Patent EA-001834-B1 (EA)
Title: Process of hydroformylation in multi-staged reactors
Inventor: BECKER MICHAEL CARL
IPC: F04D29/28
Filed: 1996-12-05
Abstract: 1. A process of hydroformylation of one or more reactants in staged reactor, which process comprises reacting in said staged reactor one or more reactants with carbon monoxide in the presence of a metal-organophosphite ligand complex catalyst and optionally free organophosphite ligand to produce one or more reaction products, wherein said selected metal-organophosphite ligand complex catalyst is not exposed substantial deactivation in the presence of carbon monoxide only, and/or effects a change in normal product selectivity of less than 0.2 percent of normal product per 6,89 kPa (1 pound per square inch) of carbon monoxide partial pressure and/or effects a change in reaction rate of less than 2 percent per 6,89 kPa (1 pound per square inch) of carbon monoxide partial pressure. 2. A process according to Claim 1, which is a hydroformylation process for producing one or more aldehydes in a staged reactor which process comprises reacting in said staged reactor one or more olefinic unsaturated compounds with carbon monoxide and hydrogen in the presence of a metal-organophosphorus ligand complex catalyst and optionally free organophosphorus ligand to produce said one or more aldehydes, wherein said metal-organophosphorus ligand complex catalyst does not undergo substantial deactivation in the presence of solely carbon monoxide and hydrogen and/or effects a change in normal aldehyde selectivity of less than 0.2 percent of normal aldehyde per 6,89 kPa (1 pound per square inch) of carbon monoxide partial pressure and/or effects a change in reaction rate of less than 2 percent per 6,89 kPa (1 pound per square inch) of carbon monoxide partial pressure. 3. The processes of Claims 1 or 2 in which the staged reactor comprises: a substantially vertically-oriented reactor means; a stirring means inside said reactor means, said stirring means being operatively associated with said reactor means and comprising an elongated rod means having a plurality of blades disposed about said rod means, said stirring means extending substantially throughout the entire length of said reactor means; at least two reactants entrance means in the lower portion of said reactor means for continuously conveying one or more olefinic compounds, one or more metal-organophosphorus ligand complex catalysts and a source of hydrogen and carbon monoxide into said reactor means; optionally at least one reactants entrance means in the upper portion of said reactor means for continuously conveying one or more olefinic compounds, one or more metal-organophosphorus ligand complex catalysts and/or a source of hydrogen and carbon monoxide into said reactor means; at least one product exit means in the upper portion of said reactor means for continuously removing product, metal-organophosphorus ligand complex catalyst and unreacted reactants from said reactor means; and at least one baffle means on the inside surface of said reactor means, said baffle means being spaced in such a manner that said baffle means are interspaced in-between said blades of said stirring means. 4. The process of Claim 3 in which the staged reactor further comprises a heat removal means comprising external loop and/or internal coils. 5. The process of Claims 1 or 2, in which the staged reactor comprises: a substantially vertically-oriented vessel; a plurality of generally horizontal baffles disposed within said vessel and dividing the interior of said vessel into a plurality of chambers, each said baffle being formed with a central hole and being mounted on the inner wall of said vessel; at least two inlet means for feeding one or more olefinic compounds, one or more metal-organophosphorus ligand complex catalysts and a source of hydrogen and carbon monoxide into one or more-lower chambers; optionally at least one inlet means for feeding one or more olefinic compounds, one or more metal-organophosphorus ligand complex catalysts and/or a source of hydrogen and carbon monoxide into one or more upper chambers; at least one outlet means for removing hydroformylation products, metal-organophosphorus ligand complex catalysts and unreacted reactants from one or more upper chambers; a rotatable generally vertical drive shaft centrally positioned to rotate in said vessel and extending generally concentrically through each said hole in each said baffle; and a plurality of impellers each mounted for rotation on said shaft and generally positioned above or below each said hole of said horizontal baffles, said impellers being of a size relative to said holes to sufficiently provide mixing of said hydroformylation reactants, metal-organophosphorus ligand complex catalysts and products as they move from a lower chamber upward to an adjacent chamber whereby said hydroformylation reactants, metal-organophosphorus ligand complex catalysts and products are caused to be well mixed within each chamber. 6. The process of Claim 5 in which the staged reactor further comprises a heat removal means comprising external loop and/or internal coils. 7. The process of Claims 1 or 2, in which the staged reactor comprises: a vertical cylindrical vessel with a plurality of spaced stationary horizontal imperforate baffles dividing said vessel into superposed compartments, said baffles having central apertures therein for communication between said compartments; an upstanding flange disposed around the circumference of the central aperture of each compartment; a shaft rotatably mounted axially of said vessel and extending through said compartments and an agitating means for the shaft; a means for admitting carbon monoxide, hydrogen, one or more metal-organophosphorus ligand complex catalysts and one or more olefinic compounds into the lower-most compartment; and a means for withdrawing product aldehyde, metal-organophosphorus ligand complex catalyst and unreacted reactants from the upper-most compartment. 8. The process of Claims 1 or 2, in which the staged reactor comprises: a vessel with an elongated generally cylindrical chamber therein; an agitator shaft extending coaxially through the chamber, the shaft extending outside the chamber and being provided with means for driving the same; a plurality of transverse partitions in the chamber open at their centers around the agitating shaft dividing the chamber into a lineal series of compartments in open communication with one another; an agitator for providing essentially complete backmixing in each compartment; vertical baffles in each compartment projecting radially toward the center to prevent swirling of fluids being agitated, designed to produce in each compartment upon rotation of the agitator a cyclical flow of fluid and gas from the periphery of the agitator to the peripheral wall of the chamber, thence lengthwise of the chamber in each direction along the walls of the compartment, and thence radially inwardly adjacent said partitions toward the shaft; a means for admitting carbon monoxide, hydrogen, one or more metal-organophosphorus ligand complex catalysts and one or more olefinic compounds into the lower-most compartment; and a means of withdrawing product aldehyde, metal-organophosphorus ligand complex catalyst and unconverted reactants from the upper-most compartment. 9. The process of Claims 1 or 2, in which the staged reactor comprises the reactive stages which are physically separated by baffle plates with passages from one reactive stage to another reactive stage where said passages are such that gas and liquid backflow is minimized. 10. The process of Claims 1 or 2, in which the staged reactor comprises the reactive stages which are separated by designed mixing patterns which create regions of varying concentrations and allow for gas and liquid flow from reactive stage to reactive stage. 11. The process of any preceding Claims, wherein said metal-organophosphorus ligand complex catalyst comprises rhodium complexed with an organophosphorus ligand having the formula selected from: (i) a triorganophosphine ligand represented by the formula:   wherein R<1> is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 24 carbon atoms or greater; (ii) a monoorganophosphite represented by the formula:   wherein R<3> represents a substituted or unsubstituted trivalent hydrocarbon radical containing from 4 to 40 carbon atoms or greater; (iii) a diorganophosphite represented by the formula:   wherein R<4> represents a substituted or unsubstituted divalent hydrocarbon radical containing from 4 to 40 carbon atoms or greater and W represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 18 carbon atoms or greater; (iv) a triorganophosphite represented by the formula:   wherein each R<8> is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon radical; and (v) an organopolyphosphite containing two or more tertiary (trivalent) phosphorus atoms represented by the formula:   wherein X<1> represents a substituted or unsubstituted _n_-valent hydrocarbon bridging radical containing from 2 to 40 carbon atoms, each R<9> is the same or different and represents a divalent hydrocarbon radical containing from 4 to 40 carbon atoms, each R<10> is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 24 carbon atoms, _a_ and _b_ can be the same or different and each have a value of 0 to 6, with the proviso that the sum of _a_+_b_ is 2 to 6 and n equals _a_+_b_.