CN115521252A - 一种氨氯吡啶酸生产废渣的处理方法 - Google Patents
一种氨氯吡啶酸生产废渣的处理方法 Download PDFInfo
- Publication number
- CN115521252A CN115521252A CN202211165407.0A CN202211165407A CN115521252A CN 115521252 A CN115521252 A CN 115521252A CN 202211165407 A CN202211165407 A CN 202211165407A CN 115521252 A CN115521252 A CN 115521252A
- Authority
- CN
- China
- Prior art keywords
- reaction
- picloram
- production waste
- waste residue
- deamination
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002699 waste material Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000005595 Picloram Substances 0.000 title claims abstract description 46
- NQQVFXUMIDALNH-UHFFFAOYSA-N picloram Chemical compound NC1=C(Cl)C(Cl)=NC(C(O)=O)=C1Cl NQQVFXUMIDALNH-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 57
- 238000006481 deamination reaction Methods 0.000 claims abstract description 33
- 230000009615 deamination Effects 0.000 claims abstract description 10
- GXFRQLQUKBSYQL-UHFFFAOYSA-N 3,4,5,6-tetrachloropyridine-2-carboxylic acid Chemical compound OC(=O)C1=NC(Cl)=C(Cl)C(Cl)=C1Cl GXFRQLQUKBSYQL-UHFFFAOYSA-N 0.000 claims description 21
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 17
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 17
- 229940045803 cuprous chloride Drugs 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 15
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 15
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 15
- -1 pyrylium tetrafluoroborate Chemical compound 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910001507 metal halide Inorganic materials 0.000 claims description 5
- 150000005309 metal halides Chemical group 0.000 claims description 5
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 4
- 239000012320 chlorinating reagent Substances 0.000 claims description 4
- 229960003280 cupric chloride Drugs 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 229910001510 metal chloride Inorganic materials 0.000 claims description 3
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 3
- 229940098124 cesium chloride Drugs 0.000 claims description 2
- 239000003880 polar aprotic solvent Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 44
- 239000002253 acid Substances 0.000 abstract description 23
- 239000002994 raw material Substances 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000006193 diazotization reaction Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 21
- DLOOKZXVYJHDIY-UHFFFAOYSA-N 2,3,4,5-tetrachloropyridine Chemical compound ClC1=CN=C(Cl)C(Cl)=C1Cl DLOOKZXVYJHDIY-UHFFFAOYSA-N 0.000 description 20
- 239000012295 chemical reaction liquid Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 238000004321 preservation Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- ATHJTJOXOQJKEC-UHFFFAOYSA-N 6-amino-3,4,5-trichloropyridine-2-carboxylic acid Chemical compound NC1=NC(C(O)=O)=C(Cl)C(Cl)=C1Cl ATHJTJOXOQJKEC-UHFFFAOYSA-N 0.000 description 9
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 229940078552 o-xylene Drugs 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- RHPUJHQBPORFGV-UHFFFAOYSA-N 4-chloro-2-methylphenol Chemical group CC1=CC(Cl)=CC=C1O RHPUJHQBPORFGV-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/127—Preparation from compounds containing pyridine rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种氨氯吡啶酸生产废渣的处理方法,该方法以氨氯吡啶酸生产废渣为原料,经过脱氨、氯化反应将废渣转化为四氯吡啶酸,此产物可以循环用于氨氯吡啶酸的制备工艺中,从而完成了原料‑产品‑废渣‑原料‑产品的有效循环,实现了化学反应的原子经济性与物质的资源化利用,避免了废渣对环境的破坏,具有较高的经济效益和环境效益。而且本发明路线避免了传统工艺路线中的重氮化危险工艺,同时避免了大量废酸、废水的产生,更绿色、高效、安全可靠。本发明整体工艺简便,反应条件温和,通过调整反应条件,产品收率更高、质量更好,有利于工业化生产。
Description
技术领域
本发明涉及一种氨氯吡啶酸生产废渣的处理方法,特别涉及一种氨氯吡啶酸生产废渣经过脱氨反应和氯化反应转化为四氯吡啶酸重新资源化回用的处理方法。
背景技术
氨氯吡啶酸,化学名称为4-氨基-3,5,6-三氯吡啶甲酸,为一种内吸性除草剂,具有广阔的市场前景。氨氯吡啶酸一般是由3,4,5,6-四氯吡啶甲酸与氨水进行氨解反应制得,反应过程中主要发生4位氯基团的氨基置换,同时也会进行3位、5位和6位氯基团的氨基置换,尤其以6位的置换反应较为明显,在结晶工序中会产生氨氯吡啶酸废渣。
氨氯吡啶酸的一次生产废渣主要成分为4-氨基-3,5,6-三氯吡啶甲酸铵盐和6-氨基-3,4,5-三氯吡啶甲酸铵盐。一次生产废渣经分离提纯氨氯吡啶酸后产生的二次残渣中含有少量4-氨基-3,5,6-三氯吡啶甲酸(氨氯吡啶酸)和大部分的6-氨基-3,4,5-三氯吡啶甲酸。氨氯吡啶酸的一次生产废渣和一次生产废渣经分离提纯氨氯吡啶酸后产生的二次残渣统称为氨氯吡啶酸生产废渣,也可以称为氨氯吡啶酸废渣。
关于如何将氨氯吡啶酸生产废渣进行处理,目前国内外文献与专利报道较少。专利CN104649965、CN107474013中将氨氯吡啶酸废渣转化成其工业生产中间体3,4,5,6-四氯吡啶甲酸,其工艺均为重氮化工艺,该工艺具有危险性高,废酸量大,安全、环保方面风险较大的不足。
发明内容
本发明的目的在于提供一种氨氯吡啶酸生产废渣的处理方法,该方法以氨氯吡啶酸生产废渣为原料,经过脱氨、氯化反应将生产废渣转化为四氯吡啶酸,此产物可以循环用于氨氯吡啶酸的制备工艺中,从而完成了原料-产品-废渣-原料-产品的有效循环,实现了化学反应的原子经济性与物质的资源化利用,避免了废渣对环境的破坏,具有较高的经济效益和环境效益。
为了实现以上技术目的,本发明采用以下技术方案:
一种氨氯吡啶酸生产废渣的处理方法,该方法包括对氨氯吡啶酸生产废渣进行脱氨反应得到中间体、然后将中间体进行氯化反应得到四氯吡啶酸的步骤。
进一步的,所述氨氯吡啶酸生产废渣包括氨氯吡啶酸一次生产废渣或/和氨氯吡啶酸一次生产废渣经提纯后产生的二次生产废渣,废渣中含有6-氨基-3,4,5-三氯吡啶甲酸、氨氯吡啶酸等成分,主要为6-氨基-3,4,5-三氯吡啶甲酸。
进一步的,脱氨反应指的是:氨氯吡啶酸生产废渣与脱氨剂进行反应,得到中间体。氯化反应指的是:脱氨反应得到的中间体进一步与氯化试剂进行反应,得到四氯吡啶酸。
进一步的,以6-氨基-3,4,5-三氯吡啶甲酸为例,本发明的反应式如下:
进一步的,氨氯吡啶酸生产废渣与脱氨剂的摩尔比1:1-1.5,例如1:1、1:1.1、1:1.2、1:1.3、1:1.4、1:1.5。
进一步的,脱氨反应在催化剂存在下进行,催化剂为金属卤化物,卤化物可以是氯化物、氟化物、溴化物等,金属卤化物的金属可以为铜、铯等。
优选的,金属卤化物为金属氯化物,例如氯化铜、氯化亚铜、氯化铯等,更优选为氯化亚铜。
进一步的,脱氨反应的催化剂与氨氯吡啶酸生产废渣的摩尔比为0.1-1:1,例如0.1:1、0.2:1、0.3:1、0.4:1、0.5:1、0.6:1、0.7:1、0.8:1、0.9:1、1:1,优选为0.2:1。
进一步的,脱氨反应的温度为30-80℃,例如30℃、40℃、50℃、60℃、70℃、80℃,优选为50-60℃。
进一步的,氯化反应在氯化试剂下进行,所述氯化试剂为氯化氢气体、氯化镁、三甲基氯硅烷等,其中氯化氢气体更为绿色环保。其中,氯化试剂可以一次性加入,也可以连续性加入,也可以分批次加入。
进一步的,氨氯吡啶酸生产废渣与氯化试剂的摩尔比为1:1-1.5,例如1:1、1:1.1、1:1.2、1:1.3、1:1.4、1:1.5。
进一步的,氯化反应的温度为80-140℃,例如80℃、90℃、100℃、110℃、120℃、130℃、140℃,优选为80-120℃。
进一步的,脱氨反应和氯化反应均在溶剂存在下进行,脱氨反应和氯化反应的溶剂均可以选自极性非质子溶剂,例如乙腈、苯甲腈、邻二甲苯等。
进一步的,脱氨反应和氯化反应优选在同一反应容器内进行,生产废渣经脱氨反应得到中间体后,可以在反应产物中进一步加入氯化试剂进行反应,因此脱氨反应和氯化反应优选为同一溶剂。溶剂为反应提供反应介质,其用量可以根据需要进行选择,一般的氨氯吡啶酸生产废渣与溶剂的质量比为1:4-5。
本发明的优点在于:
1、本发明以氨氯吡啶酸生产废渣为原料, 经过脱氨、氯化反应将生产废渣转化为四氯吡啶酸,此产物可以循环用于氨氯吡啶酸的制备工艺中,从而完成了原料-产品-废渣-原料-产品的有效循环,实现了化学反应的原子经济性与物质的资源化利用,避免了废渣对环境的破坏,具有较高的经济效益和环境效益。
2、本发明以脱氨反应替代传统的重氮化反应,危险性降低,提高了反应的安全性,同时避免了重氮化反应时产生大量废酸、废水的问题,更绿色、经济、高效、安全可靠。
3、本发明整体工艺简便,反应条件温和,经济环保,通过对反应条件的优化,可以提高脱氨反应和氯化反应的转化率、选择性,提高所得产品的收率和纯度,提升产品质量,有利于工业化生产。
具体实施方式
下面结合实施例对本发明做进一步说明。应该明白的是,下述说明仅是为了解释本发明,并不对其内容进行限定。如无特别说明,所用浓度均为质量百分浓度。
本发明以氨氯吡啶酸生产废渣为原料,经脱氨反应得到中间体, 中间体经氯化得到产品四氯吡啶酸。生产废渣的主要成分为6-氨基-3,4,5-三氯吡啶甲酸及其同分异构体,分子量为242g/mol,四氯吡啶酸分子量为260.89g/mol。
以6-氨基-3,4,5-三氯吡啶甲酸为例,反应式如下 :
下面列举几个本发明的优选实施例,以对本发明的技术方案进行详细的说明。
下述实施例中,四氯吡啶酸收率的计算公式为:
四氯吡啶酸收率=[m(四氯吡啶酸)×Wt(四氯吡啶酸)/M(四氯吡啶酸)/n(6-氨基-3,4,5-三氯吡啶甲酸)×100%],其中m(四氯吡啶酸)表示四氯吡啶酸质量,Wt(四氯吡啶酸)表示四氯吡啶酸质量含量,M(四氯吡啶酸)表示四氯吡啶酸相对分子质量,n(6-氨基-3,4,5-三氯吡啶甲酸)表示6-氨基-3,4,5-三氯吡啶甲酸摩尔量。
四氯吡啶酸含量的测定方法为液相定量检测,四氯吡啶酸的选择性计算方法为:[四氯吡啶酸收率/6-氨基-3,4,5-三氯吡啶甲酸转化率]。
实施例1
将生产废渣100g、乙腈500g、氯化亚铜7.87g(0.2mol当量)投入到玻璃四口烧瓶中,开启搅拌,用油浴锅升温至50-60℃,加入80.06g吡喃鎓四氟硼酸盐,保温反应2h,后取样检测未转,未转<1%为合格;未转合格后将油浴锅升温至100-120℃,开始向体系中通入17.38g氯化氢气体进行氯化反应,控制氯化反应温度不超过120℃,通入完毕,保温1h,取样未转<1%为合格,合格后的反应液经脱溶、降温结晶、过滤、烘干后得到四氯吡啶酸干品101.26g,含量95.3%,选择性95.63%,收率94.03%。
实施例2
按照实施例1的方法进行操作,不同的是:氯化亚铜的加入量为3.93g(0.1mol当量)。具体步骤为:将废渣100g、乙腈500g、氯化亚铜3.93g(0.1mol当量)投入到玻璃四口烧瓶中,开启搅拌,用油浴锅升温至50-60℃,加入80.06g吡喃鎓四氟硼酸盐,保温反应2h;将油浴锅升温至100-120℃,开始向体系中通入17.38g氯化氢气体进行氯化反应,控制氯化反应温度不超过120℃,通入完毕,保温1h,取样未转<1%为合格,合格后的反应液经脱溶、降温结晶、过滤、烘干后得到四氯吡啶酸干品98.54g,含量93.08%,选择性93.75%,收率89.37%。
实施例3
按照实施例1的方法进行操作,不同的是:将氯化亚铜替换为0.2mol当量的氯化铜。具体步骤为:将废渣100g、乙腈500g、氯化铜10.68g(0.2mol当量)投入到玻璃四口烧瓶中,开启搅拌,用油浴锅升温至50-60℃,加入80.06g吡喃鎓四氟硼酸盐,保温反应2h;将油浴锅升温至100-120℃,开始向体系中通入17.38g氯化氢气体进行氯化反应,控制氯化反应温度不超过120℃,通入完毕,保温1h,取样未转<1%为合格,合格后的反应液经脱溶、降温结晶、过滤、烘干后得到四氯吡啶酸干品95.67g,含量93.2%,选择性90.88%,收率86.88%。
实施例4
按照实施例1的方法进行操作,不同的是:将氯化亚铜替换为0.2mol当量的氯化铯。具体步骤为:将废渣100g、乙腈500g、氯化铯13.38g(0.2mol当量)投入到玻璃四口烧瓶中,开启搅拌,用油浴锅升温至50-60℃,加入80.06g吡喃鎓四氟硼酸盐,保温反应2h;将油浴锅升温至100-120℃,开始向体系中通入17.38g氯化氢气体进行氯化反应,控制氯化反应温度不超过120℃,通入完毕,保温1h,取样未转<1%为合格,合格后的反应液经脱溶、降温结晶、过滤、烘干后得到四氯吡啶酸干品94.21g,含量93.9%,选择性90.82%,收率86.20%。
实施例5
按照实施例1的方法进行操作,不同的是:脱氨反应的温度为30-40℃。具体步骤为:将废渣100g、乙腈500g、氯化亚铜7.87g(0.2mol当量)投入到玻璃四口烧瓶中,开启搅拌,用油浴锅升温至30-40℃,加入80.06g吡喃鎓四氟硼酸盐,保温反应2h,未转合格;未转合格后将油浴锅升温至100-120℃,开始向体系中通入17.38g氯化氢气体进行氯化反应,控制氯化反应温度不超过120℃,通入完毕,保温1h,取样未转<1%为合格,合格后的反应液经脱溶、降温结晶、过滤、烘干后得到四氯吡啶酸干品92.93g,含量91.3%,选择性91.54%,收率82.67%。
实施例6
按照实施例1的方法进行操作,不同的是:脱氨反应的温度为70-80℃。具体步骤为:将废渣100g、乙腈500g、氯化亚铜7.87g(0.2mol当量)投入到玻璃四口烧瓶中,开启搅拌,用油浴锅升温至70-80℃,加入80.06g吡喃鎓四氟硼酸盐,保温反应2h,未转合格;未转合格后将油浴锅升温至100-120℃,开始向体系中通入17.38g氯化氢气体进行氯化反应,控制氯化反应温度不超过120℃,通入完毕,保温1h,取样未转<1%为合格,合格后的反应液经脱溶、降温结晶、过滤、烘干后得到四氯吡啶酸干品90.08g,含量89.4%,选择性80.81%,收率78.47%。
施例7
按照实施例1的方法进行脱氨反应,未转合格后将油浴锅升温至130-140℃,开始向体系中通入17.38g氯化氢气体进行氯化反应,控制氯化反应温度不超过140℃,通入完毕,保温1h,取样未转<1%为合格,合格后的反应液经脱溶、降温结晶、过滤、烘干后得到四氯吡啶酸干品90.71g,含量86.1%,选择性78.37%,收率76.1%。
实施例8
按照实施例1的方法进行脱氨反应,未转合格后将油浴锅升温至100-120℃,向体系中分批加入52.96g氯化镁固体进行氯化反应,控制氯化反应温度不超过120℃,保温1h,取样未转<1%为合格,合格后的反应液经脱溶、降温结晶、过滤、烘干后得到四氯吡啶酸干品97.71g,含量92.1%,选择性91.24%,收率87.69%。
实施例9
按照实施例1的方法进行操作,不同的是:氯化亚铜的加入量为19.67g(0.5mol当量)。具体步骤为:将废渣100g、乙腈500g、氯化亚铜19.67g(0.5mol当量)投入到玻璃四口烧瓶中,开启搅拌,用油浴锅升温至50-60℃,加入80.06g吡喃鎓四氟硼酸盐,保温反应2h,未转合格;未转合格后将油浴锅升温至100-120℃,开始向体系中通入17.38g氯化氢气体进行氯化反应,控制氯化反应温度不超过120℃,通入完毕,保温1h,取样未转<1%为合格,合格后的反应液经脱溶、降温结晶、过滤、烘干后得到四氯吡啶酸干品100.83g,含量94.92%,选择性95.13%,收率93.26%。
实施例10
按照实施例1的方法进行操作,不同的是:氯化亚铜的加入量为39.34g(1.0mol当量)。具体步骤为:将废渣100g、乙腈500g、氯化亚铜39.34g(1.0mol当量)投入到玻璃四口烧瓶中,开启搅拌,用油浴锅升温至50-60℃,加入80.06g吡喃鎓四氟硼酸盐,保温反应2h,未转合格;未转合格后将油浴锅升温至100-120℃,开始向体系中通入17.38g氯化氢气体进行氯化反应,控制氯化反应温度不超过120℃,通入完毕,保温1h,取样未转<1%为合格,合格后的反应液经脱溶、降温结晶、过滤、烘干后得到四氯吡啶酸干品100.95g,含量95.3%,选择性95.63%,收率93.74%。
实施例11
按照实施例1的方法进行脱氨反应,未转合格后将油浴锅升温至100-120℃,向体系滴加入60.44g三甲基氯硅烷进行氯化反应,滴加过程温度控制不超过120℃,滴加完毕,保温1h,取样未转<1%为合格,合格后的反应液经脱溶、降温结晶、过滤、烘干后得到四氯吡啶酸干品99.71g,含量94.1%,选择性95.13%,收率91.43%。
实施例12
按照实施例1的方法进行操作,不同的是:溶剂采用邻二甲苯。具体步骤为:将废渣100g、邻二甲苯500g、氯化亚铜7.87g(0.2mol当量)投入到玻璃四口烧瓶中,开启搅拌,用油浴锅升温至50-60℃,加入80.06g吡喃鎓四氟硼酸盐,保温反应2h,未转合格;未转合格后将油浴锅升温至100-120℃,开始向体系中通入17.38g氯化氢气体进行氯化反应,控制氯化反应温度不超过120℃,通入完毕,保温1h,取样未转<1%为合格,合格后的反应液经脱溶、降温结晶、过滤、烘干后得到四氯吡啶酸干品99.54g,含量95.08%,选择性95.95%,收率92.22%。
实施例13
按照实施例1的方法进行操作,不同的是:溶剂采用苯甲腈。具体步骤为:将废渣100g、苯甲腈500g、氯化亚铜7.87g(0.2mol当量)投入到玻璃四口烧瓶中,开启搅拌,用油浴锅升温至50-60℃,加入80.06g吡喃鎓四氟硼酸盐,保温反应2h,未转合格;未转合格后将油浴锅升温至100-120℃,开始向体系中通入17.38g氯化氢气体进行氯化反应,控制氯化反应温度不超过120℃,通入完毕,保温1h,取样未转<1%为合格,合格后的反应液经脱溶、降温结晶、过滤、烘干后得到四氯吡啶酸干品100.03g,含量95.06%,选择性96.19%,收率92.66%。
实施例14
按照实施例1的方法进行操作,不同的是:氯化反应温度为80-100℃。脱氨反应未转合格后,将油浴锅升温至80-100℃,开始向体系中通入17.38g氯化氢气体进行氯化反应,控制氯化反应温度不超过100℃,通入完毕,保温1h,取样未转<1%为合格,合格后的反应液经脱溶、降温结晶、过滤、烘干后得到四氯吡啶酸干品100.2g,含量94.96%,选择性96.70%,收率92.72%。
Claims (10)
1.一种氨氯吡啶酸生产废渣的处理方法,其特征是:包括对氨氯吡啶酸生产废渣进行脱氨反应得到中间体、然后将中间体进行氯化反应得到四氯吡啶酸的步骤。
2.根据权利要求 1 所述的处理方法,其特征是:所述氨氯吡啶酸生产废渣包括氨氯吡啶酸一次生产废渣或/和氨氯吡啶酸一次生产废渣经提纯后产生的二次生产废渣。
3.根据权利要求 1 所述的处理方法,其特征是:脱氨反应所用的脱氨剂为吡喃鎓四氟硼酸盐;优选的,氨氯吡啶酸生产废渣与脱氨剂的摩尔比1:1-1.5。
4.根据权利要求 1或3 所述的处理方法,其特征是:脱氨反应在催化剂存在下进行,催化剂为金属卤化物;优选的,金属卤化物为金属氯化物。
5.根据权利要求 4 所述的处理方法,其特征是:金属氯化物为氯化铜、氯化亚铜或氯化铯,优选为氯化亚铜。
6.根据权利要求 4所述的处理方法,其特征是:脱氨反应的催化剂与氨氯吡啶酸生产废渣的摩尔比为0.1-1:1,优选为0.2:1。
7.根据权利要求 1 所述的处理方法,其特征是:氯化反应在氯化试剂下进行;优选的,所述氯化试剂为氯化氢气体、氯化镁或三甲基氯硅烷。
8.根据权利要求 7所述的处理方法,其特征是:氨氯吡啶酸生产废渣与氯化试剂的摩尔比为1:1-1.5。
9.根据权利要求 1 、3、7或8所述的处理方法,其特征是:脱氨反应的温度为30-80℃,优选为50-60℃;氯化反应的温度为80-140℃,优选为80-120℃。
10.根据权利要求 1 所述的处理方法,其特征是:脱氨反应和氯化反应均在溶剂存在下进行;优选的,所用溶剂均选自极性非质子溶剂。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211165407.0A CN115521252A (zh) | 2022-09-23 | 2022-09-23 | 一种氨氯吡啶酸生产废渣的处理方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211165407.0A CN115521252A (zh) | 2022-09-23 | 2022-09-23 | 一种氨氯吡啶酸生产废渣的处理方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN115521252A true CN115521252A (zh) | 2022-12-27 |
Family
ID=84698672
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211165407.0A Pending CN115521252A (zh) | 2022-09-23 | 2022-09-23 | 一种氨氯吡啶酸生产废渣的处理方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115521252A (zh) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104628635A (zh) * | 2015-02-10 | 2015-05-20 | 湖南比德生化科技有限公司 | 一种从氨氯吡啶酸生产废渣中分离提纯出高含量氨氯吡啶酸的方法 |
CN104649965A (zh) * | 2015-02-10 | 2015-05-27 | 湖南比德生化科技有限公司 | 3,4,5,6-四氯吡啶甲酸的制备方法 |
CN107474013A (zh) * | 2016-06-08 | 2017-12-15 | 湖南比德生化科技股份有限公司 | 一种氨氯吡啶酸生产废渣选择性转化方法 |
CN111285800A (zh) * | 2020-02-07 | 2020-06-16 | 山东潍坊润丰化工股份有限公司 | 一种氨氯吡啶酸废渣的处理方法 |
-
2022
- 2022-09-23 CN CN202211165407.0A patent/CN115521252A/zh active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104628635A (zh) * | 2015-02-10 | 2015-05-20 | 湖南比德生化科技有限公司 | 一种从氨氯吡啶酸生产废渣中分离提纯出高含量氨氯吡啶酸的方法 |
CN104649965A (zh) * | 2015-02-10 | 2015-05-27 | 湖南比德生化科技有限公司 | 3,4,5,6-四氯吡啶甲酸的制备方法 |
CN107474013A (zh) * | 2016-06-08 | 2017-12-15 | 湖南比德生化科技股份有限公司 | 一种氨氯吡啶酸生产废渣选择性转化方法 |
CN111285800A (zh) * | 2020-02-07 | 2020-06-16 | 山东潍坊润丰化工股份有限公司 | 一种氨氯吡啶酸废渣的处理方法 |
Non-Patent Citations (2)
Title |
---|
CL EMENT GHIAZZA等: "Constitutional isomerism in heterocycles: A structural revision of benzofused isothiazoles", 《TETRAHEDRON》, vol. 120, pages 132888 * |
CLÉMENT GHIAZZA等: "Deaminative chlorination of aminoheterocycles", 《NATURE CHEMISTRY》, vol. 14, pages 78 - 84, XP037663177, DOI: 10.1038/s41557-021-00812-0 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Duan et al. | Palladium-catalyzed stereoselective reductive coupling reactions of organic halides with 7-heteroatom norbornadienes | |
CN111072517B (zh) | 一种4-氨基-2-三氟甲基苯腈的制备方法 | |
CN106589013B (zh) | 一种在液液两相体系中制备三氯蔗糖-6-乙酸酯的方法 | |
CN104788341B (zh) | 一种制备2,6-二氟苯腈的方法 | |
CN115521252A (zh) | 一种氨氯吡啶酸生产废渣的处理方法 | |
CN107235891B (zh) | 一种4-溴咔唑的制备方法 | |
US3984487A (en) | Preparation of petachloronitrobenzene | |
JP7482125B2 (ja) | 2,6-ジクロロベンゾニトリルの調製のためのプロセス | |
JPH0149137B2 (zh) | ||
CN111269144A (zh) | 一种氨基苯甲腈的制备方法 | |
US4508922A (en) | Process for the preparation of optionally halogenated anilines | |
CN109232398A (zh) | 一种农药中间体2-氯-5-甲基吡啶的制备方法 | |
CN115650877B (zh) | 一种制备2,2-二异丙基丙腈的工艺方法 | |
CN117486728B (zh) | 一种高效循环的氟化试剂及其制备方法与应用 | |
JPH0230298B2 (zh) | ||
CN110950809B (zh) | 一种芳基三唑啉酮化合物的合成后处理方法 | |
JPS6011986B2 (ja) | ジオキサジン系化合物の製造方法 | |
CN115197085B (zh) | 2-氨基-5-氯-n,3-二甲基苯甲酰胺的制备方法 | |
EP0164409B1 (en) | Method for making n-substituted nitrophthalimides | |
CN112479995A (zh) | 2-氯-n,n-二甲基烟酰胺的制备方法 | |
JPS638104B2 (zh) | ||
CN112500310A (zh) | 一种2-甲氧基-4,4’-二硝基苯酰替苯胺的制备方法 | |
JP4153573B2 (ja) | 1−ニトロベンジル−2−ピロールカルボキサルデヒドの製法 | |
JPH01153669A (ja) | 芳香族ニトリルの製造方法 | |
WO2023241960A1 (en) | A process for the photolytic chlorination of 3-halopyridine with molecular chlorine |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |