阅读说明：本技术 一种氯代特戊烷的合成方法 (Synthesis method of chloro-tert-pentane ) 是由 李超 朱振亚 吕宜飞 侯义杰 丁菲 于 2021-08-10 设计创作，主要内容包括：本发明涉及一种氯代特戊烷的合成方法。异戊烯与第一浓度盐酸反应后分相,得到第一水相和第一有机相,第一有机相与第二浓度盐酸反应后分相,得到第二水相和第二有机相,第二有机相即所述的氯代特戊烷；第一浓度盐酸的浓度小于第二浓度盐酸的浓度；第二水相回用为所述的第一浓度盐酸；合成方法采用连续反应方式。本发明的合成方法能够实现氯代特戊烷的连续生产,且具有优异的原料转化率和收率,产品质量稳定、盐酸利用率高、反应周期短、能耗低、操作简单,具有很高的实用价值,有利于工程化自动化实施与产能提升,尤其适合工业化生产,应用前景广阔。(The invention relates to a synthesis method of chloro-tertiary pentane. Reacting isoamylene with hydrochloric acid with a first concentration, and then carrying out phase splitting to obtain a first water phase and a first organic phase, reacting the first organic phase with hydrochloric acid with a second concentration, and then carrying out phase splitting to obtain a second water phase and a second organic phase, wherein the second organic phase is the chloro-tert-pentane; the concentration of the first concentration hydrochloric acid is less than that of the second concentration hydrochloric acid; the second water phase is recycled as the hydrochloric acid with the first concentration; the synthesis method adopts a continuous reaction mode. The synthesis method disclosed by the invention can realize continuous production of chlorinated special pentane, has excellent raw material conversion rate and yield, stable product quality, high utilization rate of hydrochloric acid, short reaction period, low energy consumption, simplicity in operation and very high practical value, is favorable for engineering automation implementation and capacity improvement, is especially suitable for industrial production, and has a wide application prospect.)

1. The synthesis method of chloro-tert-pentane is characterized in that isoamylene reacts with hydrochloric acid with a first concentration and then phase separation is carried out to obtain a first water phase and a first organic phase, the first organic phase reacts with hydrochloric acid with a second concentration and then phase separation is carried out to obtain a second water phase and a second organic phase, and the second organic phase is the chloro-tert-pentane;

the concentration of the hydrochloric acid with the first concentration is less than that of the hydrochloric acid with the second concentration;

the second water phase is recycled as the hydrochloric acid with the first concentration;

the synthesis method adopts a continuous reaction mode.

2. The synthesis method according to claim 1, wherein the concentration of the first-concentration hydrochloric acid is 3-30%; the concentration of the second-concentration hydrochloric acid is 10-36%.

3. The synthesis method according to claim 1, wherein the concentration of the first-concentration hydrochloric acid is 15-25%; the concentration of the second-concentration hydrochloric acid is 20-36%.

4. The method of claim 1, wherein the feed flow ratio of isoamylene to the second concentration of hydrochloric acid is 1:1 to 10.

5. The method of claim 4, wherein the feed flow ratio of isoamylene to the second concentration of hydrochloric acid is 1:1 to 5.

6. The synthesis method according to claim 1, wherein the total reaction time of the reaction of isoamylene with hydrochloric acid of a first concentration and the reaction of the first organic phase with hydrochloric acid of a second concentration is 0.5-5 h.

7. The method of claim 1, wherein the reaction temperature of the reaction of isoamylene with the first concentration of hydrochloric acid and the reaction temperature of the reaction of the first organic phase with the second concentration of hydrochloric acid are independently 0 to 70 ℃.

8. The method of claim 7, wherein the reaction temperature of said isoamylene with said first concentration of hydrochloric acid is less than the reaction temperature of said first organic phase with said second concentration of hydrochloric acid.

9. The synthesis method according to claim 8, wherein the reaction temperature of the reaction of isoamylene with the first concentration of hydrochloric acid is 0 to 20 ℃, and the reaction temperature of the reaction of the first organic phase with the second concentration of hydrochloric acid is 30 to 60 ℃.

10. The synthesis method according to claim 8, wherein the reaction temperature of the reaction of isoamylene with the first concentration of hydrochloric acid is 0 to 10 ℃, and the reaction temperature of the reaction of the first organic phase with the second concentration of hydrochloric acid is 10 to 15 ℃.

11. The method as claimed in claim 1, wherein said isoamylene and said hydrochloric acid of a first concentration are passed through a first reaction vessel and reacted in said first reaction vessel to obtain a preliminary reaction solution, the preliminary reaction liquid enters a first automatic phase separator through overflow for phase separation to obtain the first organic phase and the first water phase, the first aqueous phase flows out from the first automatic phase separator, the first organic phase and the second concentration hydrochloric acid flow through a second reaction vessel and react in the second reaction vessel to obtain a two-step reaction liquid, the reaction liquid of the second step enters a second automatic phase separator through overflow for phase separation to obtain a second organic phase and a second water phase, the second organic phase flows out of the second automatic phase separator, and the second aqueous phase flows back to the first reaction vessel to be used as the first concentration hydrochloric acid.

12. The method of claim 11, wherein the second concentration of hydrochloric acid is produced from the first aqueous phase by adjusting the concentration of hydrochloric acid by absorption of hydrogen chloride.

Technical Field

The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis method of chloro-tert-pentane.

Background

Chlorotentane is mainly used as an intermediate for producing pinacolone, which is a main raw material of pesticides, medicines, perfumes and the like.

At present, the main synthesis method of chloro-tert-pentane is to slowly drop isoamylene into excessive hydrochloric acid at 0-20 ℃, and then the temperature is raised to convert the isoamylene into the chloro-tert-pentane as much as possible. The method needs 36% concentrated hydrochloric acid, the dosage of the concentrated hydrochloric acid is more than 3 times of the theoretical required mass, and if the concentration of the concentrated hydrochloric acid is lower than 36% or the dosage of the 36% concentrated hydrochloric acid is lower than 3 times of the theoretical dosage, the conversion rate of the isoamylene is 92-93%.

CN103265399 discloses a method for synthesizing chloro-tert-pentane. 1-2% of zinc chloride is required to be added as a catalyst, the reaction time is 4-5 h, the yield reaches 96%, and compared with the traditional process, the yield is improved.

CN111909015 discloses a pinacolone continuous production process, in which isoamylene and hydrochloric acid are fed and cooled by a cooler, then the cooled isoamylene and hydrochloric acid are fed into a primary addition reactor for reaction, then reaction liquid in the primary addition reactor is fed into a secondary addition reactor for continuous reaction, then the reaction liquid in the secondary addition reactor is refluxed to the primary addition reactor by a circulating pump for continuous reaction, and then enters a secondary reactor for continuous reaction after passing through the primary addition reactor, and the reaction liquid is circulated in the primary addition reactor and the secondary addition reactor to continuously prolong the reaction time, so that the conversion rate of the isoamylene is over 99 percent, the reaction period is long, and the energy consumption is high.

In addition, the synthesis methods do not realize continuous production of chloro-tert-pentane, belong to batch reaction, have long reaction period and are not suitable for industrial automatic production.

Disclosure of Invention

The invention aims to provide a method for continuously synthesizing chloro-tertiary pentane, which is suitable for industrial production and has the advantages of high utilization rate of hydrochloric acid, high conversion rate of raw materials, high yield of products, short reaction period and low energy consumption.

In order to achieve the purpose, the invention adopts the technical scheme that:

the invention provides a synthesis method of chloro-tert-pentane, which comprises the steps of reacting isoamylene with hydrochloric acid with a first concentration, then carrying out phase separation to obtain a first water phase and a first organic phase, reacting the first organic phase with hydrochloric acid with a second concentration, then carrying out phase separation to obtain a second water phase and a second organic phase, wherein the second organic phase is the chloro-tert-pentane;

the concentration of the hydrochloric acid with the first concentration is less than that of the hydrochloric acid with the second concentration;

the second water phase is recycled as the hydrochloric acid with the first concentration;

the synthesis method adopts a continuous reaction mode.

Preferably, the concentration of the first-concentration hydrochloric acid is 5-30%.

More preferably, the concentration of the first concentration hydrochloric acid is less than or equal to 28%, and still more preferably less than or equal to 25%; and the concentration of the first concentration hydrochloric acid is 10% or more, more preferably 15% or more, and still more preferably 20% or more.

Preferably, the concentration of the second-concentration hydrochloric acid is 10-36%.

More preferably, the concentration of the hydrochloric acid with the second concentration is 15-36%, still more preferably 20-36%, and still more preferably 25-36%.

According to some specific and preferred embodiments, the concentration of the first concentration of hydrochloric acid is 15 to 25%, and the concentration of the second concentration of hydrochloric acid is 28 to 36%.

More preferably, the concentration of the first concentration hydrochloric acid is 20-25%, and the concentration of the second concentration hydrochloric acid is 30-36%.

Preferably, the feed flow ratio of isoamylene to the second concentration of hydrochloric acid is 1:1 to 10.

Further preferably, the feed flow ratio of isoamylene to the second concentration of hydrochloric acid is 1:1 to 5.

Still further preferably, the feed flow ratio of isoamylene to the second concentration of hydrochloric acid is 1:2 to 4.5.

Preferably, the feeding flow ratio of the isoamylene to the hydrochloric acid with the first concentration is 1: 1-5.

Further preferably, the feeding flow ratio of the isoamylene to the hydrochloric acid with the first concentration is 1: 1.5-2.5.

Preferably, the feeding flow ratio of the second organic to the second concentration hydrochloric acid is 1.5: 1-12.

Further preferably, the feeding flow ratio of the second organic to the second concentration hydrochloric acid is 1: 1-5.

Still more preferably, the feeding flow ratio of the second organic to the second concentration hydrochloric acid is 1: 2-3.5.

Preferably, the total reaction time of the reaction of the isoamylene and the hydrochloric acid with the first concentration and the reaction of the first organic phase and the hydrochloric acid with the second concentration is 0.5-5 h.

The reaction time is determined mainly by the ratio of the sum of the liquid holding volumes of the first reaction vessel and the second reaction vessel to the feed flow rate, for example, the total volume of the material feed per hour is 500ml, the sum of the liquid holding volumes of the first reaction vessel and the second reaction vessel is 300ml, and the reaction time is 0.6 h.

When the feeding flow is fixed, the reaction time can be adjusted by adjusting the liquid holding volume of the first reaction vessel or the second reaction vessel; when the liquid holding volume of the first reaction container or the second reaction container is fixed, the reaction time can be adjusted through the feeding flow, and the reaction device is more flexible and convenient.

Preferably, the ratio of the reaction time of the isoamylene and the first concentration of hydrochloric acid to the reaction time of the first organic phase and the second concentration of hydrochloric acid is 0.2-5: 1, more preferably 0.4 to 2.5: 1.

preferably, the reaction temperature of the reaction between the isoamylene and the hydrochloric acid with the first concentration is 0-70 ℃, more preferably 0-60 ℃, and even more preferably 0-50 ℃.

Preferably, the reaction temperature of the reaction of the first organic phase and the second concentration hydrochloric acid is independently 0-70 ℃, more preferably 0-60 ℃, and still more preferably 0-50 ℃.

Preferably, the reaction temperature of the reaction of the isoamylene with the first concentration of hydrochloric acid is lower than the reaction temperature of the reaction of the first organic phase with the second concentration of hydrochloric acid.

According to some specific and preferred embodiments, the reaction temperature of the reaction of isoamylene with the first concentration of hydrochloric acid is 0 to 20 ℃, and the reaction temperature of the reaction of the first organic phase with the second concentration of hydrochloric acid is 30 to 60 ℃.

Still more preferably, the reaction temperature of the reaction between isoamylene and the hydrochloric acid with the first concentration is 10-15 ℃, and the reaction temperature of the reaction between the first organic phase and the hydrochloric acid with the second concentration is 40-45 DEG C

According to other specific and preferred embodiments, the reaction temperature of the reaction of isoamylene with the first concentration of hydrochloric acid is 0 to 10 ℃, and the reaction temperature of the reaction of the first organic phase with the second concentration of hydrochloric acid is 10 to 15 ℃.

According to one embodiment, said isoamylene and said hydrochloric acid of first concentration are passed through a first reaction vessel and reacted in said first reaction vessel to obtain a preliminary reaction solution, the preliminary reaction liquid enters a first automatic phase separator through overflow for phase separation to obtain the first organic phase and the first water phase, the first aqueous phase flows out from the first automatic phase separator, the first organic phase and the second concentration hydrochloric acid flow through a second reaction vessel and react in the second reaction vessel to obtain a two-step reaction liquid, the reaction liquid of the second step enters a second automatic phase separator through overflow for phase separation to obtain a second organic phase and a second water phase, the second organic phase flows out of the second automatic phase separator, and the second aqueous phase flows back to the first reaction vessel to be used as the first concentration hydrochloric acid.

Specifically, the reaction device for the continuous reaction comprises a first reaction vessel, a first automatic phase separator communicated with the first reaction vessel in an overflow manner, a second reaction vessel communicated with the first automatic phase separator through a pipeline provided with a pump, and a second automatic phase separator communicated with the second reaction vessel in an overflow manner, the second automatic phase separator is also communicated with the first automatic phase separator through a return pipe provided with a pump, said first automatic phase separator capable of separating a preliminary reaction liquid from said first reaction vessel into said first aqueous phase and said first organic phase, the second automatic phase separator is capable of separating the two-step reaction solution from the second reaction vessel into the second aqueous phase and the second organic phase, and the second aqueous phase is transferred to the first vessel through the return pipe as the first concentration hydrochloric acid.

Specifically, the isoamylene and the hydrochloric acid enter from the bottom of the first reaction vessel, the reaction liquid in the first reaction vessel enters the first automatic phase separator through an overflow direction, the first organic phase from the first automatic phase separator enters from the bottom of the second reaction vessel through a pump, the hydrochloric acid with the second concentration simultaneously enters from the bottom of the second reaction vessel, the reaction liquid in the second reaction vessel enters the second automatic phase separator through an overflow direction, the second aqueous phase from the second automatic phase separator is conveyed to the first reaction vessel through a pump, and the second organic phase from the second automatic phase separator is collected.

Preferably, the liquid holding volume ratio of the first reaction vessel to the second reaction vessel is 0.2-3: 1.

preferably, the second concentration of hydrochloric acid is prepared from the first aqueous phase by adjusting the concentration of hydrochloric acid by absorbing hydrogen chloride.

The invention can achieve more than 99 percent of conversion rate and more than 99 percent of yield while realizing the continuous production of the chloro-tertiary pentane, and is easier to realize the industrial continuous production.

Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:

the synthesis method disclosed by the invention can realize continuous production of chlorinated special pentane, has excellent raw material conversion rate and yield, stable product quality, high utilization rate of hydrochloric acid, short reaction period, low energy consumption, simplicity in operation and very high practical value, is favorable for engineering automation implementation and capacity improvement, is especially suitable for industrial production, and has a wide application prospect.

Drawings

FIG. 1 is a schematic diagram of the synthesis process of chloro-tert-pentane of the example.

Detailed Description

All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations where mutually exclusive features or steps are expressly stated.

The invention will now be further described with reference to specific examples, but the invention should not be limited to these examples, but may be substituted by other equivalent or similarly purposed alternative features unless specifically stated. Unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features. Terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art, unless otherwise specified.

In the following examples, various procedures and methods not described in detail are conventional methods well known in the art. The concentration of hydrochloric acid refers to mass concentration, for example, hydrochloric acid with a concentration of 31% refers to the mass fraction of HCl in the hydrochloric acid aqueous solution being 31%.

Example 1

In this embodiment, the reaction apparatus for continuous reaction includes a first reaction vessel, a first auto phase separator, a second reaction vessel, and a second auto phase separator. The bottom of the first reaction container is communicated with a sample loading device used for conveying isoamylene, the top of the first reactor is provided with an overflow port and is communicated with the first automatic phase splitting device through the overflow port, a water phase outlet of the first automatic phase splitting device is communicated with a water phase recovery working section, an organic phase outlet of the first automatic phase splitting device is communicated with the bottom of the second reaction container through a pipeline provided with a pump, the bottom of the second reaction container is also communicated with the sample loading device used for conveying hydrochloric acid with second concentration, the top of the second reaction container is provided with an overflow port and is communicated with the second automatic phase splitting device through the overflow port, a water phase outlet of the second phase splitting device is communicated with the bottom of the first reaction container through a pipeline provided with a pump, and an organic phase outlet of the second automatic phase splitting device is communicated with a chlorinated special pentane product collecting device.

In the implementation, the volumes of the first reaction container and the second reaction container are respectively 100mL, at the beginning, isoamylene is introduced into the first reaction container, second-solubility hydrochloric acid is introduced into the second reaction container, all pumps are opened, and after the whole device is filled with liquid and circulates for a short time, the liquid enters the formal continuous reaction and a second organic phase, namely chloro-tert-pentane, in the second automatic phase separator is collected. The reaction is maintained to be continuously carried out by adjusting the pump.

In this example, the liquid holdups of the first reaction vessel and the second reaction vessel were each 100mL, the feed rate of isoamylene was controlled to 100g per hour, the concentration of hydrochloric acid of the second concentration introduced into the second reaction vessel was 31%, the feed rate of hydrochloric acid of the second concentration was controlled to 261.6g per hour, the feed rate of the second aqueous phase (23% as hydrochloric acid of the first concentration) from the second automatic phase separator into the first reaction vessel was 241.6g per hour, the reaction temperature in the first reaction vessel was set to 10 to 15 ℃, and the reaction temperature in the second reaction vessel was set to 40 to 45 ℃.

The content of chlorinated tripentane collected in this example was 99.5% with a yield of 99.1%.

Example 2

The reaction apparatus used in this example was substantially the same as that used in example 1 except that the volume of the first reaction vessel was 250mL and the volume of the second reaction vessel was 100 mL.

In this example, the feed rate of isoamylene was controlled to 100g per hour, the concentration of hydrochloric acid of the second concentration introduced into the second reaction vessel was 31%, the feed rate of hydrochloric acid of the second concentration was controlled to 261.6g per hour, the feed rate of the second aqueous phase (as hydrochloric acid of the first concentration, the concentration was 23%) from the second automatic phase separator into the first reaction vessel was 241.6g per hour, the reaction temperature in the first reaction vessel was set to 10 to 15 ℃, and the reaction temperature in the second reaction vessel was set to 40 to 45 ℃.

The content of chlorinated tripentane collected in this example was 99.7% with a yield of 99.3%.

Example 3

The reaction apparatus used in this example was substantially the same as that used in example 1 except that the volume of the first reaction vessel was 100mL and the volume of the second reaction vessel was 250 mL.

In this example, the feeding rate of isoamylene was controlled to 100g per hour, the concentration of hydrochloric acid of the second concentration introduced into the second reaction vessel was controlled to 20%, the feeding rate of hydrochloric acid of the second concentration was controlled to 405.5g per hour, the feeding rate of the second aqueous phase (as hydrochloric acid of the first concentration, the concentration was 16.5%) from the second automatic phase separator into the first reaction vessel was controlled to 380.5g per hour, the reaction temperature in the first reaction vessel was set to 10 to 15 ℃, and the reaction temperature in the second reaction vessel was set to 40 to 45 ℃.

The content of chlorinated tripentane collected in this example was 96.8% with a yield of 95.3%.

Example 4

The reaction apparatus used in this example was substantially the same as that used in example 1 except that the volume of the first reaction vessel was 250mL and the volume of the second reaction vessel was 100 mL.

In this example, the feed rate of isoamylene was controlled to 100g per hour, the concentration of hydrochloric acid of the second concentration introduced into the second reaction vessel was 31%, the feed rate of hydrochloric acid of the second concentration was controlled to 261.6g per hour, the feed rate of the second aqueous phase (as hydrochloric acid of the first concentration, the concentration was 23%) from the second automatic phase separator into the first reaction vessel was 239.4g per hour, the reaction temperature in the first reaction vessel was set to 0 to 10 ℃, and the reaction temperature in the second reaction vessel was set to 10 to 15 ℃.

The content of chlorinated neopentane collected in this example was 98.1%, yield 97.3%.

Comparative example 1

523.2g of hydrochloric acid with the concentration of 31 percent is added into a glass four-mouth bottle, the temperature is reduced to 2 ℃, 200g of isoamylene is added dropwise, and the heat release phenomenon exists in the dropwise adding process. The dropping time is 60-90 minutes, the temperature is kept for 60 minutes at 10 ℃ after the dropping is finished, the temperature is kept for 60 minutes after the temperature is raised to 30 ℃, the temperature is kept for 2 hours after the temperature is raised to 50 ℃, the reaction time is accumulated for 6-7 hours, and the sampling analysis is finished after the temperature is kept.

The content of chlorinated tripentane collected in this comparative example was 92.3%, yield 93.6%.

Comparative example 2

523.2g of hydrochloric acid with the concentration of 31 percent is added into a glass four-mouth bottle, the temperature is reduced to 2 ℃, 200g of isoamylene is added dropwise, and the heat release phenomenon exists in the dropwise adding process. The dropping time is 60-90 minutes, the temperature is raised to 50 ℃ after the dropping is finished, the temperature is kept for 2 hours, the reflux temperature is gradually raised to 50 ℃ along with the reaction, the reaction time is accumulated for 6-7 hours, and the sampling analysis is finished after the temperature is kept.

The content of chlorinated tripentane collected in this comparative example was 85.2%, yield 86.1%.

The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.