CN102531879A - Method for preparing 11-bromo-undecanoic acid by direct freezing crystallization and device therefor - Google Patents
Method for preparing 11-bromo-undecanoic acid by direct freezing crystallization and device therefor Download PDFInfo
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- CN102531879A CN102531879A CN2011104326317A CN201110432631A CN102531879A CN 102531879 A CN102531879 A CN 102531879A CN 2011104326317 A CN2011104326317 A CN 2011104326317A CN 201110432631 A CN201110432631 A CN 201110432631A CN 102531879 A CN102531879 A CN 102531879A
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Abstract
The invention discloses a method for preparing 11-bromo-undecanoic acid by direct freezing crystallization and a device for preparing 11-bromo-undecanoic acid, and relates to a method for preparing the 11-bromo-undecanoic acid. The preparation device comprises a burdening kettle, an addition tower, a crystallization kettle and a filter press, wherein the burdening kettle is connected with the addition tower; the addition tower is connected with the crystallization kettle; the crystallization kettle is connected with the filter press; and the filter press is connected with the top part of the burdening kettle. During work, the preparation method comprises the steps of: mixing undecylenic acid and toluene in a mass ratio of 1:(3-4) at a temperature of -5-0 DEG C in the burdening kettle; allowing the mixed liquid with hydrogen bromide in a mole ratio of 1:1.05 at a temperature of 0-30 DEGC in the addition tower to react so as to generate an addition liquid; putting the addition liquid in the crystallization kettle, carrying out freezing crystallization at a temperature of -4 DEG C to -16 DEG C, a revolving speed of 8 round/min and a vacuum degree of -0.02MPa to -0.03MPa; and filtering crystal in the filter press. The device disclosed by the invention has the advantages of a simple structure, strong continuity and operability and is suitable for industrial production. The preparation method has the advantages of a short process flow, constant reaction, high product purity and good economic benefits.
Description
Technical field
The present invention relates to the preparation method of 11-bromoundecanoic acid, be specifically related to the preparation method and the device thereof of the direct freezing and crystallizing of 11-bromoundecanoic acid.
Background technology
The method that prepare at present 11-bromoundecanoic acid generally is that the toluene solution with undecylenic acid gets into from the addition cat head, bromize hydrogen gas by the addition tower at the bottom of entering; In the addition tower, carry out the anti-Markovnikov addition reaction, reaction solution goes out from tower bottom flow, removes hydrogen bromide, washing through heating; Toluene distillation leaves standstill thermal separation then, tells thick bromo-derivative; With the bromo-derivative recrystallization; Make 11-bromoundecanoic acid, cat head tail gas absorbs through alkali lye sends to the bromine recycle section, and the toluene that steams uses through neutralization, drying, distillation, recovery.
Prior art exists technology long, the defective that the aftertreatment workload is big, and hydrogen bromide generally will need to consume a large amount of waters through 5～8 washings, and toluene solution need need a large amount of steam through the use that could reflux after the distillation, has all improved production cost.
Summary of the invention
The purpose of this invention is to provide and the preparation method of the direct freezing and crystallizing of 11-bromoundecanoic acid.
Another object of the present invention provides the preparation facilities of the direct freezing and crystallizing of 11-bromoundecanoic acid.
The present invention realizes through following technical scheme:
The preparation facilities of the direct freezing and crystallizing of 11-bromoundecanoic acid; Comprise batching still, addition tower, crystallization kettle, pressure filter; The discharge port of still bottom of wherein preparing burden is connected with the opening for feed of addition top of tower; The discharge port of addition tower bottom is connected with the opening for feed at crystallization kettle top, and the discharge port of crystallization kettle bottom is connected with the opening for feed of pressure filter, and the discharge port of pressure filter bottom is connected with the opening for feed at batching still top.
During work, may further comprise the steps:
(1) in the batching still, keeping temperature is under-5 ℃～0 ℃ the condition, with undecylenic acid and toluene mix, to obtain the undecylenic acid toluene solution, and wherein undecylenic acid and toluene mass ratio are 1: 3～4;
(2) control addition tower temperature is at 0 ℃～30 ℃; The undecylenic acid toluene solution for preparing is sent into the addition tower from the opening for feed of addition top of tower; The inlet mouth of bromize hydrogen gas at the bottom of the addition Tata sent into the addition tower; Wherein the mol ratio of undecylenic acid toluene solution and hydrogen bromide is 1:1.05, carries out the anti-Markovnikov addition reaction in the addition tower, reaction back production addition liquid;
(3) addition liquid is sent into crystallization kettle from the discharge port of addition tower bottom, keeping the crystallization kettle temperature is-4 ℃～-16 ℃, 8 rev/mins of mixing speed, and vacuum tightness-0.02MPa～-0.03MPa, carry out freezing and crystallizing;
(4) crystallisate is sent into pressure filter from the discharge port of crystallization kettle bottom, filter, filtrating is delivered to the batching still and is prepared burden with undecylenic acid once more, and the material that filters is 11-bromoundecanoic acid.
Apparatus of the present invention are simple in structure, and continuity and workable is applicable to large industrialized production, and preparing method's technical process is short; React constant, the reaction capable of circulation of unreacted 11-olefin(e) acid, toluene solution is volatilization and loss not, can realize the continuous and automatic discharging; The freezing and crystallizing product purity is high, and synthetic 11-bromoundecanoic acid quality is high, and fusing point is more than 48 ℃; Purity is more than 98%, and is good in economic efficiency, and production cost is low.
Description of drawings
Fig. 1 is the structural representation of the preparation facilities of the direct freezing and crystallizing of 11-bromoundecanoic acid of the present invention;
Among the figure: 1-batching still, 2-addition tower, 3-crystallization kettle, 4-pressure filter.
Embodiment
Below in conjunction with accompanying drawing the present invention is further specified.
Embodiment 1
The preparation facilities of the direct freezing and crystallizing of 11-bromoundecanoic acid as shown in Figure 1; Comprise batching still 1, addition tower 2, crystallization kettle 3, pressure filter 4; The discharge port of still 1 bottom of wherein preparing burden is connected with the opening for feed at addition tower 2 tops; The discharge port of addition tower 2 bottoms is connected with the opening for feed at crystallization kettle 3 tops, and the discharge port of crystallization kettle 3 bottoms is connected with the opening for feed of pressure filter 4, and the discharge port of pressure filter 4 bottoms is connected with the opening for feed at batching still 1 top.
During work, may further comprise the steps:
(1) in batching still 1, keeping temperature is under-5 ℃ the condition, with undecylenic acid and toluene mix, to obtain the undecylenic acid toluene solution, and wherein undecylenic acid and toluene mass ratio are 1: 3.5;
(2) control addition tower 2 temperature are at 20 ℃; The undecylenic acid toluene solution for preparing is sent into addition tower 2 from the opening for feed of addition top of tower; The inlet mouth of bromize hydrogen gas at the bottom of the addition Tata sent into addition tower 2; Wherein the mol ratio of undecylenic acid toluene solution and hydrogen bromide is 1:1.05, carries out the anti-Markovnikov addition reaction in the addition tower 2, reaction back production addition liquid;
(3) addition liquid is sent into crystallization kettle 3 from the discharge port of addition tower bottom, keeping crystallization kettle 3 temperature is-4 ℃, 8 rev/mins of mixing speed, and vacuum tightness-0.02MPa carries out freezing and crystallizing;
(4) crystallisate is sent into pressure filter 4 from the discharge port of crystallization kettle 3 bottoms, filter, filtrating is delivered to batching still 1 and is prepared burden with undecylenic acid once more, and the material that filters is 11-bromoundecanoic acid.
Through measuring, the fusing point of product is 48 ℃, and purity is 98%.
Embodiment 2
The preparation facilities of the direct freezing and crystallizing of 11-bromoundecanoic acid as shown in Figure 1; Comprise batching still 1, addition tower 2, crystallization kettle 3, pressure filter 4; The discharge port of still 1 bottom of wherein preparing burden is connected with the opening for feed at addition tower 2 tops; The discharge port of addition tower 2 bottoms is connected with the opening for feed at crystallization kettle 3 tops, and the discharge port of crystallization kettle 3 bottoms is connected with the opening for feed of pressure filter 4, and the discharge port of pressure filter 4 bottoms is connected with the opening for feed at batching still 1 top.
During work, may further comprise the steps:
(1) in batching still 1, keeping temperature is under-3 ℃ the condition, with undecylenic acid and toluene mix, to obtain the undecylenic acid toluene solution, and wherein undecylenic acid and toluene mass ratio are 1: 4;
(2) control addition tower 2 temperature are at 30 ℃; The undecylenic acid toluene solution for preparing is sent into addition tower 2 from the opening for feed of addition top of tower; The inlet mouth of bromize hydrogen gas at the bottom of the addition Tata sent into addition tower 2; Wherein the mol ratio of undecylenic acid toluene solution and hydrogen bromide is 1:1.05, carries out the anti-Markovnikov addition reaction in the addition tower 2, reaction back production addition liquid;
(3) addition liquid is sent into crystallization kettle 3 from the discharge port of addition tower bottom, keeping crystallization kettle 3 temperature is-10 ℃, 8 rev/mins of mixing speed, and vacuum tightness-0.02MPa carries out freezing and crystallizing;
(4) crystallisate is sent into pressure filter 4 from the discharge port of crystallization kettle 3 bottoms, filter, filtrating is delivered to batching still 1 and is prepared burden with undecylenic acid once more, and the material that filters is 11-bromoundecanoic acid.
Through measuring, the fusing point of product is 48.2 ℃, and purity is 98.6%.
Embodiment 3
The preparation facilities of the direct freezing and crystallizing of 11-bromoundecanoic acid as shown in Figure 1; Comprise batching still 1, addition tower 2, crystallization kettle 3, pressure filter 4; The discharge port of still 1 bottom of wherein preparing burden is connected with the opening for feed at addition tower 2 tops; The discharge port of addition tower 2 bottoms is connected with the opening for feed at crystallization kettle 3 tops, and the discharge port of crystallization kettle 3 bottoms is connected with the opening for feed of pressure filter 4, and the discharge port of pressure filter 4 bottoms is connected with the opening for feed at batching still 1 top.
During work, may further comprise the steps:
(1) in batching still 1, keeping temperature is under 0 ℃ the condition, with undecylenic acid and toluene mix, to obtain the undecylenic acid toluene solution, and wherein undecylenic acid and toluene mass ratio are 1: 3;
(2) control addition tower 2 temperature are at 0 ℃; The undecylenic acid toluene solution for preparing is sent into addition tower 2 from the opening for feed of addition top of tower; The inlet mouth of bromize hydrogen gas at the bottom of the addition Tata sent into addition tower 2; Wherein the mol ratio of undecylenic acid toluene solution and hydrogen bromide is 1:1.05, carries out the anti-Markovnikov addition reaction in the addition tower 2, reaction back production addition liquid;
(3) addition liquid is sent into crystallization kettle 3 from the discharge port of addition tower bottom, keeping crystallization kettle 3 temperature is-16 ℃, 8 rev/mins of mixing speed, and vacuum tightness-0.03MPa carries out freezing and crystallizing;
(4) crystallisate is sent into pressure filter 4 from the discharge port of crystallization kettle 3 bottoms, filter, filtrating is delivered to batching still 1 and is prepared burden with undecylenic acid once more, and the material that filters is 11-bromoundecanoic acid.
Through measuring, the fusing point of product is 49.2 ℃, and purity is 99.5%.
Claims (2)
1. the preparation facilities of the direct freezing and crystallizing of a 11-bromoundecanoic acid; It is characterized in that comprising batching still (1), addition tower (2), crystallization kettle (3), pressure filter (4); The discharge port of wherein said batching still (1) bottom is connected with the opening for feed at addition tower (2) top; The discharge port of described addition tower (2) bottom is connected with the opening for feed at crystallization kettle (3) top; The discharge port of described crystallization kettle (3) bottom is connected with the opening for feed of pressure filter (4), and the discharge port of described pressure filter (4) bottom is connected with the opening for feed at batching still (1) top.
2. the preparation method of the direct freezing and crystallizing of a 11-bromoundecanoic acid carries out in the described device of claim 1, it is characterized in that may further comprise the steps:
(1) the maintenance temperature is under-5 ℃～0 ℃ the condition, with undecylenic acid and toluene mix, to obtain the undecylenic acid toluene solution in batching still (1), and wherein undecylenic acid and toluene mass ratio are 1: 3～4;
(2) control addition tower (2) temperature is at 0 ℃～30 ℃; The undecylenic acid toluene solution for preparing is sent into addition tower (2) from the opening for feed of addition top of tower; The inlet mouth of bromize hydrogen gas at the bottom of the addition Tata sent into addition tower (2); Wherein the mol ratio of undecylenic acid toluene solution and hydrogen bromide is 1:1.05, carries out the anti-Markovnikov addition reaction in the addition tower (2), reaction back production addition liquid;
(3) addition liquid is sent into crystallization kettle (3) from the discharge port of addition tower bottom, keeping crystallization kettle (3) temperature is-4 ℃～-16 ℃, 8 rev/mins of mixing speed, and vacuum tightness-0.02MPa～-0.03MPa, carry out freezing and crystallizing;
(4) crystallisate is sent into pressure filter (4) from the discharge port of crystallization kettle (3) bottom, filter, filtrating is delivered to batching still (1) and is prepared burden with undecylenic acid once more, and the material that filters is 11-bromoundecanoic acid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104326317A CN102531879A (en) | 2011-12-21 | 2011-12-21 | Method for preparing 11-bromo-undecanoic acid by direct freezing crystallization and device therefor |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011104326317A CN102531879A (en) | 2011-12-21 | 2011-12-21 | Method for preparing 11-bromo-undecanoic acid by direct freezing crystallization and device therefor |
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| CN102531879A true CN102531879A (en) | 2012-07-04 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015019028A1 (en) * | 2013-08-09 | 2015-02-12 | Arkema France | Hydrobromination method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2772302A (en) * | 1952-08-07 | 1956-11-27 | Perfogit Spa | Process for the production of 11-bromoundecanoic acid |
| CN1218793A (en) * | 1997-12-04 | 1999-06-09 | 范拥军 | Process for producing bromo-undecylic acid |
| CN101289379A (en) * | 2008-06-12 | 2008-10-22 | 山西宏远科技股份有限公司 | Process for preparing bromoundecanoic acid by tower type addition of undecylenic acid |
| CN101289382A (en) * | 2008-06-12 | 2008-10-22 | 山西宏远科技股份有限公司 | Separation process of bromoundecanoic acid by freezing crystal |
-
2011
- 2011-12-21 CN CN2011104326317A patent/CN102531879A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2772302A (en) * | 1952-08-07 | 1956-11-27 | Perfogit Spa | Process for the production of 11-bromoundecanoic acid |
| CN1218793A (en) * | 1997-12-04 | 1999-06-09 | 范拥军 | Process for producing bromo-undecylic acid |
| CN101289379A (en) * | 2008-06-12 | 2008-10-22 | 山西宏远科技股份有限公司 | Process for preparing bromoundecanoic acid by tower type addition of undecylenic acid |
| CN101289382A (en) * | 2008-06-12 | 2008-10-22 | 山西宏远科技股份有限公司 | Separation process of bromoundecanoic acid by freezing crystal |
Non-Patent Citations (1)
| Title |
|---|
| 崔建兰: "11-溴代十一酸的合成研究", 《辽宁化工》, vol. 31, no. 4, 30 April 2002 (2002-04-30) * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015019028A1 (en) * | 2013-08-09 | 2015-02-12 | Arkema France | Hydrobromination method |
| FR3009554A1 (en) * | 2013-08-09 | 2015-02-13 | Arkema France | HYDROBROMURATION PROCESS |
| CN105431404A (en) * | 2013-08-09 | 2016-03-23 | 阿肯马法国公司 | Hydrobromination method |
| US10590058B2 (en) | 2013-08-09 | 2020-03-17 | Arkema France | Hydrobromination method |
| CN105431404B (en) * | 2013-08-09 | 2020-12-08 | 阿肯马法国公司 | Hydrobromination process |
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Application publication date: 20120704 |