阅读说明：本技术 一种微通道反应器合成烷基二苯醚二磺酸钠的方法 (Method for synthesizing alkyl diphenyl ether disulfonic acid sodium by micro-channel reactor ) 是由 施晓旦 赵锡亮 尹东华 于 2021-11-12 设计创作，主要内容包括：本发明公开了一种微通道反应器合成烷基二苯醚二磺酸钠的方法,在浓硫酸的催化下,α-烯烃和二苯醚通过在微通道反应器内反应得到单烷基二苯醚二磺酸钠粗产品,后经pH调节、含量调节得到产品。本发明的一种微通道反应器合成单烷基二苯醚二磺酸钠的方法,替代了传统的釜式滴加的工艺条件,通过引进微通道反应器,可实现连续高效地合成反应,缩短反应时间,节约生产成本；微通道反应器可智能远程控制,可有效节约人力,降低人力成本；本发明方法生产的产品纯度大于98％,反应收率大于88％,与传统工艺相比,具有高转化率、低能耗等优点。(The invention discloses a method for synthesizing sodium alkyl diphenyl ether disulfonate by a microchannel reactor. The method for synthesizing the sodium monoalkyl diphenyl ether disulfonate by the microchannel reactor replaces the traditional kettle-type dripping process condition, can realize continuous and efficient synthesis reaction by introducing the microchannel reactor, shortens the reaction time and saves the production cost; the microchannel reactor can be intelligently and remotely controlled, so that the labor can be effectively saved, and the labor cost is reduced; the product produced by the method has the purity of more than 98 percent and the reaction yield of more than 88 percent, and has the advantages of high conversion rate, low energy consumption and the like compared with the traditional process.)

1. A method for synthesizing alkyl diphenyl ether disulfonic acid sodium by a micro-channel reactor is characterized by comprising the following steps: under the catalysis of concentrated sulfuric acid, alpha-olefin and diphenyl ether react in the microchannel reactor module 1 to obtain an intermediate, then a discharge hole of the module 1 is connected with a feed inlet of the module 2, so that the intermediate and a sulfonating agent react in the module 2 to obtain a crude product of monoalkyl diphenyl ether disulfonic acid sodium, and finally the product is obtained through pH adjustment and content adjustment. Compared with the traditional chemical equipment, the microchannel reactor has a large specific surface area, and a sufficient contact area is formed between a fluid and a wall, so that the heat exchange efficiency and the reaction rate are remarkably improved.

2. The method for synthesizing sodium alkyl diphenyl ether disulfonate by using the microchannel reactor as recited in claim 1, wherein the method comprises the following steps:

step 1) mixing diphenyl ether and catalyst concentrated sulfuric acid, and uniformly stirring to obtain a mixture;

step 2) respectively pumping the mixture obtained in the step 1 and alpha-olefin into a micro-channel reactor reaction module 1 through a metering pump 1 and a metering pump 2;

step 3), adjusting the reaction temperature in the reaction module 1 to a proper reaction temperature, wherein the reaction residence time is 0.5min-2 min;

step 4), pumping the intermediate generated in the reaction module 1 into the reaction module 2, and simultaneously pumping the sulfonating agent into the reaction module 2 through a metering pump 3;

step 5), adjusting the reaction temperature in the reaction module 2 to a proper reaction temperature, wherein the reaction residence time is 0.5-2 min;

and 6) introducing the crude sodium alkyl diphenyl ether disulfonate product synthesized by the reaction module 2 into an adjusting device, adding liquid alkali to adjust the pH value, and adding distilled water to adjust the effective content to obtain the sodium alkyl diphenyl ether disulfonate product.

3. The method for synthesizing sodium alkyl diphenyl ether disulfonate by using the microchannel reactor as recited in claim 1, wherein: the alpha-olefin is one or more of CnH2n +2, and n is 8-18.

4. The method for synthesizing sodium alkyl diphenyl ether disulfonate by using the microchannel reactor as recited in claim 1, wherein: the molar ratio of the alpha-olefin to the diphenyl ether is 2.5 to 0.5, preferably 2.1 to 0.95.

5. The method for synthesizing sodium alkyl diphenyl ether disulfonate by using the microchannel reactor as recited in claim 1, wherein: the sulfonating agent is one of concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid and sulfur trioxide.

6. The method for synthesizing sodium alkyl diphenyl ether disulfonate by using the microchannel reactor as recited in claim 1, wherein: the molar ratio of the intermediate to the sulfonating agent is 2-3.

7. The method for synthesizing sodium alkyl diphenyl ether disulfonate by using the microchannel reactor as recited in claim 1, wherein: the microchannel reactor is made of one or more of quartz glass, high borosilicate glass, silicon carbide or RPTFE.

8. The method for synthesizing sodium alkyl diphenyl ether disulfonate by using the microchannel reactor as recited in claim 1, wherein: the inner diameter of the pipeline of the micro-channel reactor is 10-200 mu m.

9. The method for synthesizing sodium alkyl diphenyl ether disulfonate by using the microchannel reactor as recited in claim 2, wherein: in the step 1, the mass ratio of the diphenyl ether to the concentrated sulfuric acid catalyst is 1: 0.005-0.05.

10. The method for synthesizing sodium alkyl diphenyl ether disulfonate by using the microchannel reactor as recited in claim 2, wherein: in the step 2, the temperature of the reaction module 1 is 60-95 ℃; in the step 5, the temperature of the reaction module 2 is 15-80 ℃.

Technical Field

The invention relates to the technical field of compound synthesis, in particular to a method for synthesizing sodium alkyl diphenyl ether disulfonate by a microchannel reactor.

Background

The alkyl diphenyl ether disulfonic acid sodium is a novel and high-efficiency anionic surfactant with double hydrophilic groups, which is called CR-MADS for short. The special molecular structure of the emulsifier enables the emulsifier to have good water solubility, good solubility and stability in strong acid, strong alkali, inorganic salt and bleaching agent solutions, and the emulsifier gradually becomes an excellent substitute for emulsifying agents such as TX-10, K-12, OP-10 and the like.

The product has special application in the fields of emulsion polymerization, textile printing and dyeing, dye and auxiliary agent industry, cleaning agent components, petroleum industry, phenolic resin industry, coating industry, pesticide industry, building industry, film production, electroplating industry, rubber industry, environmental protection and the like.

The traditional preparation method of the alkyl diphenyl ether disulfonic acid sodium is divided into two steps, wherein the first step is alkylation reaction; the second step is sulfonation. The main achievements of the existing research all adopt kettle type reaction, and the defects are that: the method has the advantages of complex reaction process, long reaction period, more reaction equipment, high catalyst treatment cost, serious equipment corrosion, more byproducts and large wastewater amount.

Disclosure of Invention

In view of the above-mentioned drawbacks of the prior art, the present invention is directed to a method for synthesizing sodium alkyl diphenyl ether disulfonate by using a microchannel reactor.

The purpose of the invention is realized by the following technical scheme:

a method for synthesizing alkyl diphenyl ether sodium disulfonate by a microchannel reactor is characterized by comprising the following steps:

step 1) mixing diphenyl ether with catalyst concentrated sulfuric acid, and uniformly stirring;

step 2) respectively pumping the mixture obtained in the step 1 and alpha-olefin into a micro-channel reactor reaction module 1 through a metering pump 1 and a metering pump 2;

step 3), in the reaction module 1, the reaction temperature is 60-95 ℃, and the reaction retention time is 0.5-2 min;

step 4), pumping the intermediate generated in the reaction module 1 into the reaction module 2, and simultaneously pumping the sulfonating agent into the reaction module 2 through a metering pump 3;

step 5), in the reaction module 2, the reaction temperature is 15-80 ℃, and the reaction residence time is 0.5-2 min;

and 6) introducing the crude sodium alkyl diphenyl ether disulfonate product synthesized by the reaction module 2 into an adjusting device, adding liquid alkali to adjust the pH value, and adding distilled water to adjust the effective content to obtain the sodium alkyl diphenyl ether disulfonate product.

Further, the molar ratio of the intermediate to the sulfonating agent is 2-3, preferably 2.1-2.5.

Further, the molar ratio of the alpha-olefin to the diphenyl ether is 2.5 to 0.95, preferably 2 to 1.

Further, the sulfonating agent is one of concentrated sulfuric acid, fuming sulfuric acid and sulfur trioxide.

Furthermore, the microchannel reactor is made of quartz glass, high borosilicate glass, hastelloy, silicon carbide or RPTFE.

Further, the inner diameter of the pipeline of the microchannel reactor is 10-200 μm.

Further, in the step 1, the mass ratio of the diphenyl ether to the concentrated sulfuric acid catalyst is 1: 0.005-0.05.

Further, module 1 and module 2 are same material and structure, and the module chip material is pressureless sintering carborundum, and purity is more than 99.5%, and inner structure is 5 laminar structures, double-deck reaction channel + double-deck heat transfer passageway, and the reaction layer is integrative with the heat transfer layer is integrated, whole seamless bonding.

The invention has the beneficial effects that: the method for synthesizing the sodium alkyl diphenyl ether disulfonate by the microchannel reactor replaces the traditional kettle-type process condition, and adopts the microchannel reactor and a new process for optimizing the raw material adding proportion, so that the reaction condition is milder, the reaction time is shortened, the production cost is saved, and the generation of byproducts, industrial wastewater and waste acid is reduced; the microchannel reactor can be intelligently and remotely controlled, so that the labor can be effectively saved, and the cost is reduced; the product produced by the method has the purity of more than 98 percent and the reaction yield of more than 88 percent, and has the advantages of high conversion rate, low energy consumption and the like compared with the traditional process.

Drawings

FIG. 1 is a production flow chart of the present invention.

Detailed Description

The process of the present invention is illustrated below by means of specific examples, but the present invention is not limited thereto. The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.

Example 1

Step 1) mixing 1.7kg of diphenyl ether and 50g of catalyst concentrated sulfuric acid and uniformly stirring;

step 2) pumping the mixture obtained in the step 1 and 2.45kg of 1-heptene into a reaction module 1 of the microchannel reactor through a metering pump 1 and a metering pump 2 respectively;

step 3), in the reaction module 1, the reaction temperature is 60 ℃, and the reaction retention time is 1 min;

step 4) pumping the intermediate generated in the reaction module 1 into the reaction module 2, and simultaneously pumping 2.48kg of oleum (25%) into the reaction module 2 by a metering pump 3;

step 5), in the reaction module 2, the reaction temperature is 80 ℃, and the reaction retention time is 1 min;

and step 6) pouring the crude product of the sodium diheptanyl diphenyl ether disulfonate synthesized by the reaction module 2 into a separating funnel, standing and separating lower-layer waste acid, then pouring the mixture into a double-neck flask, dropwise adding a 32% sodium hydroxide solution until the pH value is 6.5-8.5, and then adding distilled water to adjust the effective content to be 49% -50% to obtain the sodium diheptanyl diphenyl ether disulfonate solution. The yield was 88.71% based on diphenyl ether.

Wherein the microchannel reactor is made of quartz glass; the inner diameter of the pipe of the microchannel reactor is 10 μm.

Example 2

Step 1) mixing 1.7kg of diphenyl ether and 20g of catalyst concentrated sulfuric acid and uniformly stirring;

step 2) respectively pumping the mixture obtained in the step 1 and 1.54kg of 1-dodecene into a reaction module 1 of the microchannel reactor through a metering pump 1 and a metering pump 2;

step 3), in the reaction module 1, the reaction temperature is 80 ℃, and the reaction retention time is 0.5 min;

step 4) pumping the intermediate generated in the reaction module 1 into the reaction module 2, and simultaneously pumping 2.75kg of oleum (15%) into the reaction module 2 by a metering pump 3;

step 5), in the reaction module 2, the reaction temperature is 60 ℃, and the reaction retention time is 0.5 min;

and step 6) pouring the crude product of the sodium dodecyl diphenyl ether disulfonate synthesized by the reaction module 2 into a separating funnel, standing and separating lower-layer waste acid, then pouring into a double-neck flask, dropwise adding a 32% sodium hydroxide solution until the pH value is 6.5-8.5, and then adding distilled water to adjust the effective content to be 49% -50% to obtain the sodium dodecyl diphenyl ether disulfonate solution. The yield was 89.95% based on diphenyl ether.

Wherein the microchannel reactor is made of high borosilicate glass; the inside diameter of the tube of the microchannel reactor was 200. mu.m.

Example 3

Step 1) mixing 1.7kg of diphenyl ether and 10g of catalyst concentrated sulfuric acid and uniformly stirring;

step 2) respectively pumping the mixture obtained in the step 1 and 4.17kg of 1-hexadecene into a reaction module 1 of the microchannel reactor through a metering pump 1 and a metering pump 2;

step 3), in the reaction module 1, the reaction temperature is 95 ℃, and the reaction retention time is 1 min;

step 4), pumping the intermediate generated in the reaction module 1 into the reaction module 2, and simultaneously pumping 1.60kg of sulfur trioxide into the reaction module 2 through a metering pump 3;

step 5), in the reaction module 2, the reaction temperature is 15 ℃, and the reaction retention time is 1 min;

and step 6) pouring the crude product of the sodium dicetyl diphenyl ether disulfonate synthesized by the reaction module 2 into a double-neck flask, dropwise adding a 32% sodium hydroxide solution until the pH value is 6.5-8.5, and then adding distilled water to adjust the effective content to 49% -50% to obtain the sodium dicetyl diphenyl ether disulfonate solution. The yield was 90.68% based on diphenyl ether.

Wherein the microchannel reactor is made of RPTFE; the inner diameter of the pipe of the microchannel reactor is 100 μm.

Example 4

Step 1) mixing 1.7kg of diphenyl ether and 5g of catalyst concentrated sulfuric acid and uniformly stirring;

step 2) pumping the mixture obtained in the step 1 and 2.53kg of 1-octadecene into a micro-channel reactor reaction module 1 through a metering pump 1 and a metering pump 2 respectively;

step 3), in the reaction module 1, the reaction temperature is 95 ℃, and the reaction retention time is 2 min;

step 4), pumping the intermediate generated in the reaction module 1 into the reaction module 2, and simultaneously pumping 2.94kg of sulfur trioxide into the reaction module 2 through a metering pump 3;

step 5), in the reaction module 2, the reaction temperature is 15 ℃, and the reaction retention time is 2 min;

and step 6) pouring the crude product of the sodium octadecyl diphenyl ether disulfonate synthesized by the reaction module 2 into a separating funnel, standing and separating the lower layer of waste acid, then pouring the mixture into a double-neck flask, dropwise adding a 32% sodium hydroxide solution until the pH value is 6.5-8.5, and then adding distilled water to adjust the effective content to be 49% -50% to obtain the sodium octadecyl diphenyl ether disulfonate solution. The yield was 88.32% based on diphenyl ether.

Wherein the microchannel reactor is made of silicon carbide; the inside diameter of the tube of the microchannel reactor was 50 μm.

The invention has various embodiments, and all technical solutions formed by adopting equivalent transformation or equivalent transformation are within the protection scope of the invention.