阅读说明：本技术 一种叔丁基丙烯酰胺磺酸的生产装置和生产方法 (Production device and production method of tert-butyl acrylamide sulfonic acid ) 是由 李斗星 穆晓蕾 贾春革 齐兰芝 于 2019-10-18 设计创作，主要内容包括：本发明提供一种叔丁基丙烯酰胺磺酸的生产装置,包括依次连接的微通道反应器、反应发生装置和固液分离装置,其中,所述微通道反应器的内径为0.1mm～20mm,长度为0.1m～10m。本发明通过使用微通道反应器混合硫酸和丙烯腈,使得硫酸与丙烯腈的放热对反应的影响减小到最少,而且提高了物料混合的均匀性,显著减少副产物生成,提高产品质量。(The invention provides a production device of tert-butyl acrylamide sulfonic acid, which comprises a microchannel reactor, a reaction generating device and a solid-liquid separation device which are sequentially connected, wherein the inner diameter of the microchannel reactor is 0.1-20 mm, and the length of the microchannel reactor is 0.1-10 m. The invention mixes the sulfuric acid and the acrylonitrile by using the microchannel reactor, so that the influence of the heat release of the sulfuric acid and the acrylonitrile on the reaction is reduced to the minimum, the uniformity of material mixing is improved, the generation of byproducts is obviously reduced, and the product quality is improved.)

1. A production device of tert-butyl acrylamide sulfonic acid comprises a microchannel reactor, a reaction generating device and a solid-liquid separation device which are sequentially connected, wherein the inner diameter of the microchannel reactor is 0.1-20 mm, preferably 1-10 mm, and the length of the microchannel reactor is 0.1-10 m, preferably 1-5 m.

2. A production method of t-butylacrylamide sulfonic acid, comprising performing the following steps with the production apparatus according to claim 1:

a) mixing sulfuric acid and acrylonitrile in a microchannel reactor to obtain a mixed solution;

b) introducing the mixed solution into a reaction generating device at a first feeding temperature, adjusting to a second feeding temperature, and introducing isobutene into the reaction generating device, so that the mixed solution and the isobutene react to obtain a reaction solution;

c) curing the reaction liquid to obtain cured liquid; and

d) and carrying out solid-liquid separation on the cured liquid in a solid-liquid separation device to obtain a crude product of tert-butyl acrylamide sulfonic acid.

3. The production method according to claim 2, wherein in step a), the concentration of the sulfuric acid is 98-103%, preferably 100-102%; the water content of the acrylonitrile is 0.05-1.00%, and preferably 0.20-0.70%.

4. The production method according to claim 2 or 3, wherein in step a), the sulfuric acid is introduced at a rate of 1 to 50g/h, preferably 2 to 25 g/h; the introduction rate of the acrylonitrile is 4 g/h-400 g/h, preferably 30 g/h-200 g/h.

5. The production method according to any one of claims 2 to 4, wherein the temperature of the mixing in step a) is from-20 ℃ to 0 ℃.

6. The production method according to any one of claims 2 to 5, wherein in the step b), the mass ratio of the mixed solution to the isobutene is (5-25: 1, preferably (8-18: 1).

7. The production process according to any one of claims 2 to 6, wherein in step b), the isobutene is introduced at a rate of from 0.5 to 25g/h, preferably from 2 to 25 g/h.

8. The production method according to any one of claims 2 to 7, wherein in step b), the first feed temperature is from-20 ℃ to 0 ℃; the second feeding temperature is 0-55 ℃.

9. The production method according to any one of claims 2 to 8, wherein in step c), the temperature of the aging treatment is 10 ℃ to 55 ℃ for 1h to 3 h.

10. The production process according to any one of claims 2 to 9, further comprising a step of refining the crude t-butylacrylamide sulfonic acid after the step d) to obtain a pure t-butylacrylamide sulfonic acid.

Technical Field

The invention relates to the technical field of production processes of chemical products, in particular to a production device and a production method of tert-butyl acrylamide sulfonic acid.

Background

Tert-butyl Acrylamide sulfonic acid (2-Acrylamide-2-methyl propane sulfonic acid, hereinafter referred to as AMPS) is one of the most widely used polymerization monomers. The molecular structure of the polymer has carbon-carbon double bonds, amido and sulfonic acid functional groups, and the homopolymer and the copolymer have a plurality of special properties, thereby having wide application prospect and being widely applied to the fields of oilfield chemistry, water treatment agents, fiber synthesis, coatings, medical hydrogel and the like.

As disclosed in JP 2904444, JP 2904465 and JP 81533062, AMPS is most commonly synthesized by using an excess amount of acrylonitrile as a reaction solvent, adding oleum at a low temperature, then introducing isobutylene under stirring to react, separating out AMPS as a product from the mixed solution to obtain a slurry-like product, and drying to obtain a crude AMPS. The crude product is purified by acetic acid aqueous solution to obtain a pure product, neutralized by an alkaline reagent to obtain an AMPS salt monomer, and subjected to polymerization reaction with acrylamide to produce the auxiliary agent for tertiary oil recovery, and the auxiliary agent has the characteristics of high molecular weight and high viscosity.

However, since the mixing of acrylonitrile with sulfuric acid and the addition of isobutylene are exothermic processes during the synthesis of AMPS, the local reaction temperature is easily increased, and the control of impurities is difficult. The control of impurities in the AMPS production process directly influences the molecular weight of the polymer, and the high-quality AMPS serving as a monomer polymer has larger molecular weight and wider application field.

Therefore, there is a problem that research and development of a production method capable of significantly reducing the content of impurities in tert-butyl acrylamide sulfonic acid is urgently needed.

Disclosure of Invention

In view of the problems in the prior art, the present invention aims to provide a production apparatus and a production method of tert-butyl acrylamide sulfonic acid, which can minimize the influence of the heat release of sulfuric acid and acrylonitrile on the reaction, improve the uniformity of material mixing, significantly reduce the generation of by-products, and improve the product quality by mixing sulfuric acid and acrylonitrile using a microchannel reactor.

The invention provides a production device of tert-butyl acrylamide sulfonic acid, which comprises a microchannel reactor, a reaction generating device and a solid-liquid separation device which are sequentially connected, wherein the inner diameter of the microchannel reactor is 0.1-20 mm, and the length of the microchannel reactor is 0.1-10 m.

According to the invention, the inner diameter of the microchannel reactor is 1 mm-10 mm, and the length is 1 m-5 m.

According to the invention, the microchannel reactor provides a location for mixing sulfuric acid and acrylonitrile.

The inventor of the application finds that compared with the traditional reactor, the microchannel reactor has remarkable advantages in mass and heat transfer, can effectively improve the reaction efficiency, reduces the occurrence of side reactions, and is easy to operate and control. The microchannel reactor with specific size is used for mixing sulfuric acid and acrylonitrile, so that the influence of the heat release of the sulfuric acid and the acrylonitrile on the reaction is reduced to the minimum, the uniformity of material mixing is improved, the generation of byproducts is obviously reduced, and the product quality is improved.

The reaction-generating apparatus according to the present invention may be any apparatus capable of providing a place for the reaction of isobutylene and sulfuric acid with acrylonitrile, such as a reaction tank and a three-necked flask.

According to the present invention, the solid-liquid separation device may be any device capable of achieving solid-liquid separation.

The invention also provides a production method of tert-butyl acrylamide sulfonic acid, which utilizes the production device to carry out the following steps:

a) mixing sulfuric acid and acrylonitrile in a microchannel reactor to obtain a mixed solution;

b) introducing the mixed solution into a reaction generating device at a first feeding temperature, adjusting to a second feeding temperature, and introducing isobutene into the reaction generating device, so that the mixed solution and the isobutene react to obtain a reaction solution;

c) curing the reaction liquid to obtain cured liquid; and

d) and carrying out solid-liquid separation on the cured liquid in a solid-liquid separation device to obtain a crude product of tert-butyl acrylamide sulfonic acid.

According to the present invention, the reaction generating apparatus may be any apparatus commonly used in the art capable of providing a reaction generating site, such as, but not limited to, a three-neck flask and a reaction kettle.

In some preferred embodiments of the present invention, in step a), the concentration of the sulfuric acid is 98% to 103%, preferably 100% to 102%; the water content of the acrylonitrile is 0.05-1.00%, and preferably 0.20-0.70%.

According to the invention, a concentration of 98% to 100% of sulfuric acid means free SO in the sulfuric acid₃The content of (A) is 0; a concentration of sulfuric acid greater than 100% means that the sulfuric acid contains free SO₃. For example, a concentration of 100.23% sulfuric acid refers to the free SO in sulfuric acid₃The content of (A) is 1%, and the concentration of the sulfuric acid is 100.45% which means that free SO in the sulfuric acid is₃The content of (A) is 2%, and the concentration of the sulfuric acid is 100.68% which means that free SO in the sulfuric acid is₃The content of (A) is 3%, and the concentration of sulfuric acid is 100.9% which means free SO in sulfuric acid₃The content of (A) is 4%, and the concentration of sulfuric acid is 101.13% which means free SO in sulfuric acid₃The content of (A) is 5%, and the concentration of the sulfuric acid is 101.35% which means that free SO in the sulfuric acid is₃The content of (A) is 6%, and the concentration of the sulfuric acid is 101.58% which means that free SO in the sulfuric acid is₃The content of (A) is 7%, and the concentration of sulfuric acid is 101.8% which means free SO in sulfuric acid₃The content of (A) is 8%, and the concentration of sulfuric acid is 102.03%, which means free SO in sulfuric acid₃The content of (A) is 9%, and the concentration of the sulfuric acid is 102.25% which means that free SO in the sulfuric acid is₃The content of (A) is 10%, and the concentration of the sulfuric acid is 102.48% which means that free SO in the sulfuric acid is₃The content of (A) is 11%, and the concentration of sulfuric acid is 102.7% which means free SO in sulfuric acid₃The content of (A) is 12%, and the concentration of the sulfuric acid is 102.93% which means that free SO in the sulfuric acid is₃The content of (B) is 13%.

In some preferred embodiments of the present invention, the sulfuric acid is introduced at a rate of 1g/h to 50g/h, preferably 2g/h to 25 g/h; the introduction rate of the acrylonitrile is 4 g/h-400 g/h, preferably 30 g/h-200 g/h.

In some preferred embodiments of the present invention, the temperature of the mixing in step a) is from-20 ℃ to 0 ℃.

In some preferred embodiments of the present invention, in the step b), the mass ratio of the mixed solution to the isobutene is (5-25): 1, preferably (8-18): 1.

In some preferred embodiments of the invention, in step b), the isobutene is introduced at a rate of from 0.5g/h to 25g/h, preferably from 2g/h to 25 g/h.

In some preferred embodiments of the invention, in step b), the first feed temperature is from-20 ℃ to 0 ℃; the second feeding temperature is 0-55 ℃.

In some preferred embodiments of the present invention, in step c), the temperature of the aging treatment is 10 to 55 ℃ for 1 to 3 hours.

According to the invention, in the step d), the separation method is any method capable of realizing liquid-solid separation, such as filtration methods, including normal pressure filtration methods, vacuum filtration methods, centrifugal separation and the like, the generated slurry-like product is cooled to room temperature, and a filter cake and a filtrate are obtained after filtration. And (3) carrying out vacuum drying on the filter cake, wherein the vacuum drying condition can be a conventional condition, for example, the drying temperature can be 50-130 ℃, the drying pressure can be less than 30KPa, and the obtained dried product is an AMPS crude product.

In some preferred embodiments of the present invention, after the step d), the method further comprises a step of refining the crude tert-butyl acrylamide sulfonic acid to obtain a pure tert-butyl acrylamide sulfonic acid.

According to the present invention, the purification method may be a conventional AMPS purification method. Preferably, the method is as disclosed in US 4337215. Mixing the AMPS crude product with an acetic acid aqueous solution with the water content of 3-20 wt%, wherein the weight ratio of the AMPS crude product to the acetic acid aqueous solution is 1: 10-1: 3, heating the mixture to 85-105 ℃ until the AMPS crude product is dissolved, cooling the obtained mixed solution for 3-5 hours, filtering and vacuum drying, wherein the vacuum drying condition can be the same as that of the vacuum drying condition, and the AMPS pure product can be obtained after drying, and the purity of the pure product is generally more than 99 wt%. In the recrystallization process, after the AMPS crude product is dissolved, partial water and acetic acid can be distilled out through reduced pressure distillation, so that the yield of the recrystallization process can be improved.

In the preparation of AMPS, side reactions occur and by-products such as methacrylic sulfonic acid are produced, which adversely affect the use of AMPS in polymerization reactions. The invention reduces the influence of the heat release on the reaction when the sulfuric acid is contacted with the acrylonitrile and the isobutene is contacted with the acrylonitrile to the minimum by using the micro-channel reactor, and can improve the uniformity of the materials in the whole process and obviously reduce the generation of byproducts. Compared with the prior art, the method provided by the invention can effectively reduce byproducts generated in the reaction process, especially sulfonated byproducts, only by controlling the addition modes of acrylonitrile, sulfuric acid and isobutene in the reaction process without introducing other substances into the reaction system, so that the byproducts of the obtained AMPS product are obviously reduced, and the molecular weight of the polymer taking AMPS as a polymerization monomer can be effectively improved.

The yield of the crude product AMPS is more than 89%, and the purity of the obtained pure product AMPS is more than 99% after the crude product AMPS is refined by a conventional method.

Detailed Description

The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.

And analyzing the purity of the obtained AMPS crude product and pure product and AMPS sodium salt monomer pure product by liquid chromatography. The analysis conditions of the liquid chromatography were: zorbax SAX chromatography column with mobile phase of 0.1mol/L KH₂PO₄Solution, flow rate of 1.0mL/min, ultraviolet detector. The purities of the AMPS crude product and the AMPS salt monomer are compared with the purities of the AMPS salt monomer in the example and the comparative example because the purities are detected in an ion form in liquid chromatography.

The yield of crude AMPS was calculated based on the amount of isobutylene feed added and the weight of crude AMPS obtained.

The method for refining the AMPS crude product comprises the following steps: and recrystallizing the AMPS crude product by using a 10% acetic acid aqueous solution to obtain the high-purity AMPS.

The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.

Example 1

Respectively pumping sulfuric acid and acrylonitrile into a Y-shaped micro-mixer through two micro-feed pumps, mixing the sulfuric acid and the acrylonitrile in a micro-channel reactor (the inner diameter is 8mm, the length is 1m), keeping the temperature at minus 5 ℃, controlling the adding speed of the acrylonitrile (the water content is less than 0.5%) to be 66g/h and the adding speed of the sulfuric acid (the concentration is 100.9%) to be 12.2g/h in the mixing process, and mixing for 1h to obtain a mixed solution.

The mixture was directly charged into a three-necked flask for reaction at-5 ℃. The mixed solution is fed for 1h, and then the feeding is stopped. Then adjusting the reaction temperature to 40 ℃, introducing isobutene at the adding rate of 7g/h to react the isobutene with the mixed solution, and stopping introducing the isobutene after 1h to obtain the reaction solution.

After completion of the addition of isobutylene, the reaction solution was further aged in a three-necked flask at 40 ℃ for 1 hour.

The reaction solution was then vacuum filtered. Filtering to obtain a filter cake and filtrate, drying the filter cake in vacuum at 100 ℃ under 10KPa to obtain a crude product AMPS. And then refining the crude product AMPS to obtain a pure product AMPS.

The yield of crude AMPS, the purity of pure AMPS and the impurity content are shown in table 1.

Example 2

AMPS is prepared as in example 1, except that isobutylene is passed in at 20 ℃.

The yield of crude AMPS, the purity of pure AMPS and the impurity content are shown in table 1.

Example 3

AMPS is prepared as in example 1, except that isobutylene is passed in at 30 ℃.

The yield of crude AMPS, the purity of pure AMPS and the impurity content are shown in table 1.

Example 4

AMPS is prepared as in example 1, except that isobutylene is passed in at 50 ℃.

The yield of crude AMPS, the purity of pure AMPS and the impurity content are shown in table 1.

Example 5

AMPS was prepared as in example 1, except that sulfuric acid and acrylonitrile were mixed in a microchannel reactor at-20 ℃.

The yield of crude AMPS, the purity of pure AMPS and the impurity content are shown in table 1.

Example 6

AMPS was prepared as in example 1, except that sulfuric acid and acrylonitrile were mixed in the microchannel reactor at 0 ℃.

The yield of crude AMPS, the purity of pure AMPS and the impurity content are shown in table 1.

Example 7

AMPS was prepared as in example 1, except that the microchannel reactor had an inner diameter of 4mm and a length of 1 m.

The yield of crude AMPS, the purity of pure AMPS and the impurity content are shown in table 1.

Example 8

AMPS was prepared as in example 1, except that the microchannel reactor had an inner diameter of 8mm and a length of 2 m.

The yield of crude AMPS, the purity of pure AMPS and the impurity content are shown in table 1.

Example 9

AMPS was prepared as in example 1, except that the acrylonitrile addition rate was 33g/h, the sulfuric acid addition rate was 6.1g/h, and the addition process continued for 2 h.

The yield of crude AMPS, the purity of pure AMPS and the impurity content are shown in table 1.

Example 10

AMPS was prepared as in example 1, except that the isobutene feed rate was 3.5g/h and the addition was continued for 2 h.

The yield of crude AMPS, the purity of pure AMPS and the impurity content are shown in table 1.

Example 11

AMPS was prepared as in example 1, except that the isobutene feed rate was 14g/h and the addition was continued for 0.5 h.

The yield of crude AMPS, the purity of pure AMPS and the impurity content are shown in table 1.

Comparative example 1

This comparative example is presented to illustrate a batch AMPS synthesis process without the use of a microchannel reactor.

A reactor equipped with a temperature control device, a stirrer, a thermometer and a gas feed device was charged with 66g of analytically pure acrylonitrile, the acrylonitrile was cooled to-5 ℃ and 2 mass% SO was slowly added₃Then regulating the temperature of the reaction system to 40 ℃, slowly introducing 7g of isobutene for reaction, keeping the temperature for one hour after the isobutene is introduced, finishing the reaction, and carrying out vacuum filtration on the reaction solution. Filtering to obtain a filter cake and filtrate, and carrying out vacuum drying on the filter cake at the drying temperature of 100 ℃ and the drying pressure of 10KPa to obtain the dried filter cake.

The yield of crude AMPS, the purity of pure AMPS and the impurity content are shown in table 1.

TABLE 1

Comparing the data of the example with the data of the comparative example 1, it can be seen that the method provided by the invention for synthesizing AMPS can effectively reduce the content of byproducts. In addition, the size of the microchannel reactor, the introduction rates of sulfuric acid and acrylonitrile, the mixing temperature, and the introduction rate of isobutylene were adjusted to optimize the reaction results.

It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.