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    • 4. 发明授权
    • Method of recovering halide values from carbonylation reaction mixtures
    • 从羰基化反应混合物中回收卤化物值的方法
    • US4582929A
    • 1986-04-15
    • US686174
    • 1984-12-24
    • Robert A. DeVries
    • Robert A. DeVries
    • C07C51/10
    • C07C51/10
    • This invention is a process for the carbonylation of an organic halide to prepare a carbonyl-containing compound, and recovery of halogen values in a useful form which comprises(a) contacting an organic halide with carbon monoxide and an esterifying agent, a primary or secondary amine, or hydrogen gas, in an inert organic solvent in the presence of a water-insoluble tertiary amine or pyridine ring-containing compound, and a catalytic amount of a Group VIII metal catalyst, under conditions such that an organic ester, amide or aldehyde is prepared and the halide generated in the process forms a salt with tertiary amine or pyridine compound wherein the halide is bromine or iodine;(b) separating the organic ester, amide or aldehyde from the reaction mixture which contains the tertiary amine or pyridine compound-halide salt;(c) contacting the reaction mixture containing the tertiary amine or pyridine compound-halide salt mixture with a concentrated aqueous solution of an alkali metal base or alkaline earth metal base under conditions such that an aqueous solution of an alkali metal halide or an alkaline earth metal halide and reaction solution containing the tertiary amine or pyridine compound is prepared;(d) separating the aqueous solution from the reaction mixture; and(e) contacting the aqueous solution containing the alkaline earth metal halide salt or alkali metal halide salt with chlorine under conditions such that an alkali metal chloride salt or alkaline earth metal chloride salt and elemental halide is prepared.
    • 本发明是用于羰基化有机卤化物以制备含羰基化合物的方法,以及以有用形式回收卤素值的方法,其包括(a)使有机卤化物与一氧化碳和酯化剂,一级或二级 胺或氢气,在惰性有机溶剂中,在不溶于水的叔胺或含吡啶环的化合物和催化量的VIII族金属催化剂存在下,在使有机酯,酰胺或醛 在该方法中产生的卤化物与叔胺或吡啶化合物形成盐,其中卤化物是溴或碘; (b)从含有叔胺或吡啶化合物 - 卤化物盐的反应混合物中分离有机酯,酰胺或醛; (c)将含有叔胺或吡啶化合物 - 卤化物盐混合物的反应混合物与碱金属碱或碱土金属碱的浓盐水接触,使碱金属卤化物或碱土金属的水溶液 制备含有叔胺或吡啶化合物的卤化物和反应溶液; (d)从反应混合物中分离水溶液; 和(e)在制备碱金属氯化物盐或碱土金属氯化物盐和元素卤化物的条件下使含有碱土金属卤化物盐或碱金属卤化物盐的水溶液与氯接触。
    • 8. 发明授权
    • Separation process for anhydrous HCl and HBr by thermal cleavage
    • 通过热裂解分离无水HCl和HBr的方法
    • US4830846A
    • 1989-05-16
    • US150184
    • 1988-01-29
    • Herbert C. Jackson, Jr.Robert A. DeVriesHughie R. Frick
    • Herbert C. Jackson, Jr.Robert A. DeVriesHughie R. Frick
    • C01B7/07C01B7/09
    • C01B7/0706C01B7/093
    • A method for the separation of anhydrous HCl and HBr from mixtures of the two acids comprising treating the mixture with a hindered pyridine to form a mixture of hindered pyridine salts of the acids, and heating the mixture of salts to a temperature at which thermal cleavage of at least the hydrochloride salt is induced. The hindered pyridines are defined as aromatic compounds having one or more nitrogen atoms in an aromatic ring, or a polymer with pendant aromatic moieties having one or more nitrogens in an aromatic ring, having an appropriate degree of steric hindrance such that the salt formed by the nitrogen atom of the aromatic compound and a strong protic base will undergo dissociation to the aromatic compound and the protic acid at a temperature below the decomposition temperature of the aromatic compound. The formation of salts and their cleavage can be done as either a one-step or two-step process. The separation process is based on the fact that the HCl salts are less stable to heat than the HBr salts, and thus will cleave at a faster rate at any given temperature. It is possible to carry out the thermal cleavage at a temperature sufficient to induce cleavage of only the HCl salts, of both simultaneously, or at two separate sequential temperatures, to cleave only the HCl salts first and then the remaining HBr salts.
    • 一种从两种酸的混合物中分离无水HCl和HBr的方法,包括用受阻吡啶处理混合物以形成酸的受阻吡啶盐的混合物,并将盐的混合物加热至热裂解 至少引起盐酸盐。 受阻吡啶被定义为在芳香环中具有一个或多个氮原子的芳族化合物,或具有在芳香环中具有一个或多个氮的侧面芳族部分的聚合物,具有适当的空间位阻程度,使得由 芳族化合物的氮原子和强质子碱将在低于芳族化合物的分解温度的温度下解离成芳族化合物和质子酸。 盐的形成及其裂解可以作为一步法或两步法进行。 分离过程基于HCl盐比HBr盐不太稳定的事实,因此在任何给定温度下以更快的速率裂解。 可以在足以诱发仅同时或两个独立的连续温度的HCl盐的裂解的温度下进行热裂解,以首先仅切割HCl盐,然后仅剩下其余的HBr盐。