase effluent of the oxo reactor (332) is cooled to a temperature at which an amount of aldehyde is condensed, which is essentially equal to the amount of aldehyde produced by oxo. The condensed liquid aldehyde (341) is separated from the effluent of the remaining oxo phase in an evaporation drum (33). The liquid aldehyde product (341) is introduced into a separation vessel (34), where it is separated with a gas free of unsaturates (333) (eg synthesis gas, hydrogen, nitrogen or light alkanes), producing an unsaturated aldehyde product (335) and a gaseous effluent (342) containing unsaturated hydrocarbons. The gaseous effluent from the separation tower (342) is combined with the vapor from the evaporation drum (33), and further cooled to produce a stream (334) which is fed to the absorption tower (35) having a portion which is at a sufficiently low temperature to provide a reflux (344) of the alkane components of the oxo effluent (eg, ethane or propane), as shown in the cooling of the upper part of the tower (343) and the drum (36) to separate the liquid from the vapor. This upper portion of the absorbent (35) functions as the rectifying section of a distillation tower, rejecting the aldehyde from the lower boiling point components, and resulting in a product stream from the top substantially free of aldehyde (336) which contains the oxo diluents (e.g., N2, methane, ethane, propane) and non-stoichiometric components (e.g., hydrogen) that boil at temperatures at or below the refluxing alkane temperature. At the bottom of the tower (35), the liquid phase becomes cold aldehyde which dissolves the highly soluble unsaturated components as if they were in an absorbent. At the bottom temperature of the tower (35), the solubilities of the alkynes and the olefins in the liquid phase are very high (see Tables 5 and 6 in Example 5). For example, acetylene concentrations of 10 mole percent can be achieved in the acetylene-rich aldehyde product under appropriate conditions. This liquid stream containing unsaturates (337) emerges from the bottom of the tower, where it can be pumped as a liquid at substantially higher pressures to be recycled to the oxo reactor (31). Once it is at a higher pressure, the liquid stream containing unsaturated can be put into heat exchange (350) to recover any cooling value it might contain. In this high pressure condition, this heat exchange can be performed with a minimized concern that the unsaturates, such as acetylene, are separated from the liquid to form a dangerous concentrated phase. The recovery of the cooling value can also be used in other cooled currents (335, 336) that leave the process. In a further variation of this scheme, the pressure of the oxo effluent (332) can be increased before the recovery process, by means of a compressor (32). The increase in pressure must not increase the partial pressure of the aldehyde product above its saturation limit, in order to avoid damage to the compressor. In addition, the acetylene partial pressure on the high pressure side must be lower than the safety limit of 0.2 MPa. The highest pressure should typically not be higher than 5 MPa, in order to avoid excessive equipment cost. This increase in pressure results in an increase in the partial pressures of the components that are being separated: the aldehyde product and the unconverted monounsaturates of 2 to 5 carbon atoms. As a result of the higher partial pressures, the evaporation tower 33 and the scrubber 35 can be operated at higher temperatures, thereby potentially reducing the cost of cooling the separation. In addition, the increase in pressure can have the additional advantage of reducing the sizes of the towers for treatment and gas separations. The need and degree of this operational compression step are determined by economic and safety factors. This recycling and recovery process is entirely different from that described in United States Patent Number 3,455,091 in several ways. First, U.S. Patent Number 3,455,091 uses oxo high-boiling by-products as scrubbing solvents, against our preferred use of the primary oxo product. Second, United States Patent Number 3,455,091 uses the scrubber system to absorb, for recovery purposes, the primary aldehyde product out of the unconverted oxo feed gases, against our absorption to be recycled to the oxo of the Unconverted power components selected from other power components. This recycling and recovery process is also entirely different from that described in United States Patent Number 5,001,274. Although U.S. Patent No. 5,001,274 employs a rhodium catalyst stream to absorb for recycling the selected unconverted feed components, the process described herein utilizes the liquid reaction product. An additional difference between the process of the present invention and the aforementioned prior art, is that the processed stream is not the effluent of an olefin oxo unit, but, in fact, the effluent of a different oxo technology where it is co-effected. convert olefins and alkynes. Therefore, the processed stream contains chemically different components - alkynes of 2 to 5 carbon atoms - in a high concentration, whose treatment and recovery require special process conditions and technology (safety). One of the most important features of the recovery-recycle process of the present invention is that it provides a solution for the safe recovery and recycling of these alkynes, especially acetylene. It should be noted that this recycling and recovery process can be employed with processes other than those mentioned above and the hydroformation / oxo processes described herein. The recovery and recycling process described herein can be used with other synthesis processes, whose reaction products can be used as absorption solvents for unreacted gaseous feed components, and whose synthesis process is not damaged by recycle these products back to the synthesis reactor. For example, certain implementations of the Fischer-Tropsch ("FT") synthesis can be made to produce oxygenates as products, and to consume olefins in the synthesis gas feed. In this implementation, the oxygenated product of FT can be used as described herein to recover and recycle the unconverted olefinic species back to the synthesis reactor. Another example is the variations of the synthesis reactions of alcohol containing olefins in the synthesis gas feed, and produce superior alcohol products. These are only examples and should not limit in any way the scope of application of the basic concept. The solvent applied in the process of recovery-recycling of unsaturates, as applied to the hydroformylation of the multi-component synthesis gas, is the aldehyde product recovered from the hydroformylation of synthesis gas of multiple components containing monoinsitutes. of 2 to 5 carbon atoms. The use of the aldehyde product as a solvent has several advantages: the separation of the aldehyde product can be integrated into the recovery and recycling process of unsaturated products, saving capital cost; the need for purchased solvent and solvent filler is reduced, and product contamination and solvent / product separation problems are reduced. A scheme of recovery and recycling of unsaturates and separation of integrated product can offer other advantages related to the need to use refrigeration for the effective separation of the aldehyde product. Since red separation of the product as the recovery of unsaturates requires the application of low temperatures, the cooling energy can be efficiently used in an integrated process, as described herein. UTILIZATION OF THE PRODUCT Aldehydes of 3 to 6 carbon atoms, which are a desired product of the hydroformylation step of the present invention, and particularly propanal, have utility as intermediates in the manufacture of many industrial chemical materials. Accordingly, a preferred embodiment of the present invention is its combination with subsequent processing steps, which further improves the value of the aldehyde product. A preferred embodiment of the present invention is the combination of the hydroformylation of a multi-component synthesis gas, with the hydrogenation of the aldehyde product of that hydroformylation, to produce an alcohol product. Particularly preferred is the production of propanol by this means. A further preferred embodiment of the present invention is the combination of the hydroformylation of a multi-component synthesis gas, with the oxidation of the aldehyde product of that hydroformylation, to produce an organic acid product. The production of propionic acid by this means is particularly preferred. The hydrogenation and oxidation of the aldehyde in the aforementioned products can be carried out according to procedures known in the art. A further preferred embodiment of the present invention is the combination of the hydroformylation of a multi-component synthesis gas with an aldol condensation step. Aldol condensation is a conversion step that is well known in this field. In this reaction, two aldehydes are bound in such a way that the carbon a of the first becomes bound with the carbonyl carbon of the second. The result is called an "aldol", which is a compound of β-hydroxycarbonyl. Typically, aldol removes H20 to give an unsaturated aldehyde. The condensation of aldol from two identical aldehydes is called "auto-aldol", while the condensation of aldol from two different aldehydes is called "cross-aldol". Additional preferred embodiments of this invention include the hydrogenation of the thus produced aldols to obtain saturated aldehydes, as well as saturated and unsaturated alcohols. A further preferred embodiment of this invention is the oxidation of the saturated and unsaturated aldehydes derived from the condensation of aldol, to obtain the corresponding saturated and unsaturated acids. Accordingly, a further preferred embodiment of the present invention is the combination of the hydroformylation of a multi-component synthesis gas with an auto-aldol of the aldehyde produced, to produce an aldol dimer. Particularly preferred is the production of 2-methylpentenal by this means, and the subsequent hydrogenation in 2-methylpentanal, and / or 2-methylpentanol, as well as the oxidation of 2-methylpentanal to 2-methylpentanoic acid. A further preferred embodiment of the present invention is the production of multi-methylolalkanes by means of the condensation of cross-linked aldol of formaldehyde with the aldehydes produced by the hydroformylation of a multi-component synthesis gas. A further preferred embodiment of the present invention is the production of multi-methylolalkanes by means of the condensation of cross-linked aldol of formaldehyde with the unsaturated or saturated (hydrogenated) aldehydes produced as aldol dimers of the aldehydes produced by means of the hydroformylation of a synthesis gas of multiple components. Typically, in this known technique, the carbonyl group (C = 0) of this cross-aldol product is reduced chemically or catalytically, in such a way that all the oxygen of the multi-methylolalkanes is in the hydroxyl form. Particularly preferred is the production of trimethylolethane by this means (by cross-linking formaldehyde with propanal), and the production of 2,2'-dimethylolpentane by this means (by cross-linking formaldehyde with 2-methylpentanal). The conversion of the aldehydes to the aforementioned products can be carried out in accordance with the processes known in the art. Therefore, the present invention includes a process for the manufacture of alcohols, wherein the aldehydes formed by the hydroformylation of a multi-component synthesis gas are hydrogenated to form the corresponding alcohols; a process for the manufacture of acids, wherein the aldehydes formed by the hydroformylation of a multi-component synthesis gas are oxidized to form the corresponding acids; a process for the manufacture of aldol dimers, wherein the aldehydes formed by the hydroformylation of a multi-component synthesis gas auto-aldolize to form the corresponding dimers; a process for the manufacture of saturated aldehydes, wherein these aldol diranes are hydrogenated in the corresponding saturated aldehydes; a process for the manufacture of alcohols or unsaturated acids, wherein the aldol dimers are hydrogenated or oxidized to form the corresponding unsaturated alcohols or acids; a process for the manufacture of saturated alcohols, wherein the alcohol dimers are hydrogenated to form the corresponding saturated alcohols; a process for the manufacture of alcohols or saturated acids, wherein the saturated aldehydes produced by the hydrogenation of the aldol dimers are hydrogenated or oxidized to form the corresponding saturated alcohols or acids; a process for the manufacture of multi-methylolalkanes, wherein the aldehydes formed by the hydroformylation of a multi-component synthesis gas are condensed in aldol with formaldehyde to form the corresponding multi-methylolalkanes; a process for the manufacture of trimethylolethane, wherein the propanal which is formed by the hydroformylation of a multi-component synthesis gas is aldol condensed with formaldehyde to form trimethylolethane; and a process for the manufacture of multi-methylolalkanes, wherein the aldol dimers and / or the saturated aldehydes produced therefrom are condensed in aldol with formaldehyde to form the corresponding multi-methylolalkanes. This invention can be used to produce the composition containing propanal which is used for the production of aldehydes, alcohols, acids, and their derivatives, described in European Patent Number EPA 95.300 301.9, and in the TCP Application based thereon, which are incorporated herein by reference. Example 1 Apparatus Experiments were performed in a stainless steel autoclave of 300 milliliters Autoclave Enginners. The reactor was connected to a 500 milliliter high pressure pH regulator pump through a regulating valve. Both the reactor and the pH regulator pump were equipped with digital temperature and pressure meters. The autoclave was also equipped with a temperature control unit, and an agitator with speed control. The total and free volumes of the different parts of the apparatus were measured by the gas volumetric method. Preparation of the Catalyst Solutions containing rhodium and phosphine were prepared in dry boxes of Vacuum Atmospheres under nitrogen or argon. Rhodium was charged either in the form of HRh (CO) PPh3) 3, or as Rh (CO) 2 (acac), where PPh3 is triphenylphosphine, and acac is the acetylacetonate ligand. Rh (CO) 2 (acac) was purchased from Strem Chemicals, and was used as received. ' HRh (CO) (PPh3) 3 was prepared from Rh (CO) 2 (acac) by the literature method (G.W. Parshall, Inorg.Synth, 1974, 15, 59). Toluene was distilled from sodium benzophenone under nitrogen. The weight of each component of the toluene solution was measured. Methylohexane was used as an internal gas chromatography standard. The solution was charged under nitrogen flow in the autoclave. Then the unit was flooded with synthesis gas (H2 / CO = 1). When the catalyst was prepared at the site, the autoclave was pressurized to about 0.5 MPa at room temperature, and then heated to 100 ° C, and kept at that temperature for about 30 minutes. Independent experiments showed that under these conditions, rhodium loosens the acetylacetonate ligand by hydrogenation, and the hydruro-carbonyl-triphenylphosphino-rhodium complexes formed (HRh (CO) x (PPh3) y, x + y = 4) catalyze hydroformylation without showing any induction period. When HRh (CO) (PPh3) 3 was used as a source of Rh, it was not necessary to preform the catalyst. Hydroformylation of Gas Mixture # 1 The reactor containing the preformed catalyst solution was flooded and pressurized with Gas Mixture # 1 containing ethylene, ethane, aethylene, carbon dioxide, hydrogen, methane, carbon monoxide and nitrogen (the composition is given in Table 2) at room temperature. The amount of gas charged in the reactor was determined by the gas volumetric method. The proportion of P / Rh in this experiment was 9.3. The composition of the charged catalyst is given in the footnote of Table 2. The reactor was heated to 100 ° C, and kept at the reaction temperature for two hours. While the reactor was at the reaction temperature, a pressure drop indicated that the reaction occurred. After two hours at 110 ° C, when no further pressure drop was observed, the reactor was cooled to 15 ° C, and samples of gas and liquid were taken. A mass balance was established for the charged materials based on gas chromatography (GC) analyzes of the gas and liquid phases. The results are given in Table 2. In the liquid phase, the only detected product of the reaction was identified by gas chromatography / mass spectrometry (GC / MS) as propanal. Propanal, found in the liquid phase gave a 60 percent conversion, based on the total amount of ethylene and acetylene charged in the reactor. Since the experiment stopped when the oxo reaction ceased, the catalyst clearly deactivated before higher conversions could have been reached. Gas analysis of the final reaction mixture indicated that both unreacted ethylene and acetylene were present in an acetylene / ethylene ratio of 3.4 at the point where the oxo conversion was stopped. The results of the analysis showed that a parallel conversion of both ethylene and acetylene had occurred. The final solution had a dark brown color which is associated in the experiments described herein with a decomposed catalyst.

Table 2. Hydroformylation of Multi-Component Synthesis Gas (Gas Blend # 1) at 110 ° C Reaction conditions: toluene: 90 milliliters, methylcyclohexane (internal standard for gas chromatography): 0.8 milliliters, Rh: 897 micromoles (1130 ppm); PPh3: 8.3 millimoles; p ° = 1545 kPa (at 20 ° C); Reaction time at 110 ° C: 2 hours. Legend: x ° = initial gas concentration; n ° = initial number of millimoles in the gas phase; nf = final number of millimoles in the gas phase,? n = change in the molar number in the gas phase.

* Results of liquid gas chromatography. Example 2 The apparatus, the catalyst preparation method, and the experimental procedures were the same as in Example 1. Gas Mixture # 2, used in this experiment, contained ethylene, ethane, acetylene, carbon dioxide, hydrogen , methane and carbon monoxide (the composition is given in Table 3). The reaction temperature was 100 ° C, and the P / Rh ratio was 300. The composition of the catalyst solution is given in Table 3. After heating the reaction mixture to 100 ° C, a rapid pressure drop in the autoclave, indicating that a gas consuming reaction took place. This pressure drop became significantly slower after a reaction time of about 45 minutes, when the reaction was stopped by cooling the reaction mixture to 15 ° C. After cooling the system, samples of gas and liquid were taken and analyzed by gas chromatography. The results are given in Table 3. Analysis of the gas and liquid phases gave a higher conversion (88.5 percent) at a lower temperature of 10 ° C, a concentration of catalyst 14 times lower, and in times 2.7 times shorter than that observed in Example 1. In addition, the color of the sample in solution taken at the end of the experiment was bright orange-yellow. An orange-yellow color in the experiments described herein is associated with an active catalyst system in the conversion of multicomponent synthesis gas mixtures containing acetylene and ethylene. Table 3. Hydroformylation of Multi-Component Synthesis Gas (Gas Blend # 2) at 100 ° C * Results of liquid gas chromatography. Reaction conditions: toluene: 60 milliliters, methylcyclohexane (internal standard for gas chromatography): 0.8 milliliters, Rh: 64.3 micromoles (110 ppm); PPh3: 19.3 millimoles; p ° = 800 kPa (at 100 ° C); Reaction time at 100 ° C: 45 minutes. Legend: x ° = initial gas concentration, - n ° = initial number of millimoles in the gas phase; nf = final number of millimoles in the gas phase,? n = change in the molar number in the gas phase. EXAMPLE 3 This example demonstrates the effect of the P / Rh ratio on the hydroformylation of oxo feed streams of multi-component synthesis gas containing acetylene and ethylene. The preparation and loading procedures of the catalyst solutions were the same as in Example 1. The solvent, tetraethylene glycol dimethyl ether (tetraglima), was degassed before use. It also served as an internal standard in the gas chromatography analyzes of the product of the liquid samples. The volume of the solution, and the total initial gas load in each experiment were equal, 70 milliliters, and 95 millimoles, respectively. The apparatus was the same as in Example 1, with the exception that a calibrated volume high pressure injection pump was mounted on the feed line after the high precision pressure regulator between the pH regulator cylinder and the autoclave. This injection pump was used to inject known amounts of ethylene / acetylene mixtures into the autoclave. The charges of ethylene and acetylene in each experiment were around 15.4 and 6.4, respectively. Batch kinetic experiments were performed at a constant total caliper pressure of 1 MPa and at 120 ° C. As the reaction proceeded, a constant pressure was maintained by supplying synthesis gas (CO / H2 = 1) from the calibrated volume high pressure pH regulator pump through a precision gauge regulating valve. The reaction was monitored by reading the pressures on the pH regulator (measured to an accuracy of 1 kPa) as a function of time (recorded to an accuracy of 1 second). After each execution, the global ethylene and acetylene conversions were determined by gas chromatography analysis of the liquid and gas products. The only two products of the reactions detected were propanal as a major product, and minor amounts of ethane. Then, the overall conversion was correlated with the total pressure drop and the total gas consumption in moles from the pH regulator pump during the experiment. The reaction rates were calculated assuming a linear correlation between the pressure drops and the conversion. The catalyst compositions, and the results of seven different experiments are shown in Table 4.

Table 4. Effect of PPh3 Concentration on Oxo Reaction Speed and Conversion of Acetylene-Ethylene Mixed Feeds Volume in Solution: 70 milliliters; H2 / C0 = 1; Total Pressure = 1 MPa; Initial Gas Load: 95 millimoles in total, 15.4 millimoles of C2H4, 6.4 millimoles of C2H2, the rest of CO and H2; the rhodium concentration is 54 ppm and 27 ppm for 38 and 19 micromoles, respectively. The kinetic data in Table 4 demonstrate that the activity of the catalyst is increased significantly by increasing the phosphine concentration. The color of the final solutions was orange-yellow, with the exception of the test with a PPh3 / Rh ratio of 10, which was brown after 120 minutes of reaction time. This color variation indicates that a stable catalyst system at a PPh3 / Rh ratio of 10 is not present in the hydroformylation of multi-component synthesis gas feeds containing acetylene and ethylene. Under the preferred proportions of PPh3 / Rh greater than 30, significant improvements in speed, conversion and stability are achieved. Example 4 The example demonstrates the effect of the proportion of H2 / CO on the hydroformylation of alkene (ethylene) in the presence of an accumulated diene (aleño). The preparation and loading procedures of the catalyst solutions were the same as in Example 1. The experimental method and the kinetic evaluation of the experimental values were the same as in Example 3, with the exception that 15 millimoles of ethylene were co-injected with 0.13 millimoles of aleño and with different amounts of hydrogen to adjust the proportions of H2 / C0 in the autoclave. The catalyst load was 18.8 micromoles Rh (27.7 ppm), and 8.3 millimoles PPh3 (3.1 weight percent) in each experiment. After injecting alene-ethylene mixtures in the autoclave at 120 ° C, the. reaction proceeded first at a very slow speed. Gas analysis of the gas reaction mixture showed a slow accumulation of propylene during this first slow stage of the reaction. The hydroformylation of ethylene took place only after it became essential in all (typically 95 to 99 percent) of the charged alloy. The duration of this first phase of the reaction depended on the proportion of H2 / CO (see Table 5).

Table 5. The Effect of the H2 / CO Ratio on the Conversion Rate of Volume in Solution: 70 milliliters; H2 / C0 = 1; Total Pressure = 1 MPa; Initial Gas Load: 95 millimoles in total, 15 millimoles of CH4, 0.13 millimoles of C3H42, the rest of CO and H2; Rh = 27.7 ppm; [PPh3 = 3.1 percent. Example 5 Gas solubilities were measured, either by the gas volumetric method using the same autoclave as in Example 1, or by 1H nuclear magnetic resonance. In the autoclave experiments5, the solvent was completely degassed in the autoclave before the gas was charged without agitation. After a short temperature equilibrium, the pressure and temperature in the autoclave were recorded, and then the solvent was stirred until another pressure drop could no longer be observed. From the known gas volume and the pressure drop, the amount of dissolved gas was calculated. In the 1H nuclear magnetic resonance experiments, the solvent (propanal) or hexamethylbenzene, served as an internal standard. The values obtained are mentioned in Table 6.

Table 6, ExperimentaIntente Solubilities Determined for Hydrogen, Carbon Monoxide, Methane, Ethylene and Acetylene, at a Partial Pressure of 0.1 MPa Legend: X¿ = mole fraction of the gas component in the liquid phase; C ^ = molarity of the gaseous component in the liquid phase. Note: * Tetraglima containing 7.8 percent by weight of PPh3.

The experimentally determined values (see Table 6) and the literature (see Table 7) reflect high solubilities of ethylene and acetylene in oxygenates, especially in propanal. There is a large difference in the solubility between ethylene and acetylene against all other major components of typical multi-component synthesis gas mixtures, such as hydrogen, carbon monoxide, and methane. It can also be seen that the difference in solubility increases with decreasing temperature.

Table 7. Gas Solubilities in Oxygenated Solvents Legend: XL = mole fraction of the gas component in the liquid phase; C = molarity of the gaseous component in the liquid phase. References of Table 7: e) R.A. Aronovich, 1.1. Vasil'eva, S.M. Loktev, A.A. Polyakov, E.V. Slivinskii, T.N. Tyvina Theor. Eksp. Khi 1991, 27 (2), 241. g) L.P. Lizano, M.C. López, F.M. Royo, J.S. Urieta J. Solution Chem. 1990, 19 (7), 721. k) 1.1. Vasil'eva, A.A. Naumova, A.A. Polyakov, T.N. Tyvina, V.V. Fokina Zh. Prikl. Khim. 1987, 60 (2), 408. t) E. Brunner J. Chem. Thermodynamics 1980, 12, 993. v) N.G. Raginskaya, N.G. Tyurikova, N.L. Nechitai-lo Khim. Prom-st., 1979, 1.21. w) E. Brunner Ber. Bunsenges, Phys. Chem. 79, 83 (7), 715. Example 6 The preparation and loading procedures of the catalyst solutions were the same as in Example 1. The experimental method and the kinetic evaluation of the experimental values were the same as in Example 3, with the exception that 15 millimoles of ethylene were coinjected with 0.13 millimoles of one of the following dienes or acetylenes: 1,3-butadiene, aleño, propino and acetylene. The catalyst load was 18.8 micromoles Rh (27.7 ppm), and 8.3 millimoles PPh3 (3.1 weight percent) in each experiment. The gas analysis of the gas reaction mixtures indicated a parallel conversion of ethylene with 1,3-butadiene, propyne and acetylene. However, in the case of the ethylene-alene mixtures, the conversion of ethylene could only begin after essentially all of the propylene-injected fume had been hydrogenated, as described in Example 4. The final reaction mixtures essentially contained propanal, ethane, and the hydrogenated product of the highly unsaturated component co-injected. Therefore, 1,3-butadiene produced butenes, and propylene and propylene produced propylene. At an ethylene conversion of 95 to 98 percent, typical conversions of 1,3-butadiene and propyne in the corresponding olefins were about 60 percent. Since the acetylene hydrogenation product is ethylene, its intermediation in the hydroformylation of ethylene-acetylene mixtures could not be detected. The reaction rates observed showed a different degree of inhibition on the oxo ethylene index by the highly unsaturated component. Therefore, the rotation frequencies observed in the hydroformylation of ethylene with aleño, 1,3-butadiene, propino, and acetylene as co-injected reagents in an ethylene conversion of 33 percent, were 3, 5.5, 7, and 9 moles. of propanal / moles of Rh / second, respectively. Example 7 This example demonstrates the effect of small acetylene concentrations on the stabilization of the rhodium catalyst against deactivation. The experiment involves two stages; an aging step and a kinetic measurement step. The preparation and loading procedures of the catalyst solutions were the same as in Example 3, with the exception that the volumes of the autoclave and the pH regulator pump are 500 and 325 milliliters, respectively. For the aging stage of the experiment, 300 milliliters of catalyst solution was charged, whose solution contained 1400 millimoles of tetraglima, 30 millimoles of triphenylphosphine, and 0.3 millimoles of rhodium (96 ppm). These solutions were heated to 140 ° C at 1 MPa, and contacted with one of three gas streams; (a) synthesis gas (H2 / C0 = 1) only, (b) synthesis gas with 5 mole percent of ethylene, or (c) synthesis gas with 0.51 mole percent acetylene. In cases (b) and (c), the flow of the gas stream was controlled so that the concentration of the substrate in the effluent was maintained at about 0.5 mole percent. After aging times of 0 (initial solution), 80, 140 and 260 minutes, 30 milliliter samples were removed from the catalyst solution and set aside. For the stage of the kinetic measurement experiment, 200 milliliters of catalyst solution were loaded, the solutions of which were prepared using the 30 milliliter samples of the aging step, and adding tetraglime and triphenylphosphine to make a solution containing 860 millimoles of tetraglirase, 35 millimoles of triphenylphosphine, and 0.02 millimoles of rhodium (10 ppm). The experimental method for the kinetic evaluation was the same as in Example 3 (1 MPa, 120 ° C, H2 / C0 = 1), with the exception that 20 millimoles of ethylene were co-injected with 3 millimoles of acetylene. The velocity (moles of oxo / second) was found to be of first order in ethylene, and a rate constant for each kinetic experiment was calculated as moles of oxo per mole of ethylene, per ppm by weight of Rh, per second. For each aging experiment, the rate constants were then normalized as a percentage of the initial activity of the catalyst (zero aging). A summary of the conditions and results of these catalyst deactivation experiments is shown in Table 8. It is well known that deactivation of the catalyst is rapid under conditions where a substrate (olefin, alkyne) is absent, and this is confirmed in experiment (a), where activity drops by 90 percent in 260 minutes at 140 ° C. The hydroformylation of olefin is commonly carried out under conditions of low conversion per pass, in order to maintain the presence of the substrate to mitigate this deactivation. Experiment (b) confirms that the presence of olefin reduces deactivation (now only 50 percent after 260 minutes), but also demonstrates that, under conditions of high conversion that would be reflected in an output concentration of approximately 0.5 percent molar, considerable deactivation occurs. In contrast, experiment (c) shows that low concentrations (approximately 0.5 mole percent) of acetylene dramatically reduce deactivation (now only 5 percent after 260 minutes). This preservation of the catalyst activity makes the operation possible at higher conversion per pass, as well as at higher temperatures.

Table 8. Deactivation of the Catalyst Against Presence of the Substrate EXAMPLE 8 This example demonstrates the continuous hydroformylation of olefin and accumulated diene mixtures, more specifically of ethylene and aleño. The experiments were carried out in an autoclave of stainless steel Autoclave Engineers Zipperclave of 500 cubic centimeters. The autoclave was equipped with a continuous gas feed system, with back pressure control, and with gas feed and product characterization by gas chromatography. The catalyst solution was prepared by mixing under nitrogen 210 grams of tetraglima, 15.8 grams of triphenylphosphine, and 8.8 milligrams of rhodium (added as Rh (CO) 2 (acac), where acac is the acetylacetonate ligand. 39 ppm by weight of Rh, and at a P / Rh ratio of 700. The catalyst solution was transferred to the autoclave under nitrogen, the autoclave was purged with nitrogen, and then the gas flows began as indicated in Table 9. Then the pressure was accumulated to the position of 1000 kPa (absolute) of the back pressure control, after which the autoclave and the contents were heated to a reaction temperature of 90 ° C. Gas samples were taken afterwards. at least 20 hours of continuous reaction.

Table 9. Continuous Hydroformylation of Ethylene and Aleño As shown in Table 9, ethylene and aleño were simultaneously converted to these hydroformylation conditions. By maintaining the high proportion of ethylene to aleño, the products of these tests were predominantly propanal. However, butanal was observed as a reaction product.

Claims (43)

1. NOVELTY OF THE INVENTION Having described the foregoing invention, it is considered as a novelty, and therefore, the content of the following is claimed as property: CLAIMS 1. A process for the production of aldehydes of 3 to 6 carbon atoms, which comprises hydroformylating a mixture containing: (i) olefins of 2 to 5 carbon atoms and mixtures thereof, and (ii) alkynes of 2 to 5 carbon atoms and mixtures thereof, and optionally (iii) dienes accumulated by reaction with CO and H2 in the presence of a solution of a rhodium organophosphorus complex catalyst, at a rhodium concentration in solution of 1 to 1000 ppm by weight.
2. 2. A process for the production of aldehydes from 3 to 6 carbon atoms, which hydroformillary comprises a mixture containing: (i) olefins of 2 to 5 carbon atoms and mixtures thereof, and (ii) alkynes of 2 to 5 carbon atoms and mixtures thereof , and optionally (iii) accumulated dienes, - by reaction with CO and H2 in the presence of a solution of a rhodium organophosphorus complex catalyst, in a rhodium concentration in solution where the proportion of rhodium phosphorus is higher 30.
3. A process for the production of aldehydes of 3 to 6 carbon atoms, which comprises hydroformylating a mixture containing: (i) olefins of 2 to 5 carbon atoms and mixtures thereof, and (ii) alkynes of 2 to 5 carbon atoms and mixtures thereof, and optionally (iii) accumulated dienes, - by reaction with CO and H2 in the presence of a solution of a rhodium organophosphorus complex catalyst, wherein the solution of catalyst has a higher P / Rh ratio than the RL value, where: (30-RB) »10 (pKaTPp-pKa) L P (? S / R) e B where RB is the ratio of P / Rh sufficient for a catalytically active Rh complex, pKatpp is the pKa value for triphenylphosphine, pKaL is the pKa value for the triorganophosphorus compound, R is the gas constant, and SB SB is 35 (N-1) cal / mol °, where N is the number of P-Rh bonds per ligation molecule, to produce the aldehydes of 3 to 6 carbon atoms corresponding.
4. 4. A process in accordance with claim 1 or claim 3, wherein the ratio of phosphorus to rhodium is greater than 30.
5. 5. A process according to claim as claimed in any of the preceding claims, wherein the organophosphorus compound is triorganophosphorus.
6. 6. A process according to claim 1 in any of the preceding claims, wherein the rhodium organophosphorus complex is oil soluble.
7. 7. A process according to claim as claimed in any of the preceding claims, wherein the rhodium is of low valence.
8. 8. A process according to claim as claimed in any of the preceding claims, wherein the feed is a synthesis gas of multiple components.
9. 9. A process according to claim 1 in any of the preceding claims, wherein the hydroformylation is carried out at a temperature greater than 80 ° C.
10. 10. A process according to claim 1 in any of the preceding claims, wherein, on average, the mixture is in contact with the catalyst for not more than four hours.
11. 11. A process according to claim as claimed in any of the preceding claims, wherein a total concentration of coordinatively active P is used of at least about 0.01 mol / liter.
12. 12. A process according to claim 1, wherein a ratio of [P] / pco of at least 0.1 millimoles / liter / kPa is used, where [P] is the total concentration of the phosphorus is active in the solution, and pco is the partial pressure of CO used.
13. 13. A process according to claim 1 in any of the preceding claims, wherein the olefin is essentially ethylene, and the alkyne is essentially acetylene. 1 .
14. A process according to claim as claimed in any of the preceding claims, wherein the mixture also contains dienes.
15. 15. A process according to claim as claimed in any of the preceding claims, wherein the H2 / CO partial pressure ratio is from 1 to 100, the partial pressure ratio of CO / monounsaturated is from 0.5 to 100, and from H2 / monounsaturated is from 0.5 to 100.
16. 16. The process according to claim as claimed in any of the preceding claims, wherein the triorganophosphorus ligand soluble in oil is selected from the group consisting of triarylphosphines, trialkylphosphines, alkyldiarylphosphines, aryldialkylphosphines, trialkylphosphites. , and triaryl phosphites, soluble in oil, having at least one phosphorus atom per molecule.
17. 17. The process according to claim 1 in any of the preceding claims, wherein the reaction temperature is from 80 ° C to 180 ° C, the total pressure is from about 0.05 to about 5 MPa, the partial pressure of carbon is up to 50 mole percent of the total pressure, the molar percentage of H2 is 1 to 98 mole percent, and the mole percentage of ethylene and acetylene, each alone and in combination, is 0.1 to 35 percent molar.
18. 18. The process according to claim 1 in any of the preceding claims, wherein the molar ratio of the olefin to the alkyne is at least 2.
19. 19. The process according to claim as claimed in any of the preceding claims, wherein the contact is made in at least two stages of the reactor.
20. The process according to claim 19, wherein the first stage is optimized under conditions for the conversion of olefins in the presence of alkynes, and the second stage is optimized under hydrogenation conditions for the conversion of alkynes into olefins.
21. 21. A process for the recovery of unreacted unsaturated hydrocarbons from an effluent stream of a process in accordance with that claimed in any of the preceding claims, which comprises: (a) absorbing unreacted unsaturated hydrocarbons and the oxygenated hydrocarbons of the effluent stream of the synthesis process in a solvent, where this solvent is a depleted stream of unsaturated oxygenated product from said synthesis process; and (b) separating the unsaturated hydrocarbons from the solvent to produce a first stream concentrated in unsaturates, and a second stream of oxygenated product depleted from unsaturates, wherein this stream exhausted from unsaturates is the absorption solvent and the product of the synthesis process.
22. 22. The process according to claim 21, wherein the absorption is carried out at a temperature between -100 ° C and + 100 ° C.
23. 23. A process for recovering unreacted unsaturated hydrocarbons from an effluent stream of a process according to claim 1, which comprises: (a) partially condensing the effluent from the synthesis process to produce a liquid condensate enriched in the oxygenated product, and a gaseous stream enriched in the low-boiling gaseous components; (b) separating the liquid condensate with a gas essentially free of unsaturates, to produce an oxygenated product free of unsaturates, and a gaseous stream enriched in unsaturated and low-boiling gaseous components; (c) combining the gaseous streams from step (a) and step (b), and cooling the combined stream; (d) treating the combined stream from step (c) in an absorber having reflux of the saturated hydrocarbon species in the upper part, to produce a higher stream containing the low-boiling gaseous components, and substantially free of the product of the synthesis process and of unsaturated hydrocarbons, and a bottom stream of the product of the synthesis process containing concentrated unsaturated hydrocarbons; and (e) recycle bottom streams to the synthesis reactor.
24. 24. The process according to claim 23, wherein the bottom stream of step (e) is pumped at a high pressure, and exchanging heat with the combined stream of step (c), to recover the value of cooling.
25. 25. The process according to claim 23 or claim 24, wherein the treatment of step (d) is carried out at a temperature between -100 ° C and + 100 ° C.
26. 26. A process for the preparation of a feed stream useful in the process according to claim 1 of any of claims 1 to 25, which preferably comprises removing a variable amount of alkynes and multiinsaturates from a gas stream containing at least hydrogen, olefins, alkynes, and multiunsaturated, which comprises contacting the gas stream with a stream containing metal complex, at a sufficient rate to form adducts of the alkynes and the multiunsaturates to be removed, and remove a stream containing the alkyne and multi-unsaturated adducts from the metal complex.
27. 27. A process according to claim 26, wherein the metal complex stream is a liquid or a paste.
28. The process according to claim 26 or claim 27, wherein the metal complex is an oil-soluble rhodium complex containing a triorganophosphorus ligand selected from the group consisting of triarylphosphines, trialkylphosphines, alkyldiarylphosphines , aryldialkylphosphines, trialkyl phosphites and triaryl phosphites, containing at least one phosphorus atom per molecule.
29. 29. The process according to claims 26 to 28, wherein the multiunsaturates are selected from the group consisting of conjugated and accumulated dienes of 3 to 5 carbon atoms, diinos, and enines, and the alkynes are selected from the group consisting of a group consisting of alkynes of 2 to 5 carbon atoms, and the olefins are selected from the group consisting of olefins of 2 to 5 carbon atoms.
30. 30. The process according to claim 29, wherein the gas stream is a multi-component synthesis gas mixture., which further comprises one or more of the gases selected from the group consisting of CO, C02, alkanes of 1 to 5 carbon atoms, oxygenated hydrocarbons of 1 to 5 carbon atoms, nitrogen, water vapor, helium and argon.
31. 31. The process as claimed in any of claims 26 to 30, which further comprises a separate regeneration step, wherein the multi-unsaturated adducts and the alkyne removed from the metal complex are brought into contact with a gas rich in hydrogen and depleted of CO, to form hydrogenated and multiinsaturated alkynes, and a regenerated multiinsunsaturated metal complex stream.
32. 32. The process according to claim 31, wherein the contact of the regeneration step is carried out at a partial pressure ratio of H2 / CO of at least about 10, a total pressure of about 0.1 to 50 MPa, and at a temperature of about 50 ° C to about 180 ° C.
33. 33. The process as claimed in any of claims 26 to 32, wherein the stream containing metal complex is introduced at a sufficient rate to form adducts of the multi-unsaturated, without forming adducts of the alkynes.
34. 34. A process comprising hydrogenating the aldehyde produced in accordance with claim 1 in any of the preceding claims, to form the corresponding alcohol.
35. 35. A process comprising oxidizing the aldehyde produced in accordance with claim 1 in any of the preceding claims, to form the corresponding acid.
36. 36. A process comprising aldolizing the aldehyde produced in accordance with claim 1 in any of the preceding claims, to form the corresponding aldol dimer.
37. 37. A process according to claim 36, which further comprises hydrogenating the aldol dimer to form a saturated aldehyde or a saturated alcohol.
38. 38. The process according to claim 36, which further comprises oxidizing the aldol dimer to form the corresponding unsaturated acid.
39. 39. A process comprising oxidizing the saturated aldehyde produced in accordance with claim 37, to form the corresponding saturated acid.
40. 40. A process comprising the condensation in aldol of the aldehyde produced according to claim 1 in any of the preceding claims, with formaldehyde, to form multi-methylolalkanes.
41. 41. The process according to claim 40, wherein the aldehyde is propanal, and the multi-methylolalkan is trimethylolethane.
42. 42. A process further comprising condensing aldol the aldol dimer of claim 36 with formaldehyde, to form the corresponding multi-methylolalkane.
43. 43. A process further comprising condensing aldol the saturated aldehyde of claim 37 with formaldehyde, to form the corresponding multi-methylolalkal-cano.