CN113198531A - 一种复合催化剂及制备邻氯苯甲酸的方法 - Google Patents
一种复合催化剂及制备邻氯苯甲酸的方法 Download PDFInfo
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- IKCLCGXPQILATA-UHFFFAOYSA-N 2-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Cl IKCLCGXPQILATA-UHFFFAOYSA-N 0.000 title claims abstract description 60
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- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 claims abstract description 12
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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Abstract
一种复合催化剂,包括醋酸钴、醋酸锰、醋酸锆、四溴乙烷;以重量比,醋酸钴∶醋酸锰∶醋酸锆∶四溴乙烷=1:0.5~3:0.5~3:0.5~3;一种制备邻氯苯甲酸的方法,以邻氯甲苯为原料,醋酸为溶剂,空气为氧化剂,使用复合催化剂,以重量比,邻氯甲苯∶醋酸∶复合催化剂=1:1~10:0.01~0.1,制备步骤包括:先混合,再将物料转入氧化釜,通空气加压至0.5~0.9MPa,反应温度150~190℃,反应结束得到邻氯苯甲酸混合液;然后转入脱酸釜,蒸馏出醋酸和水;在脱酸釜中升温,得到邻氯苯甲酸粗品,最后精馏;使用的混合釜、氧化釜、脱酸釜、脱酸釜、精馏釜均使用钛制成。本发明解决了传统的生产方法能耗和成本较高,生产时间过长以及在高温反应时收率不高的问题。
Description
技术领域
本发明涉及化学合成领域,尤其涉及一种制备邻氯苯甲酸的方法。
背景技术
邻氯苯甲酸是一种用途极广的农药、医药和燃料行业的重要中间体,在农药上主要用于合成杀虫剂(苏脲一号)和防霉剂,在医药上主要永夜合成抗精神病药奋乃静、拟肾上腺药曾鲁本辛和喘通、抗真菌药克霉唑、氯丙嗪、***和双氯灭痛等药物,是减量法和碘量法的标准试剂,用作胶黏剂和油漆的防腐剂,还可用于有机合成的原料、燃料及彩色胶片,其市场前景较为广阔。
邻氯苯甲酸的合成有多种路线,主要有重氮化法、氧化法、氯化水解法等合成方法。重氮化法是以苯酐为原料,首先与NaOH和NH4OH进行酰胺化反应,生产邻甲酰胺基苯甲酸钠,经NaOCl降解反应,生产邻氨基苯甲酸钠,中和,精制而得邻氨基苯甲酸,然后进行重氮化反应,所得重氮盐在亚铜盐催化下发生桑德迈耶尔反应,重氮基置换成氯基,得邻氯苯甲酸粗品经精制得成品。此法的反应条件温和,但工艺路线较长,成本高设备腐蚀严重,产生的废水、废气多,环境污染严重,已逐渐被淘汰。氧化法以邻氯甲苯为原料,采用氧化的方法制备邻氯苯甲酸,用钴、锰等作为催化剂,以低级脂肪族羧酸为溶剂,在加压下一步氧化而成。此法工艺路线短,废气废水少,成本低等优点,但生产周期长,产品后处理较为繁琐。氯化法以邻氯甲苯为原料,先在PCl3催化剂存在下通Cl2制得邻氯三氯甲苯,再水解为邻氯苯甲酸。催化光氯化法与重氮化法和氧化法相比具有工艺流程短,反应条件易于控制、收率高、成本低、环境污染小等诸多优点,但水解有大量废水产生。
中国专利(CN103601639A)公开了一种邻氯苯甲酸的合成工艺,以邻氯甲苯为原料,醋酸作为溶剂,在复合催化剂乙酸钴、乙酸锰和溴化钠的作用下加热升温至134~136℃;然后充入氧气进行反应,反应温度控制在135~145℃之间,反应压力为1.0Mpa,反应时间5.5~6.5小时;反应结束后降温,出料,降温,过滤,水洗,得到邻氯苯甲酸。采用该工艺,需要充入纯氧进行反应,用纯氧增加了成本,且纯氧的氧化反应剧烈,反应过程不易控制,易出现过氧化的情况;如果在更高的温度下,脱羧反应会增加,只能使用较低温度加长反应时间来保证产品收率,额外又增加了生产成本。
发明内容
本发明要解决的技术问题是针对现有技术的不足,提供一种催化剂及制备邻氯苯甲酸的方法,解决传统的生产方法能耗和成本较高,生产时间过长以及在高温反应时收率不高的问题。
本发明解决其技术问题所采用的技术方案是:
本发明提供一种复合催化剂,所述的复合催化剂包括醋酸钴、醋酸锰、四溴乙烷、醋酸锆;所述的复合催化剂中各成分按重量比,醋酸钴∶醋酸锰∶四溴乙烷∶醋酸锆=1:0.5~3:0.5~3:0.5~3。其中四溴乙烷作为复合催化剂中的引发剂,而醋酸锆还作为复合催化剂中的稳定剂。
本发明还提供一种制备邻氯苯甲酸的方法,以邻氯甲苯为原料,醋酸为溶剂,该法使用上述的复合催化剂,并利用空气为氧化剂;按重量比,邻氯甲苯∶醋酸∶复合催化剂=1:1~10:0.01~0.1。主要制备方法步骤包括:
混合:在混合釜中将含氯甲苯、醋酸和复合催化剂按比例计量,开动搅拌混合,并升温使含氯甲苯与溶剂互溶;
氧化:将混合物料转入氧化釜,通入空气加压,并保持氧化釜的压力为0.5~0.9MPa,控制反应温度在150~190℃,当尾气氧含量达15~20%时,反应结束,得到邻氯苯甲酸混合液;氧化生成的尾气进行有组织排放;加入的醋酸锆后能在150~190℃高温时明显降低脱羧反应,而高温时氧化反应速率也能大大提升,并且能保证产品收率。
脱酸:将邻氯苯甲酸混合液转入脱酸釜,加热至110~130℃蒸馏出醋酸和水,对反应剩余的醋酸进行浓缩回收,废水进行后续处理;在脱酸釜中继续升温至130~160℃,得到液态邻氯苯甲酸粗品。
精馏:将液态邻氯苯甲酸粗品转入精馏釜中精馏,得到成品邻氯苯甲酸。精馏后的残渣利用焚烧炉焚烧处理。
进一步地,为了原材料的充分混合溶解,在混合步骤中,控制混合釜中的温度为60~150℃。
进一步地,为了更好地保证精馏效果,在精馏步骤中,控制精馏釜中的温度为150~250℃,真空度为0.01~0.1MPa。
进一步地,为了防止设备腐蚀,所述的混合釜、氧化釜、脱酸釜、精馏釜均使用金属钛制成。
传统制备方法在氧化反应过程中,在达到一定温度后脱羧副反应随即发生,因此需控制氧化反应时的温度不宜过高,而复合催化剂中加入的醋酸锆能在高温时明显降低脱羧反应,稳定反应过程。
需注意的是,复合催化剂若加入过多,会出现过氧化,甚至出现燃烧反应,导致副产物增多,收率减少;若复合催化剂的配比使用不当,也会出现反应时间过长、副产物增多或过氧化等情况。
本发明的有益效果是:本发明方法中采用空气中的氧气是最廉价的氧化剂,不用化学氧化剂,也就没有对资源的要求,更没有由于使用化学氧化剂而产生的各种污染;同时使用空气能避免过度氧化,反应过程易于控制;催化剂方面采用复合型,能在高温环境下有效减少副反应的发生,在保证收率的同时反应时间大大缩短,在成本控制上有更大的优势;同时设备均采用钛制成,耐用抗腐蚀。
以下将结合附图和实施例,对本发明进行较为详细的说明。
附图说明
图1为本发明中制备邻氯苯甲酸的方法流程图。
具体实施方式
如图1所示,本发明方法主要流程包括混合、氧化、脱酸和精馏,先在混合釜中将含氯甲苯、醋酸和复合催化剂按比例计量,开动搅拌混合,并升温使含氯甲苯与溶剂互溶;再将混合物料转入氧化釜,通入空气加压进行氧化反应得到邻氯苯甲酸混合液;然后将邻氯苯甲酸混合液转入脱酸釜,加热蒸馏出醋酸和水,对反应剩余的醋酸进行浓缩回收,废水进行后续处理,得到液态邻氯苯甲酸粗品;最后将液态邻氯苯甲酸粗品转入精馏釜中精馏,得到成品邻氯苯甲酸,精馏后的残渣利用焚烧炉焚烧处理。
实施例1:
先在混合釜中加入含氯甲苯200kg、醋酸600kg和复合催化剂6kg,其中复合催化剂中醋酸钴1.88kg,醋酸锰1.5kg,四溴乙烷1.7kg,醋酸锆0.94kg,并开动搅拌混合,并升温控制混合釜中的温度为120℃,使含氯甲苯与溶剂完全互溶;
然后将混合物料转入氧化釜,通入空气加压,并保持氧化釜的压力为0.5MPa,控制反应温度在160℃,当尾气氧含量达15~20%时,反应结束得到邻氯苯甲酸混合液,反应时间为120分钟;
然后将邻氯苯甲酸混合液转入脱酸釜,加热至120℃蒸馏出醋酸和水;在脱酸釜中继续升温至140℃,得到液态邻氯苯甲酸粗品。
最后将液态邻氯苯甲酸粗品转入精馏釜中精馏,控制精馏釜中的温度为200℃,真空度为0.1MPa,最后得到成品邻氯苯甲酸239.6kg。
实施例2:
先在混合釜中加入含氯甲苯200kg、醋酸800kg和复合催化剂20kg,其中复合催化剂中醋酸钴3.22kg,醋酸锰6.44kg,四溴乙烷3.22kg,醋酸锆7.08kg,并开动搅拌混合,并升温控制混合釜中的温度为130℃,使含氯甲苯与溶剂完全互溶;
然后将混合物料转入氧化釜,通入空气加压,并保持氧化釜的压力为0.9MPa,控制反应温度在190℃,当尾气氧含量达15~20%时,反应结束得到邻氯苯甲酸混合液,反应时间为60分钟;
然后将邻氯苯甲酸混合液转入脱酸釜,加热至120℃蒸馏出醋酸和水;在脱酸釜中继续升温至160℃,得到液态邻氯苯甲酸粗品。
最后将液态邻氯苯甲酸粗品转入精馏釜中精馏,控制精馏釜中的温度为220℃,真空度为0.1MPa,最后得到成品邻氯苯甲酸238.6kg。
实施例3:
先在混合釜中加入含氯甲苯100kg、醋酸300kg和复合催化剂1kg,其中复合催化剂中醋酸钴0.2kg,醋酸锰0.36kg,四溴乙烷0.14kg,醋酸锆0.3kg,并开动搅拌混合,并升温控制混合釜中的温度为120℃,使含氯甲苯与溶剂完全互溶;
然后将混合物料转入氧化釜,通入空气加压,并保持氧化釜的压力为0.7MPa,控制反应温度在170℃,当尾气氧含量达15~20%时,反应结束得到邻氯苯甲酸混合液,反应时间为90分钟;
然后将邻氯苯甲酸混合液转入脱酸釜,加热至120℃蒸馏出醋酸和水;在脱酸釜中继续升温至140℃,得到液态邻氯苯甲酸粗品。
最后将液态邻氯苯甲酸粗品转入精馏釜中精馏,控制精馏釜中的温度为200℃,真空度为0.1MPa,最后得到成品邻氯苯甲酸119.6kg。
实施例4:
先在混合釜中加入含氯甲苯300kg、醋酸600kg和复合催化剂15kg,其中复合催化剂中醋酸钴3.13kg,醋酸锰7.8kg,四溴乙烷1.56kg,醋酸锆2.49kg,并开动搅拌混合,并升温控制混合釜中的温度为120℃,使含氯甲苯与溶剂完全互溶;
然后将混合物料转入氧化釜,通入空气加压,并保持氧化釜的压力为0.8MPa,控制反应温度在180℃,当尾气氧含量达15~20%时,反应结束得到邻氯苯甲酸混合液,反应时间为60分钟;
然后将邻氯苯甲酸混合液转入脱酸釜,加热至120℃蒸馏出醋酸和水;在脱酸釜中继续升温至140℃,得到液态邻氯苯甲酸粗品。
最后将液态邻氯苯甲酸粗品转入精馏釜中精馏,控制精馏釜中的温度为200℃,真空度为0.1MPa,最后得到成品邻氯苯甲酸361.2kg。
实施例5:
先在混合釜中加入含氯甲苯100kg、醋酸300kg和复合催化剂8kg,其中复合催化剂中醋酸钴1.7kg,醋酸锰4.25kg,四溴乙烷1.19kg,醋酸锆0.85kg,并开动搅拌混合,并升温控制混合釜中的温度为120℃,使含氯甲苯与溶剂完全互溶;
然后将混合物料转入氧化釜,通入空气加压,并保持氧化釜的压力为0.6MPa,控制反应温度在150℃,当尾气氧含量达15~20%时,反应结束得到邻氯苯甲酸混合液,反应时间为110分钟;
然后将邻氯苯甲酸混合液转入脱酸釜,加热至120℃蒸馏出醋酸和水;在脱酸釜中继续升温至140℃,得到液态邻氯苯甲酸粗品。
最后将液态邻氯苯甲酸粗品转入精馏釜中精馏,控制精馏釜中的温度为200℃,真空度为0.1MPa,最后得到成品邻氯苯甲酸120.1kg。
上面结合附图对本发明进行了示例性描述,显然本发明具体实现并不受上述方式限制,只要采用了本发明的方法构思和技术方案进行的各种改进,或未经改进直接应用于其它场合的均落在本发明的保护范围之内。
Claims (5)
1.一种复合催化剂,其特征是,所述的复合催化剂包括醋酸钴、醋酸锰、四溴乙烷、醋酸锆;所述的复合催化剂中各成分按重量比,醋酸钴∶醋酸锰∶四溴乙烷∶醋酸锆=1:0.5~3:0.5~3:0.5~3。
2.一种制备邻氯苯甲酸的方法,以邻氯甲苯为原料,醋酸为溶剂,其特征是,该法使用权利要求1所述的复合催化剂,并利用空气为氧化剂;按重量比,邻氯甲苯∶醋酸∶复合催化剂=1:1~10:0.01~0.1,主要制备方法步骤包括:
(1)混合:在混合釜中将含氯甲苯、醋酸和复合催化剂按比例计量,开动搅拌混合,并升温使含氯甲苯与溶剂互溶;
(2)氧化:将混合物料转入氧化釜,通入空气加压,并保持氧化釜的压力为0.5~0.9MPa,控制反应温度在150~190℃,当尾气氧含量达15~20%时,反应结束,得到邻氯苯甲酸混合液;
(3)脱酸:将邻氯苯甲酸混合液转入脱酸釜,加热蒸馏出醋酸和水;在脱酸釜中继续升温,得到液态邻氯苯甲酸粗品。
(4)精馏:将液态邻氯苯甲酸粗品转入精馏釜中精馏,得到成品邻氯苯甲酸。
3.根据权利要求2所述的制备邻氯苯甲酸的方法,其特征是,在混合步骤中,控制混合釜中的温度为60~150℃。
4.根据权利要求2所述的制备邻氯苯甲酸的方法,其特征是,在精馏步骤中,控制精馏釜中的温度为150~250℃,真空度为0.01~0.1MPa。
5.根据权利要求2所述的制备邻氯苯甲酸的方法,其特征是,所述的混合釜、氧化釜、脱酸釜、精馏釜均使用钛制成。
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CN111744452A (zh) * | 2020-08-05 | 2020-10-09 | 上海常恒生物医药科技有限公司 | 一种2-氯苯甲酸的连续流合成装置及合成2-氯苯甲酸的方法 |
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CN111744452A (zh) * | 2020-08-05 | 2020-10-09 | 上海常恒生物医药科技有限公司 | 一种2-氯苯甲酸的连续流合成装置及合成2-氯苯甲酸的方法 |
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