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    • 3. 发明授权
    • Process for production of allyl carboxylate
    • 生产烯丙基羧酸酯的方法
    • US4567292A
    • 1986-01-28
    • US695024
    • 1985-01-25
    • Nobuyuki NagatoKenichiro MakiTomoe UematsuRyoji Ishioka
    • Nobuyuki NagatoKenichiro MakiTomoe UematsuRyoji Ishioka
    • C07C67/05
    • C07C67/055
    • A process for producing an allyl carboxylate comprising the step of reacting propylene, oxygen or oxygen-containing gas, and a lower saturated carboxylic acid in the presence of a catalyst at a temperature of 100.degree. C. to 300.degree. C. and a pressure of 0 to 30 atm (gauge) in a vapor phase. The catalyst is prepared by supporting, on a carrier, at least one alkali metal acetate and at least one bivalent palladium salt in the presence of: (A) at least one organic base selected from the group consisting of (i) aliphatic amines having the formula: ##STR1## wherein R.sup.1, R.sup.2, and R.sup.3 may be the same or different and represent hydrogen, or an alkyl group having 1 to 10 carbon atoms or benzyl group optionally substituted with --CN, --OR, --COOR, or a --N(R).sub.2 group wherein R is H or an alkyl group having 1 to 3 carbon atoms, or any two groups of R.sup.1, R.sup.2, and R.sup.3 may together form a ring provided that R.sup.1, R.sup.2, and R.sup.3 are not simultaneously hydrogen; (ii) aromatic amines having the formula: ##STR2## wherein X represent --R, --CN, --OR, --COOR, --NO.sub.2, or --N(R).sub.2 wherein R is the same as defined above, R.sup.2 and R.sup.3 are the same as defined above; and (iii) nitrogen-containing cyclic compounds having the formula: ##STR3## wherein X is the same as defined above; and/or (B) at least one carboxylic acid having the formula:Y--CH.sub.2).sub.n COOHwherein Y represents --OR, --CN, --COOR, --CH(R)NH.sub.2, --COR, --N(CH.sub.2 COOH).sub.2, --NHCH.sub.2 COOH, or --CH(R.sup.1)X group wherein R, R.sup.1, and X are the same as defined in (A) above, and n is an integer of 1 to 4.This catalyst has a high activity and a long durability and can produce the desired allyl carboxylate at a high selectivity.
    • 一种制备烯丙基羧酸酯的方法,包括在催化剂存在下,在100℃至300℃的温度下,使丙烯,氧或含氧气体和较低饱和羧酸反应的步骤, 0〜30atm(表压)气相。 所述催化剂是通过在载体上负载至少一种碱金属乙酸盐和至少一种二价钯盐来制备的:(A)至少一种有机碱,所述有机碱选自:(i)具有 式:其中R 1,R 2和R 3可以相同或不同,表示氢,或具有1-10个碳原子的烷基或任选被-CN,-OR,-COOR或 - N(R)2基团,其中R为H或具有1至3个碳原子的烷基,或任何两个R 1,R 2和R 3可以一起形成环,条件是R 1,R 2和R 3不同时为氢; (ii)具有下式的芳香胺:其中X表示-R,-CN,-OR,-COOR,-NO 2或-N(R)2,其中R与上述定义相同,R 2和R 3为 与上述相同; 和(iii)具有下式的含氮环状化合物:其中X与上述定义相同; 和/或(B)至少一种具有下式的羧酸:Y-CH 2)n COOH其中Y表示-OR,-CN,-COOR,-CH(R)NH 2,-COR,-N(CH 2 COOH) -NHCH 2 COOH或-CH(R 1)X基团,其中R,R 1和X与上述(A)中所定义相同,n为1至4的整数。该催化剂具有高活性和长的耐久性, 可以以高选择性产生所需的烯丙基羧酸酯。
    • 5. 发明授权
    • Process for production of epichlorohydrin
    • 表氯醇生产工艺
    • US4634784A
    • 1987-01-06
    • US741053
    • 1985-06-04
    • Nobuyuki NagatoHideki MoriKenichiro MakiRyoji Ishioka
    • Nobuyuki NagatoHideki MoriKenichiro MakiRyoji Ishioka
    • C07C29/62C07D301/26C07D303/08
    • C07D301/26C07C29/62
    • A process for producing epichlorohydrin comprising the steps of:(a) reacting allyl alcohol with chlorine at a temperature of -30.degree. C. to 20.degree. C. under a pressure of 0 to 10 atm (gauge) in an aqueous hydrogen chloride solution containing more than 45% but not more than 70% by weight of hydrogen chloride to form 2,3-dichloro-1-propanol;(b) separating at least a portion of the hydrogen chloride by heating the reaction mixture obtained at step (a) to recover the hydrogen chloride in the form of gas;(c) recycling the hydrogen chloride recovered at step (b) to step (a);(d) separating the resultant liquid mixture after recovering at least the portion of the hydrogen chloride at step (b) into an aqueous phase and an oil phase by cooling the resultant liquid mixture to a temperature of 40.degree. C. or less;(e) recycling at least a portion of the separated aqueous phase at step (d) to step (a); and(f) reacting the oil phase separated at step (d) directly or after increasing the purity of 2,3-dichloro-1-propanol contained in the oil phase by a separation operation with an aqueous alkaline solution or suspension at a temperature of 40.degree. C. to 110.degree. C. to form epichlorohydrin.According to this process, the desired epichlorohydrin can be industrially and advantageously produced at a high yield and selectivity.
    • 一种制备表氯醇的方法,包括以下步骤:(a)在0至10atm(表压)的压力下,在-30℃至20℃的温度下,使烯丙醇与氯反应, 大于45重量%但不大于70重量%的氯化氢以形成2,3-二氯-1-丙醇; (b)通过加热步骤(a)获得的反应混合物来分离至少一部分氯化氢以回收气体形式的氯化氢; (c)将步骤(b)回收的氯化氢再循环到步骤(a); (d)在步骤(b)将至少一部分氯化氢回收至水相和油相后,将所得液体混合物冷却至40℃或更低的温度,分离所得液体混合物; (e)在步骤(d)至步骤(a)中将至少一部分分离的水相再循环; 和(f)使步骤(d)分离的油相与在碱性溶液或悬浮液中分离操作之后,在油相中包含的2,3-二氯-1-丙醇的纯度提高之后,在步骤(d) 40℃至110℃以形成表氯醇。 根据该方法,所需的表氯醇可以在工业上有利地以高产率和选择性生产。