Processes for preparing halogenated alkanes

Patent metadata

Field	Value
Publication number	US-10513478-B2
Application number	US-201716067700-A
Country	US
Kind code	B2
Filing date	Jan 4, 2017
Priority date	Jan 4, 2016
Publication date	Dec 24, 2019
Grant date	Dec 24, 2019

Abstract

The present invention provides improved processes for preparing halogenated alkanes. In particular, the processes comprise reacting an alkene, a halogenated alkene, or combinations thereof and a halogenated methane with at least one chlorine atom.

First claim

What is claimed is:

1. A process for producing halogenated alkanes, the process comprising:
a. forming a reaction mixture in a reactor by contacting: a liquid phase comprising a halogenated methane comprising at least one chlorine atom, at least one phosphorus containing compound comprising a trialkylphosphate, a trialkylphosphite, or combinations thereof; and at least one catalyst comprising a metal, metal salt, or combinations thereof; an alkene, halogenated alkene, or combinations thereof, thereby forming a reaction mixture; wherein the alkene, halogenated alkene, or combinations thereof and is at least partially absorbed into the liquid phase;
b. stirring the reaction mixture;
c. heating the reaction mixture; and
d. producing halogenated alkanes and heavy by-products;
wherein there is a gas phase above the reaction mixture and wherein the order of steps b. and c. may be switched or conducted at the same time;
wherein the process further comprises at least one of the following:
(I) stirring the reaction mixture comprising jet mixing;
(II) the process further comprises step e., wherein step e. comprises:
i. transferring at least part of the reactor contents into a first separator where two product streams (a) and (b) are formed: wherein product stream (a) comprises the halogenated alkane, halogenated methane comprising at least one chlorine atom, and an alkene or halogenated alkene; wherein product stream (b) comprises the heavy by-products, the at least one phosphorous containing compound, and at least one catalyst;
ii. contacting at least a portion of product stream (b) with an ion exchange resin to form product stream (c) wherein product stream (c) contains less of at least one metal ion when compared to product stream (b); and
iii. returning at least a portion of product stream (c) to the reactor; and
(III) the process further comprises step f, wherein step f comprises:
i. transferring at least part of the reactor contents into a first separator where two product streams (a) and (b) are formed, wherein product stream (a) comprises the halogenated alkane, halogenated methane with at least one chlorine atom, and the alkene, halogenated alkene, or combinations thereof and product stream (b) comprises the heavy by-products, the at least one phosphorous containing compound, and the at least one catalyst;
ii. transferring at least a portion of product stream (b) back into the reactor;
iii. transferring product stream (a) into a second separator and producing two product streams (d) and (e), wherein product stream (d) comprises the halogenated alkane and product stream (e) comprises halogenated methane with at least one chlorine atom and the alkene, halogenated alkene, or combinations thereof;
iv. optionally introducing at least a portion of product stream (e) into the reactor;
wherein at least one of the first separator and the second separator comprises a reboiler, bottom stage, or both;
wherein the first separator or the second separator may be separate or contained in a single separation device;
wherein when the first and second separation devices are contained in a single separation device, the single separation device will separate at least a portion of product stream (d) from product streams (b) and (e);
wherein one or more of the separators is a multistage distillation column in which a stripping gas or low boiling stripping liquid comprising an alkane, alkene, halogenated alkane, halogenated alkene, or nitrogen is introduced into the first separator reboiler, the second separator reboiler, the first separator bottom stage, the second separator bottom stage, or combinations thereof; and wherein the stripping gas or low boiling stripping liquid is in addition to any components originating from the reactor.

2. The process of claim 1 , wherein the process comprises (I).

3. The process of claim 1 , wherein the process comprises (II).

4. The process of claim 1 , wherein the process comprises (III).

5. The process of claim 1 , wherein jet mixing withdraws a portion of the liquid phase of the reaction mixture from the reactor and pumps the liquid phase back into the reactor through at least one nozzle to create a jet, thereby creating turbulence in the liquid phase.

6. The process of claim 1 , wherein jet mixing withdraws a portion of the liquid phase of the reaction mixture from the reactor and pumps the liquid phase back into the reactor through at least one nozzle to create a jet directed through the gas phase and into the liquid phase of the reaction mixture, thereby entraining gas into the liquid phase.

7. The process of claim 1 , wherein jet mixing withdraws a portion of the liquid phase of the reaction mixture from the reactor and pumps the liquid phase back into the reactor through at least one gas educting nozzle, wherein the suction of the eductor pulls gas from the gas phase of the reaction mixture, mixes the gas with the circulated liquid, and returns the resulting mixture of liquid and gas back into the liquid phase of the reactor.

8. The process of claim 1 , wherein a portion of the liquid phase is withdrawn from the reaction mixture and pumped through a spray nozzle, wherein the spray leaving the spray nozzle goes through the gas phase and absorbs some of the gas phase and returns to the reaction mixture.

9. The process of claim 1 , wherein the reactor further comprises a draft tube to produce an internal recirculation inside the reactor.

10. The process of claim 1 , wherein the halogenated methane with at least one chlorine atom is carbon tetrachloride.

11. The process of claim 1 , wherein the alkene comprises ethylene and the halogenated alkene comprises vinyl chloride.

12. The process of claim 1 , wherein the halogenated alkane is a chloroalkane, and the chloroalkane comprises 1,1,1,3-tetrachloropropane or 1,1,1,3,3-pentachloropropane.

13. The process of claim 1 , wherein at least one catalyst comprises iron metal, copper metal, iron containing compound, copper containing compound, iron containing alloy, copper containing alloy, or combinations thereof.

14. The process of claim 13 , wherein the at least one catalyst further comprises a trialkylphosphate, trialkylphosphite, or combinations thereof and wherein the trialkylphosphate, trialkylphosphite, or combinations thereof is complexed to Fe(II), Fe(III), Cu(I), Cu(II), or combinations thereof.

15. The process of claim 1 , wherein the trialkylphosphate comprises triethylphosphate, tripropylphosphate, triisopropylphosphate, tributylphosphate, or combinations thereof; and wherein the trialkylphosphite comprises trimethylphosphite, triethylphosphite, tripropylphosphite, triisopropylphosphite, tributylphosphite, tri-tertbutylphosphite, or combinations thereof.

16. The process of claim 1 , wherein the reaction mixture is maintained at a temperature from about 80° C. to about 140° C.; and the process is conducted at a pressure from about atmospheric pressure (˜14.7 psi) to about 200 psi.

17. The process of claim 1 , wherein the process is continuous.

18. The process of claim 1 , wherein the weight % of the halogenated alkane is at least 50 weight % in the liquid phase of the reactor.

19. The process of claim 1 , wherein the reaction is conducted in a series of stirred tank reactors.

20. The process of claim 1 , wherein the ion exchange resin comprises a cation exchange resin.

21. The process of claim 17 , wherein the phosphorous compound and halogenated methane comprising at least one chlorine atom are continuously add

Assignees

• Blue Cube Ip Llc

Inventors

• Myers John D
• Tirtowidjojo Max M
• Luebbe Thomas U
• Sell Marc

Classifications

• C07C17/389

  by adsorption on solids · CPC title

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C07C17/383

  by distillation · CPC title

• C07C17/386

  with auxiliary compounds · CPC title

• C07C17/275 Primary

  of hydrocarbons and halogenated hydrocarbons · CPC title