Method for making bromides

Patent metadata

Field	Value
Publication number	US-9688543-B2
Application number	US-201414538838-A
Country	US
Kind code	B2
Filing date	Nov 12, 2014
Priority date	Dec 9, 2013
Publication date	Jun 27, 2017
Grant date	Jun 27, 2017

Abstract

Bromine containing compounds, such as calcium bromide, sodium bromide and the like, are prepared in high purity and more quickly with less waste by using a process with two bromination stages and often a third step wherein the crude product mixture can be adjusted to meet specific product requirements. In the first bromination stage, the majority, but not all, of a substrate is brominated using a reductive bromination reaction, the remaining unreacted substrate is converted to product in the second stage through another a reductive bromination reaction, although the specific reagents may be different, wherein the addition of bromine and a reducing agent are carefully monitored.

First claim

What is claimed:

1. A process for producing a compound of formula RBr n , wherein R is an alkali or alkali earth metal and n is 1 or 2, said process comprising:
I) a first stage wherein a mixture comprising a first reducing agent and a substrate of formula R p X m ,
wherein R is a Group 1 metal or a Group 2 metal; m is a number 1 or 2; p is a number 1 or 2; and X is oxygen atom, carbonate, bicarbonate or OH;

is reacted with an amount of bromine necessary to brominate from about 70 to about 98% of RX m to RBr n to provide an intermediate mixture comprising RBr n and residual substrate RX m , wherein at least a portion of the first stage is run at a reaction temperature of 50° C. or higher and/or at greater than atmospheric pressure, and
II) a second stage wherein a second reducing agent, different from the first reducing agent, and an amount of bromine needed to provide 100% conversion of residual substrate RX m are separately added to the intermediate mixture from I), forming a reaction product mixture, wherein addition of the second reducing agent and bromine in the second stage are continuously adjusted to maintain or re-establish the pH and oxidation/reduction potential of the reaction mixture during the second stage within predetermined ranges by increasing, suspending or slowing addition of bromine when the pH of the reaction mixture is outside of a predetermined range until the predetermined pH range is re-established, and by increasing, suspending or slowing addition of the second reducing agent when the oxidation/reduction potential of the reaction mixture is outside of a predetermined range until the predetermined oxidation/reduction potential range is re-established.

2. The process according to claim 1 wherein R in formula RBr n and R p X m is selected from the group consisting of Li, Na, K, Mg, Ca, preferably wherein X is oxygen atom or OH.

3. The process according to claim 2 wherein X is oxygen atom or OH.

4. The process according to claim 1 wherein the first reducing agent and the second reducing agent are selected from the group consisting of ammonia, ammonium salts, formamide, urea, cyanamide, carbamates, hydrazine and hydrazine derivatives.

5. The process according to claim 1 wherein the first reducing agent is ammonia.

6. The process according to claim 1 wherein in the first stage, Br 2 is added in an amount necessary to convert from about 70 to about 90% of the substrate of formula R p X m to RB n .

7. The process according to claim 1 wherein in the second stage, bromine addition is under cascade control linked to the measured pH of the reaction and reducing agent addition is under cascade control linked to the measured oxidation/reduction potential of the reaction, wherein rate of bromine addition is continuously adjusted based on any difference between a desired pH value and the measured pH of the reaction mixture; rate of addition of the second reducing agent is continuously adjusted based on any difference between a desired oxidation/reduction potential value and the measured oxidation/reduction potential of the reaction mixture, using an automated system designed to calculate necessary addition rate adjustments through a continuous feedback loop using the measured pH and oxidation/reduction potential values, the desired pH and oxidation/reduction potential values and existing addition rate set points, and then automatically reset the addition rates.

8. The process according to claim 1 wherein in stage 2 the predetermined range for pH has an upper limit of 1.

9. The process according to claim 1 comprising one or more additional stage for pH adjustment of the reaction product, concentration adjustment of the reaction product, isolation of the reaction product and/or purification of the reaction product.

10. The process according to claim 1 which is a continuous process.

11. The process according claim 1 wherein the first or second stage is run in a loop reactor comprising an inline static mixer and heat exchanger.

12. The process according to claim 7 wherein the second stage is run in a loop reactor comprising an inline static mixer, heat exchanger and pH and oxidation/reduction potential cascade control systems.

13. The process according to claim 12 , wherein the first stage is run in a loop reactor comprising an inline static mixer and heat exchanger.

14. The process according to claim 4 wherein the first reducing agent is selected from the group consisting of ammonia, ammonium salts, formamide and urea and the second reducing agent is selected from the group consisting of hydrazine and hydrazine derivatives.

15. The process according to claim 1 wherein the second reducing agent is hydrazine.

16. The process according to claim 5 wherein the second reducing agent is hydrazine.

Assignees

• Chemtura Corp
• Lanxess Solutions Us Inc

Inventors

• Ray Thomas G
• Bartley David W
• Broadhurst Hugh
• Goodwin Nate

Classifications

• C01D15/04

  Halides · CPC title

• B01J2219/00087

  with heat exchange elements outside the reactor · CPC title

• C01F11/34 Primary

  Bromides · CPC title

• C01B9/04

  Bromides · CPC title

• B01J2219/00772

  in a helix · CPC title