Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons

1. A process comprising:

reacting at least gaseous alkanes and a halogen to produce at least a halogenation product stream, wherein the halogenation product stream comprises alkyl halides, hydrogen halide, and unreacted alkanes;

separating the halogenation product stream into at least a gaseous stream and a liquid alkyl halides stream, wherein the gaseous stream comprises hydrogen halide and unreacted alkanes, and wherein the liquid alkyl halides stream comprises alkyl halides;

separating the liquid alkyl halides stream into at least a monohalides stream and a polyhalides stream, wherein the monohalides stream comprises monohalogenated alkanes, and wherein the polyhalides stream comprises polyhalogenated alkanes; and

reacting at least a portion of the monohalogenated alkanes from the monohalides stream in the presence of a catalyst to produce at least a synthesis product stream, wherein the synthesis product stream comprises higher molecular weight hydrocarbons and hydrogen halide.

2. The process of claim 1 wherein the halogen comprises bromine.

3. The process of claim 1 wherein the gaseous alkanes comprise alkanes having 2 or more carbons in an amount of less than about 0.1 mole % to less than about 10 mole %.

4. The process of claim 1 wherein the step of separating the halogenation product stream comprises:

cooling the halogenation product stream;

separating the halogenation product stream into a liquid fractionator feed stream and a gaseous fractionator feed stream; and

feeding the liquid fractionator feed stream and the gaseous fractionator feed stream into a fractionator, wherein the gaseous stream and the liquid alkyl halides stream are withdrawn from the fractionator.

5. The process of claim 4 wherein the fractionator operates at a pressure of about 20 bars to about 40 bars.

6. The process of claim 4 further comprising:

withdrawing a second liquid stream from the fractionator and heating the second liquid stream to a temperature of about 100° C. to about 200° C. in a reboiler; and

withdrawing an overhead vapor stream from the fractionator and cooling the overhead vapor stream to a temperature warmer than about −40° C. in a condenser.

7. The process of claim 6 further comprising cooling the overhead vapor stream against the gaseous stream.

8. The process of claim 4 further comprising:

cooling the gaseous fractionator feed stream against the gaseous stream; and

cooling the halogenation product stream against a halogenation feed stream comprising the gaseous alkanes and the halogen from the step of reacting at least gaseous alkanes and a halogen.

9. The process of claim 1 wherein the liquid alkyl halides stream comprises less than about 2% by weight of the hydrogen halide from the halogenation product stream.

10. The process of claim 1 wherein the unreacted alkanes in the gaseous stream comprises methane and alkanes having 2 or more carbons in an amount of less than about 1% by mole.

11. The process of claim 1 wherein the gaseous stream comprises less than about 10 mppm alkyl halides.

12. The process of claim 1 further comprising reducing the liquid alkyl halides stream to a pressure of about 1 bar to about 30 bars.

13. The process of claim 1 wherein the step of separating the liquid alkyl halides stream into at least a monohalides stream and a polyhalides stream comprises: feeding the liquid alkyl halides stream into a second fractionator, wherein the monohalides stream and the polyhalides stream are withdrawn from the second fractionator.

14. The process of claim 13 further comprising:

withdrawing a liquid stream from the second fractionator and heating the liquid stream to a temperature of about 150° C. to about 250° C. in a reboiler; and

withdrawing an overhead vapor stream from the second fractionator and cooling the overhead vapor stream to a temperature warmer than about 37° C. in a condenser.

15. The process of claim 12 wherein the monohalides stream comprises monohalogenated methane, wherein polyhalogenated alkanes are present in the monohalides stream in an amount less than about 100 mppm.

16. The process of claim 1 further comprising:

recovering at least a portion of the hydrogen halide from the gaseous stream; and

recovering at least a portion of the hydrogen halide from the synthesis product stream, wherein recovery of the hydrogen halide from the synthesis product stream occurs in the same unit as the recovery of the hydrogen halide from the gaseous stream.

17. The process of claim 1 further comprising:

recovering at least a portion of the hydrogen halide from the gaseous stream; and

recovering at least a portion of the hydrogen halide from the synthesis product stream; wherein recovery of the hydrogen halide from the synthesis product stream occurs in a different unit than the recovery of the hydrogen halide from the gaseous stream.

18. The process of claim 1 further comprising reacting the gaseous alkanes with at least a portion of the polyhalogenated alkanes from the polyhalides stream to convert at least a portion of the polyhalogenated alkanes to monohalogenated alkanes.

19. The process of claim 1 further comprising reacting at least a portion of the polyhalogenated alkanes from the polyhalides stream with light end hydrocarbons to convert at least a portion of the alkyl halides from polyhalogenated alkanes to monohalogenated alkanes.

20. The process of claim 1 further comprising separating light end hydrocarbons from at least the higher molecular weight hydrocarbons and a natural gas feed, the light end hydrocarbons having from 2 carbons to 4 carbons.

21. The process of claim 20 further comprise reacting at least a portion of the light-end hydrocarbons with a halogen to form a stream comprising alkyl halides and hydrogen halide; and reacting at least a portion alkyl halides in the presence of the catalyst.

22. The process of claim 1 wherein the catalyst comprises a synthetic crystalline alumino-silicate catalyst.

23. A process comprising

reacting at least gaseous alkanes and bromine in a bromination reactor to produce at least a bromination product stream, wherein the bromination product stream comprise alkyl bromides, hydrogen bromide, and unreacted alkanes;

separating the bromination product stream into at least a gaseous alkane/HBr stream and a liquid alkyl bromides stream, wherein the gaseous alkane/HBr stream comprises hydrogen bromide and unreacted alkanes, and wherein the liquid alkyl bromides stream comprises alkyl bromides;

separating the liquid alkyl bromides stream into at least a monobromides stream and a polybromides stream, wherein the monobromides stream comprises monobrominated alkanes, and wherein the polybromides stream comprises polybrominated alkanes;

reacting at least a portion of the monobrominated alkanes from the monobromides stream in a synthesis reactor to produce at least a synthesis product stream, wherein the synthesis product stream comprises higher molecular weight hydrocarbons and hydrogen bromide;

recovering at least a portion of the hydrogen bromide from the synthesis product stream in a hydrogen bromide separator;

providing a natural gas stream;

separating at least the synthesis product stream and the natural gas stream into at least a light ends product stream, a heavy ends product stream, and a feed gas stream, wherein the light ends product stream comprises light end hydrocarbons having from 2 carbons to 4 carbons, wherein the heavy ends product stream comprises heavy end hydrocarbons having 5 or more carbons, and wherein the feed gas stream comprises methane;

compressing the feed gas stream in a feed compressor;

feeding the feed gas stream into the bromination reactor;

generating a recycle alkane stream by recovering at least a portion of the hydrogen bromide from the gaseous alkane/HBr stream in a second hydrogen bromide separator operating at a higher pressure than the hydrogen bromide separator;

compressing the recycle alkane stream in a recycle compressor; and

feeding the recycle alkane stream to the bromination reactor.

24. The process of claim 23 wherein the step of separating the bromination product stream comprises:

cooling the bromination product stream;

separating the bromination product stream into a liquid fractionator feed stream and a gaseous fractionator feed stream; and

feeding the liquid fractionator feed stream and the gaseous fractionator feed stream into an alkyl bromides fractionator, wherein the gaseous alkane/HBr stream and the liquid alkyl bromides stream are withdrawn from the alkyl bromides fractionator, and wherein the alkyl bromides fractionator operates at a pressure of about 20 bars to about 40 bars.

25. The process of claim 23 wherein the liquid alkyl bromides stream comprises less than about 2% by weight of the hydrogen bromide from the bromination product stream.

26. The process of claim 23 wherein the gaseous alkane/HBr stream comprises less than about 10 mppm alkyl bromides.

27. The process of claim 23 further comprising feeding the polybromides stream to the bromination reactor such that at least a portion of the polybrominated alkanes react with the gaseous alkanes to convert at least a portion of the polybrominated alkanes to monobrominated alkanes.

28. The process of claim 23 further comprising reacting at least a portion of the polybrominated alkanes from the polybromides stream with at least a portion of the light end hydrocarbons from the light-ends product stream to convert at least a portion of the polybrominated alkanes to monobrominated alkanes.

29. The process of claim 23 further comprising:

reacting bromine and at least a portion of the light end hydrocarbons from the light-end hydrocarbon stream to form a brominated stream comprising brominated light end hydrocarbons, hydrogen bromide, and unreacted light end hydrocarbons; and

reacting at least a portion of the brominated light end hydrocarbons in the presence of the catalyst in the synthesis reactor.

30. The process of claim 23 wherein the catalyst comprises a synthetic crystalline alumino-silicate catalyst.