WO2021088456A1 - 一种双季铵盐的连续化生产方法 - Google Patents

一种双季铵盐的连续化生产方法 Download PDF

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WO2021088456A1
WO2021088456A1 PCT/CN2020/109679 CN2020109679W WO2021088456A1 WO 2021088456 A1 WO2021088456 A1 WO 2021088456A1 CN 2020109679 W CN2020109679 W CN 2020109679W WO 2021088456 A1 WO2021088456 A1 WO 2021088456A1
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ammonium salt
amine
reaction
continuous
stage
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French (fr)
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程终发
周响
李响
王宁宁
齐晓婧
陈成效
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山东泰和水处理科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
    • C07C209/12—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of quaternary ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/40—Static mixers
    • B01F25/42—Static mixers in which the mixing is affected by moving the components jointly in changing directions, e.g. in tubes provided with baffles or obstructions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/80—Mixing plants; Combinations of mixers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/80—Mixing plants; Combinations of mixers
    • B01F33/81—Combinations of similar mixers, e.g. with rotary stirring devices in two or more receptacles
    • B01F33/811—Combinations of similar mixers, e.g. with rotary stirring devices in two or more receptacles in two or more consecutive, i.e. successive, mixing receptacles or being consecutively arranged
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/80—Mixing plants; Combinations of mixers
    • B01F33/836—Mixing plants; Combinations of mixers combining mixing with other treatments
    • B01F33/8362—Mixing plants; Combinations of mixers combining mixing with other treatments with chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/242—Tubular reactors in series
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
    • 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
    • C07D213/20—Quaternary compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C07D215/10—Quaternary compounds

Definitions

  • the patent of the invention relates to the technical field of fine chemicals, in particular to a continuous production method of double quaternary ammonium salt.
  • Double quaternary ammonium salt is a product developed on the basis of single quaternary ammonium salt. It is a broad-spectrum bactericide. Its bactericidal ability is stronger than that of single quaternary ammonium salt such as 1227. Its principle of action is the same as that of single quaternary ammonium salt.
  • the positive charge is selectively adsorbed by the negatively charged bacteria on the surface, and enters the cell membrane through the cell surface through permeation and diffusion, thereby affecting the semi-permeability of the cell membrane, and further penetrating into the cell, inactivating cell enzymes, and unable to produce protein enzymes , To denature the protein so as to achieve the effect of killing bacterial cells.
  • double quaternary ammonium salt fungicide Compared with the monoquaternary ammonium salt, the double quaternary ammonium salt fungicide not only has the characteristics of high efficiency, low toxicity, and less susceptibility to changes in pH, but also has the characteristics of not being prone to drug resistance.
  • the structure of double quaternary ammonium salt generally contains three parts: an alkyl chain or a heterocyclic terminal hydrophobic group, a hydrophilic group composed of two quaternary ammonium cations, and a linker.
  • the linker generally includes polymethylene and p-xylene. Group and polyoxyethylene group, located in the middle of the double quaternary ammonium salt molecule, play a role in connecting two hydrophilic groups.
  • double quaternary ammonium salts have been used as fungicides in fresh water, sea water, wastewater, industrial water treatment and other fields. From the practical application point of view, the performance of mismatched double quaternary ammonium salts is generally better than that of symmetrical double quaternary ammonium salts. .
  • CN101531635B discloses an imidazoline asymmetric biquaternary ammonium salt and a preparation method thereof. The method uses diethylenetriamine and long-chain alkyl organic acid to synthesize alkyl imidazolines under xylene conditions, and uses long-chain alkyl tertiary amines.
  • Ethyl lauric acid tertiary amine, and the intermediate long-chain alkyl monoquaternary ammonium salt to synthesize an ester group-containing asymmetric diquaternary ammonium salt (Fine Chemical Industry, 2004).
  • the synthesis process generally has the problems of long reaction cycle and large use of organic solvents, resulting in high production costs, low resource utilization and environmental protection in the existing processes.
  • the high processing cost limits the large-scale industrial production of double quaternary ammonium salt products.
  • the patent of the present invention provides a continuous, environmentally friendly, continuous production method of diquaternary ammonium salt.
  • a continuous production method of double quaternary ammonium salt which specifically includes:
  • the mixture After premixing the amine R 1 , the linking group C and pure water, the mixture is uniformly mixed through the first-stage static mixer at a uniform speed, and after the reaction through the first-stage continuous reactor, the intermediate monoquaternary ammonium salt aqueous solution is obtained after reaching the reaction end point ;
  • the amine R 1 and the amine R 2 are one of the following amines: alkyl dimethyl tertiary amines with an alkyl carbon chain of 10-20, alkyl imidazolines, pyridine and its alkyl derivatives, quinone
  • the linking group C is a linear alkane with halogenated at both ends, a linear alcohol with an odd number of carbons halogenated at both ends, methyl/ethyl ether with halogenated at both ends, epihalohydrin, etc.;
  • the alcohol is methanol and ethanol.
  • the ratio of the amount of amine R 1 , amine R 2 and the amount of the linking group C n amine R1 : n amine R2 : n c is 0.8 to 1.5: 0.8 to 1.5:1; preferably n amine R1 : n Amine R2 : n c is (0.9 to 1.2): (0.9 to 1.2): 1, more preferably n amine R1 : n amine R2 : n c is (0.95 to 1.05): (0.95 to 1.05):1.
  • the pure water feeding amount is 10-50% of the total mass of other feeding materials.
  • reaction temperature of the continuous reactor is controlled at 60-120°C. Preferably 80 ⁇ 120°C
  • the raw material liquid changes from turbidity to clear as the end of the reaction.
  • the continuous reactor is a closed tubular reactor.
  • a second-stage static mixer is installed in the first-stage and second-stage continuous reactor, and the intermediate monoquaternary ammonium salt aqueous solution and the amine R 2 are passed into the second-stage static mixer for mixing and then passed into the second-stage continuous reactor for reaction.
  • the raw materials are mixed in the first-stage static mixer to prevent the local raw material concentration ratio from being too high and side reaction products appearing.
  • the oil phase (raw material) and the water phase (quaternary ammonium salt intermediate) are mixed in the two-stage static mixer to increase the contact area of the two phases to prevent overheating and insufficient reaction of local reactions.
  • the present invention realizes the industrialized assembly line production of continuous feeding, continuous mixing, continuous reaction, and continuous discharging through static mixer and continuous reactor;
  • Figure 1 is a reaction flow chart of the invention patent.
  • the dodecyl dimethyl tertiary amine is added at a constant rate of 111.8kg/h, and the mixture is passed through the second stage. After mixing in the static mixer, it enters the two-stage continuous reactor for reaction. After 4.03 hours of reaction, the materials are pumped into the dilution kettle, and a certain amount of methanol is added to dilute into N-dodecyl propylene diamine with a mass fraction of 70 ⁇ 1%.
  • the ammonium chloride product based on one reaction cycle, 1482.4 kg of N-dodecyl propylene diamine diammonium chloride solution with a mass fraction of 70.11% is obtained, and the ammonium salt content is 0.55%.
  • the material was flowed from the first-stage continuous reactor to the second-stage static mixer. At this time, the tetradecyldimethyl was added at a constant rate of 126.5kg/h.
  • Tertiary amine the mixture is mixed by the two-stage static mixer and then enters the two-stage continuous reactor for reaction. After the reaction for 4.12h, the material is pumped into the dilution kettle, and a certain amount of ethanol is added to dilute into a diquaternary ammonium salt with a mass fraction of 70 ⁇ 1%
  • the product based on one reaction cycle, obtains 1594.0 kg of an asymmetric biquaternary ammonium salt solution with a mass fraction of 70.43% and an ammonium salt content of 0.63%.
  • the cetyl dimethyl tertiary amine was added at a constant rate of 152.5 kg/h, and the mixture was passed through the second stage. After mixing in a two-stage static mixer, it enters a two-stage continuous reactor for reaction. After 4.06 hours of reaction, the material is pumped into the dilution kettle, and a certain amount of methanol is added to dilute into a diquaternary ammonium salt product with a mass fraction of 70 ⁇ 1%, which is calculated as a reaction cycle , 1547.1 kg of asymmetric biquaternary ammonium salt solution with a mass fraction of 70.67% was obtained, and the ammonium salt content was 0.52%.
  • the mixing kettle Into the mixing kettle, add the materials at a uniform rate at a flow rate of 85.2kg/h of 4-n-hexylpyridine, 62.1kg/h of 1,3-dichloropropane, and 57.5kg/h of pure water. At the same time, start the stirring. After stirring for 10 minutes, the mixture The material is pumped into the first-stage static mixer at a constant speed with a flow rate of 258.8kg/h, and the temperature in the continuous reactor is controlled to 118 ⁇ 2°C through the jacket. The materials are mixed by the first-stage static mixer and enter the first-stage continuous reactor at a uniform speed for reaction After the reaction for 3.91h, the material changed from turbidity to clarification.
  • the material was flowed from the first-stage continuous reactor to the second-stage static mixer. At this time, the tetradecyldimethyl tertiary amine was added at a constant rate of 139.2kg/h. After mixing by the two-stage static mixer, it enters the two-stage continuous reactor for reaction. After 4.22h of reaction, the material is pumped into the dilution kettle, and a certain amount of pure water is added to dilute into a diquaternary ammonium salt product with a mass fraction of 50 ⁇ 1%. Based on the reaction period, 2174.8 kg of asymmetric biquaternary ammonium salt solution with a mass fraction of 50.30% was obtained, and the ammonium salt content was 0.55%.
  • the material was pumped into the secondary continuous reactor at a constant rate of 228.5kg/h, and at the same time, the tetradecyl group was pumped at a constant rate of 126.5kg/h.
  • Dimethyl tertiary amine the mixture is reacted in the secondary continuous reactor.
  • the material flows out from the outlet of the secondary continuous reactor, and the material is pumped into the dilution tank, and a certain amount of ethanol is added to dilute to 70 ⁇ 1% by mass.
  • a certain amount of ethanol is added to dilute to 70 ⁇ 1% by mass.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明专利采用先生成单季铵盐中间体，再生成目标双季铵盐产品的生产方式，整个生产过程主要通过静态混合器和连续反应器来实现连续进料、连续混料、连续反应、连续出料的连续化生产。本发明专利生产方法简单，易于操作，可合成多种双季铵盐，通过连续化生产方式极大提高设备利用率，缩短生产周期。本发明在生产过程中避免了有机溶剂的使用和回收处理，整个过程无三废产生，绿色环保。

Description

一种双季铵盐的连续化生产方法 技术领域
本发明专利涉及精细化学品技术领域，特别涉及一种双季铵盐的连续化生产方法。
背景技术
双季铵盐是在单季铵盐基础上发展起来的产品，属广谱杀菌剂，其杀菌能力要比单季铵盐如1227强，其作用原理与单季铵盐一样，是分子中的正电荷被表面荷负电的细菌选择性吸附，通过渗透和扩散作用，穿过细胞表面进入细胞膜，从而影响细胞膜的半渗透作用，并进一步穿入细胞内部，使细胞酶钝化，不能产生蛋白质酶，使蛋白质变性从而达到杀死细菌细胞的作用。与单季铵盐相比，双季铵盐杀菌剂不但具有高效、低毒、不易受酸碱度变化影响等特点，还具有不易产生抗药性的特点。双季铵盐的结构一般包含烷基链或杂环组成的端基疏水基、两个季铵正离子组成的亲水基和连接基三部分，连接基一般有聚亚甲基、对二甲苯基和聚氧乙烯基等组成，位于双季铵盐分子的中间，起到连接两个亲水基的作用。近年来，双季铵盐作为杀菌剂开始应用于淡水、海水、废水、工业水处理等多个领域，从实际应用来看，不对成双季铵盐的使用性能普遍优于对称双季铵盐。
目前，针对双季铵盐的合成研究已取得一定成果，尤其在不对成双季铵盐上。CN101531635B公布了一种咪唑啉不对称双季铵盐及其制备方法，该方法以二乙烯三胺好长链烷基有机酸在二甲苯条件下合成烷基咪唑啉，以长链烷基叔胺和环氧氯丙烷在乙醇条件下合成N-(3-氯-2-羟丙基)-N,N-二甲基长链烷基季铵盐中间体，再与烷基咪唑啉在乙醇条件下合成出咪唑啉不对称双季铵盐。蒋斌等以咪唑啉为母体，环氧氯丙烷为连接基合成了一种含咪唑啉环的不对称双季铵盐(精细化工，2009)。与此同时，含有不对称烷基脂肪链的双季铵盐也逐渐成为研究热点。李杰等以十二胺、甲酸和甲醛合成中间体长链叔胺，在乙醇条件下再与1,3-二溴丙烷合成了双季铵盐杀菌剂(化学工程师，2005)。王留成等以十烷基二甲基叔胺、十二烷基二甲基叔胺和1,2-二溴乙烷，在异丙醇条件下，合成了一种C10-C2-C12型不 对称双季铵盐表面活性剂(郑州大学学报，2010)。徐群等在一种新型的双子表面活性剂的合成中，利用十二烷基二甲基叔胺、盐酸、环氧氯丙烷，在乙醇条件下，和不同烷基链烷基叔胺合成一系列含较长疏水链的不对称双季铵盐(西华师范大学学报，2004)。徐群等利用长链烷基叔胺、盐酸和环氧氯丙烷生成中间体长链烷基单季铵盐，用月桂酸和2-二甲基乙醇以二甲苯做溶剂，酯化合成二甲基月桂酸乙基叔胺，再与中间体长链烷基单季铵盐合成一种含酯基不对称双季铵盐(精细化工，2004)。有关双季铵盐的合成工艺已经取得了一定的进展，但是还不够成熟，合成工艺普遍存在反应周期长、大量使用有机溶剂的问题，造成现有工艺的生产成本高，资源利用率低，环保处理成本高，限制了双季铵盐产品的大规模工业化生产。
发明内容
为了克服上述现有技术的不足，本发明专利提供了一种可连续化、绿色环保的双季铵盐的连续化生产方法。
一种双季铵盐的连续化生产方法，具体包括：
(1)将胺R 1、连接基C、纯水预混合后，按匀速通过一级静态混合器混合均匀，通过一级连续反应器反应后，到达反应终点后得到中间体单季铵盐水溶液；
(2)将中间体单季铵盐和胺R 2，连续进入二级连续反应器内反应，二级连续反应器出口得双季铵盐水溶液，再经纯水或醇稀释后得到不同含量规格的双季铵盐产品。
其中，所述胺R 1、胺R 2为以下胺中的一种：含烷基碳链10～20的烷基二甲基叔胺、烷基咪唑啉、吡啶及其烷基衍生物、喹啉及其烷基衍生物；所述连接基C为两端卤代的直链烷烃，两端卤代的奇数碳直链醇，两端卤代的甲/乙醚，环氧卤丙烷等；所述醇为甲醇、乙醇。
其中，所述投料胺R 1、胺R 2和连接基C的物质的量之比n 胺R1：n 胺R2：n c为0.8～1.5：0.8～1.5：1；优选为n 胺R1：n 胺R2：n c为(0.9～1.2)：(0.9～1.2)：1，更进一步优选为n 胺R1：n 胺R2：n c为(0.95～1.05)：(0.95～1.05)：1。
所述纯水投料量为其他投料总质量的10～50％。
其中，所述连续反应器反应温度控制在60～120℃。优选为80～120℃
其中，原料通过连续反应器时，原料液由浑浊变为澄清为反应终点。
其中，所述的连续反应器为封闭管式反应器。
其中，在一二级连续反应器中加装二级静态混合器，中间体单季铵盐水溶液和胺R 2通入二级静态混合器进行混合后再通入二级连续反应器反应。
工业化连续化合成不对称季铵盐，去掉现有技术中使用的醇溶剂，改用水作为原料之一，将现有技术中的单相反应改为两相反应，增大了反应速度、改变了反应平衡；反应终点易于明确，方便掌握反应进度。
一级静态混合器中混匀原料，防止局部原料浓度配比过高，出现副反应产物。二级静态混合器中混匀油相(原料)与水相(季铵盐中间体)，增加两相接触面积，防止局部反应过热和反应不充分。
本发明专利有益效果为：
1、本发明通过静态混合器和连续反应器来实现连续进料、连续混料、连续反应、连续出料的工业化流水线生产；
2、采用纯水作用原料之一，避免了使用现有技术中的有机溶剂，提高了产率，且能通过原料的浑浊程度，明确反应终点，从而控制在连续反应器中的反应时间。
附图说明
图1为本发明专利的反应流程图。
具体实施方式
实施例1
向混料釜中按十二烷基二甲基叔胺101.2kg/h、1,3-二氯丙烷56.5kg/h、纯水57.5kg/h的流量匀速加入物料，同时开启搅拌，10min后，将混合物料以220.5kg/h的流量匀速泵入一级静态混合器，通过夹套控制连续反应器内温度为118±2℃，物料经一级静态混合器混合后匀速进入一级连续反应器内反应，反应3.78h后，将物料从一级连续反应器流向二级静态混合器，此时以111.8kg/h的流量匀速加入十二烷基二甲基叔胺，混合物料经二级静态混合器混合后进 入二级连续反应器反应，反应4.03h后，物料泵入稀释釜，加入一定量的甲醇稀释成质量分数70±1％的N-十二烷基亚丙基二胺双氯化铵产品，以一个反应周期计，得质量分数70.11％的N-十二烷基亚丙基二胺双氯化铵溶液1482.4kg，铵盐含量0.55％。
实施例2
向混料釜中按十二烷基二甲基叔胺101.2kg/h、1,3-二氯丙醇64.5kg/h、纯水57.5kg/h的流量匀速加入物料，同时开启搅拌，搅拌10min后，将混合物料以228.5kg/h的流量匀速泵入一级静态混合器，通过夹套控制连续反应器内温度为118±2℃，物料经一级静态混合器混合后匀速进入一级连续反应器内反应，反应4.02h后，物料由浑浊变澄清，将物料从一级连续反应器流向二级静态混合器，此时以126.5kg/h的流量匀速加入十四烷基二甲基叔胺，混合物料经二级静态混合器混合后进入二级连续反应器反应，反应4.12h后，物料泵入稀释釜，加入一定量的乙醇稀释成质量分数70±1％的双季铵盐产品，以一个反应周期计，得质量分数70.43％的不对称双季铵盐溶液1594.0kg，铵盐含量0.63％。
实施例3
向混料釜中按喹啉66.2kg/h、1,3-二氯丙醇69.7kg/h、纯水57.5kg/h的流量匀速加入物料，同时开启搅拌，搅拌10min后，将混合物料以196.9kg/h的流量匀速泵入一级静态混合器，通过夹套控制连续反应器内温度为118±2℃，物料经一级静态混合器混合后匀速进入一级连续反应器内反应，反应3.85h后，物料由浑浊变澄清，将物料从一级连续反应器流向二级静态混合器，此时以152.5kg/h的流量匀速加入十六烷基二甲基叔胺，混合物料经二级静态混合器混合后进入二级连续反应器反应，反应4.06h后，物料泵入稀释釜，加入一定量的甲醇稀释成质量分数70±1％的双季铵盐产品，以一个反应周期计，得质量分数70.67％的不对称双季铵盐溶液1547.1kg，铵盐含量0.52％。
实施例4
向混料釜中按4-正己基吡啶85.2kg/h、1,3-二氯丙烷62.1kg/h、纯水57.5kg/h的流量匀速加入 物料，同时开启搅拌，搅拌10min后，将混合物料以258.8kg/h的流量匀速泵入一级静态混合器，通过夹套控制连续反应器内温度为118±2℃，物料经一级静态混合器混合后匀速进入一级连续反应器内反应，反应3.91h后，物料由浑浊变澄清，将物料从一级连续反应器流向二级静态混合器，此时以139.2kg/h的流量匀速加入十四烷基二甲基叔胺，混合物料经二级静态混合器混合后进入二级连续反应器反应，反应4.22h后，物料泵入稀释釜，加入一定量的纯水稀释成质量分数50±1％的双季铵盐产品，以一个反应周期计，得质量分数50.30％的不对称双季铵盐溶液2174.8kg，铵盐含量0.55％。
对比例1
保持连续反应器内温度在88±2℃，其他条件不变，均同实施例2，以一个反应周期计，得质量分数70.11％的不对称双季铵盐溶液1600.3kg，铵盐含量15.17％。
对比例2
向反应釜中投加十二烷基二甲基叔胺101.2kg、1,3-二氯丙醇64.5kg、纯水57.5kg，同时开启搅拌混合和均匀，保持搅拌，反应釜迅速升温至118±2℃，反应4h后，向反应釜中缓慢加入十四烷基二甲基叔胺123.4kg，继续在118±2℃温度下，搅拌反应4h，物料泵入稀释釜，加入一定量的乙醇稀释成质量分数70.25％的双季铵盐产品1603.5kg，铵盐含量0.59％。
对比例3
向混料釜中按十二烷基二甲基叔胺101.2kg/h、1,3-二氯丙醇64.5kg/h、纯水57.5kg/h的流量匀速加入物料，同时开启搅拌，搅拌10min后，将混合物料以228.5kg/h的流量匀速泵入一级静态混合器，通过夹套控制连续反应器内温度为118±2℃，物料经一级静态混合器混合后匀速进入一级连续反应器内反应，反应4.02h后，物料由浑浊变澄清，将物料以228.5kg/h的流量匀速泵入二级连续反应器，同时以126.5kg/h的流量匀速泵入十四烷基二甲基叔胺，混合物料在二级连续反应器反应，4.12h后，物料从二级连续反应器出口流出，物料泵入稀释釜，加入一定量的乙醇稀释成质量分数70±1％的双季铵盐产品，以一个反应周期计，得质量分数 70.68％的不对称双季铵盐溶液1556.6kg，铵盐含量2.48％。
对比例4
向混料釜中按十二烷基二甲基叔胺71kg/h、1,3-二氯丙醇43kg/h、纯水57kg/h的流量匀速加入物料，同时开启搅拌，20min后，将混合物料以171kg/h的流量匀速泵入一级连续反应器内反应，通过夹套控制一级连续反应器内温度为118±2℃，反应3.97h后，物料由浑浊变澄清，将物料泵入稀释釜，加入一定量的水稀释成质量分数40±1％的单季铵盐水溶液。以一个反应周期计，得质量分数40.12％的十二烷基二甲基氯化铵溶液785.1kg，铵盐含量0.48％，1,3-二氯丙醇含量0.66％，N-十二烷基亚丙基二胺双氯化铵含量2.83％。

Claims (7)

  1. 一种双季铵盐的连续化生产方法，其特征在于，具体包括：
    (1)将胺R 1、连接基C、纯水预混合后，按匀速通过一级静态混合器混合均匀，通过一级连续反应器反应后，到达反应终点后得到中间体单季铵盐水溶液；
    (2)将中间体单季铵盐和胺R 2，连续进入二级连续反应器内反应，二级连续反应器出口得双季铵盐水溶液，再经纯水或醇稀释后得到不同含量规格的双季铵盐产品。
  2. 根据权利要求1所述的一种双季铵盐的连续化生产方法，其特征在于，所述胺R 1、胺R 2为以下胺中的一种：含烷基碳链10～20的烷基二甲基叔胺、烷基咪唑啉、吡啶及其烷基衍生物、喹啉及其烷基衍生物；所述连接基C为两端卤代的直链烷烃，两端卤代的奇数碳直链醇，两端卤代的甲/乙醚，环氧卤丙烷等；所述醇为甲醇、乙醇。
  3. 根据权利要求1所述的一种双季铵盐的连续化生产方法，其特征在于，所述投料胺R 1、胺R 2和连接基C的物质的量之比n 胺R1：n 胺R2：n c为0.8～1.5：0.8～1.5：1；所述纯水投料量为其他投料总质量的10～50％。
  4. 根据权利要求1所述的一种双季铵盐的连续化生产方法，其特征在于，所述连续反应器反应温度控制在60～120℃。
  5. 根据权利要求1所述的一种双季铵盐的连续化生产方法，其特征在于，原料通过连续反应器时，原料液由浑浊变为澄清为反应终点。
  6. 根据权利要求1所述的一种双季铵盐的连续化生产方法，其特征在于，所述的连续反应器为封闭管式反应器。
  7. 根据权利要求1或6任一所述的一种双季铵盐的连续化生产方法，其特征在于，在一二级连续反应器中加装二级静态混合器，中间体单季铵盐水溶液和胺R 2通入二级静态混合器进行混合后再通入二级连续反应器反应。
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113582861A (zh) * 2021-09-03 2021-11-02 上海有火虫动力技术有限公司 一种双子多羟基季铵盐改性松香表面活性剂的制备方法
CN114807804A (zh) * 2022-03-09 2022-07-29 仙桃市环美化工有限公司 一种多功能防爆剂
CN115594593A (zh) * 2022-09-09 2023-01-13 四川博利恒药业有限公司（Cn） 一种苯扎氯铵生产工艺

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110746308B (zh) * 2019-11-06 2022-04-08 山东泰和水处理科技股份有限公司 一种双季铵盐的连续化生产方法
CN111408319B (zh) * 2020-03-26 2022-01-28 北京理工大学 一种制备对叔丁基甲苯的方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105875606A (zh) * 2014-12-24 2016-08-24 秦皇岛胜利化工有限公司 氯化双十二烷基二甲基羟丙基双季铵盐杀菌剂
CN106543014A (zh) * 2016-10-18 2017-03-29 中国石油化工股份有限公司 一种双季铵盐阳离子表面活性剂的合成方法
CN106674018A (zh) * 2015-11-06 2017-05-17 中国石油化工股份有限公司 一种合成不对称双季铵盐的方法及其应用
CN106674017A (zh) * 2015-11-06 2017-05-17 中国石油化工股份有限公司 一种不对称双季铵盐的合成方法及其应用
CN108840803A (zh) * 2018-07-11 2018-11-20 山东泰和水处理科技股份有限公司 一种不对称双季铵盐杀菌剂的合成方法
CN110746308A (zh) * 2019-11-06 2020-02-04 山东泰和水处理科技股份有限公司 一种双季铵盐的连续化生产方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1276367A (zh) * 1999-06-05 2000-12-13 中国石化集团齐鲁石油化工公司 一种不饱和季铵盐的制备方法
SE0104346L (sv) * 2001-12-21 2003-06-22 Akzo Nobel Nv Process för kontinuerlig kvartärnering av tertiära aminer med en alkylhalid

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105875606A (zh) * 2014-12-24 2016-08-24 秦皇岛胜利化工有限公司 氯化双十二烷基二甲基羟丙基双季铵盐杀菌剂
CN106674018A (zh) * 2015-11-06 2017-05-17 中国石油化工股份有限公司 一种合成不对称双季铵盐的方法及其应用
CN106674017A (zh) * 2015-11-06 2017-05-17 中国石油化工股份有限公司 一种不对称双季铵盐的合成方法及其应用
CN106543014A (zh) * 2016-10-18 2017-03-29 中国石油化工股份有限公司 一种双季铵盐阳离子表面活性剂的合成方法
CN108840803A (zh) * 2018-07-11 2018-11-20 山东泰和水处理科技股份有限公司 一种不对称双季铵盐杀菌剂的合成方法
CN110746308A (zh) * 2019-11-06 2020-02-04 山东泰和水处理科技股份有限公司 一种双季铵盐的连续化生产方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113582861A (zh) * 2021-09-03 2021-11-02 上海有火虫动力技术有限公司 一种双子多羟基季铵盐改性松香表面活性剂的制备方法
CN114807804A (zh) * 2022-03-09 2022-07-29 仙桃市环美化工有限公司 一种多功能防爆剂
CN115594593A (zh) * 2022-09-09 2023-01-13 四川博利恒药业有限公司（Cn） 一种苯扎氯铵生产工艺

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