Methods for the decomposition of contaminated plastic waste
This invention relates to the field of contaminated plastic waste decomposition. More specifically, the invention comprises methods and systems to decompose contaminated plastic waste and transform it into value-added products.
1. A method for decomposing polyethylene, comprising:
a. adding polyethylene to a reaction vessel;
b. adding aqueous nitric acid (HNO 3 ) to the reaction vessel to give a mixture, wherein the wt. ratio of polyethylene to aqueous nitric acid is greater than 1:3; and
c. subjecting the mixture obtained in b. to conditions effective to decompose the polyethylene to produce decomposition products, wherein the conditions comprise a temperature of 120-140° C., and the decomposition products comprise:
i. succinic acid, glutaric acid, adipic acid, pimelic acid, and azelaic acid, and
ii. at least one of oxalic acid, suberic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, 2-octenedioic acid, 2-nonenedioic acid, 2-decenedioic acid, and 2-undecenedioic acid, or the salts or esters thereof; or at least one of C 8 -C 20 dicarboxylic acid substituted with a single nitro group, or the salts or esters thereof.
2. The method of claim 1 , wherein in c.ii., the decomposition products comprise at least one of oxalic acid, suberic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, or the salts or esters thereof.
3. The method of claim 1 , wherein in c.ii., the decomposition products comprise at least one of C 8 -C 20 dicarboxylic acid substituted with a single nitro group, or the salts or esters thereof.
4. The method of claim 3 , wherein in c.ii., the at least one C 8 -C 20 dicarboxylic acid substituted with a single nitro group is (1) nitro-suberic acid, nitro-azelaic acid, nitro-sebacic acid, nitro-undecanedioic acid, nitro-dodecanedioic acid, nitro-brassylic acid, nitro-tetradecanedioic acid, nitro-pentadecanedioic acid, nitro-hexadecanedioic acid, nitro-heptadecanedioic acid, nitro-octadecanedioic acid, nitro-nonadecanedioic acid, or nitro-icosanedioic acid, or the salts or esters thereof; or (2) 2-nitro-suberic acid, 2-nitro-azelaic acid, 2-nitro-sebacic acid, 2-nitro-undecanedioic acid, 2-nitro-dodecanedioic acid, 2-nitro-brassylic acid, 2-nitro-tetradecanedioic acid, 2-nitro-pentadecanedioic acid, 2-nitro-hexadecanedioic acid, 2-nitro-heptadecanedioic acid, 2-nitro-octadecanedioic acid, 2-nitro-nonadecanedioic acid, or 2-nitro-icosanedioic acid, or the salts or esters thereof.
5. The method of claim 3 , wherein in c.ii., the at least one C 8 -C 20 dicarboxylic acid substituted with a single nitro group is present up to 1 wt % in the decomposition products.
6. The method of claim 1 , wherein the polyethylene further comprises at least one non-plastic waste.
7. The method of claim 1 , wherein the nitric acid has a concentration of 10-90 wt %.
8. The method of claim 1 , wherein the nitric acid has a concentration of about 67 to about 70 wt %.
9. The method of claim 1 , wherein the weight ratio of polyethylene to nitric acid is 1:10 to 1:100.
10. The method of claim 1 , further comprising adding at least one solid state catalyst to the reaction vessel.
11. The method of claim 10 , wherein the at least one solid state catalyst is a zeolite, alumina, silico-alumino-phosphate, sulfated zirconia, zinc oxide, titanium oxide, zirconium oxide, niobium oxide, iron carbonate, calcium carbide, or combinations thereof.
12. The method of claim 1 , wherein the conditions effective comprise an initial pressure of 0-1000 psi.
13. The method of claim 1 , wherein the conditions effective comprise a batch process with a residence time in the reaction vessel of about 1 hour to about 10 hours.
14. The method of claim 1 , wherein the conditions effective comprise a batch process with a residence time in the reaction vessel of about 3 hours to about 6 hours.
15. The method of claim 1 , wherein the conditions effective comprise a continuous process.
16. The method of claim 15 , wherein the continuous process comprises the continuous addition of polyethylene and aqueous nitric acid to the reaction vessel and the continuous removal of decomposition products.
17. The method of claim 1 , wherein the decomposition products comprise:
a. succinic acid is present in an amount of from about 5 to about 18 wt %, glutaric acid is present in an amount of from about 8 to about 28 wt %, adipic acid is present in an amount of about 10 to about 29 wt %, pimelic acid is present in an amount of about 10 to about 20 wt %, and azelaic acid is present in an amount of about 8 to about 13 wt %, and
b. if present, oxalic acid is present in an amount up to 10 wt %, if present suberic acid is present in an amount of about 9 to about 20 wt %, if present sebacic acid is present in an amount of about 1 to about 10 wt %, if present undecanedioic acid is present in an amount of about 1 to about 8 wt %, if present dodecanedioic acid is present up to about 5 wt %, if present tridecanedioic acid is present up to about 4 wt %, if present tetradecanedioic acid is present up to about 2 wt %, and if present pentadecanedioic acid is present up to about 0.4 wt %.
18. The method of claim 1 , wherein the decomposition products comprise:
a. succinic acid is present in an amount of from about 10 to about 11 wt % glutaric acid is present in an amount of from about 15 to about 18 wt %, adipic acid is present in an amount of about 16 to about 18 wt %, pimelic acid is present in an amount of about 15 to about 17 wt %, and azelaic acid is present in an amount of about 10 to about 12 wt %, and
b. if present, oxalic acid is present in an amount up to 10 wt %, if present suberic acid is present in an amount of about 13 to about 15 wt %, if present sebacic acid is present in an amount of about 5 to about 9 wt %, if present undecanedioic acid is present in an amount of about 3 to about 6 wt %, if present dodecanedioic acid is present in an amount of 1-3 wt %, if present tridecanedioic acid is present in an amount of about 0.5 to about 1.5 wt %, if present tetradecanedioic acid is present up to about 0.2 wt %, and if present pentadecanedioic acid is present up to about 0.2 wt %.
19. The method of claim 1 , wherein
a. succinic acid is present in an amount of from about 5 to about 40 wt %, glutaric acid is present in an amount of from about 8 to about 27 wt %, adipic acid is present in an amount of about 10 to about 29 wt %, pimelic acid is present in an amount of about 10 to about 20 wt %, and azelaic acid is present in an amount of about 1 to about 13 wt %, or an equivalent amount of the salts or esters thereof, and
b. if present, oxalic acid is present in an amount up to 10 wt %, if present suberic acid is present in an amount of to about 4 to about 20 wt %, if present sebacic acid is present up to about 10 wt %, if present undecanedioic acid is present up to about 8 wt %, if present dodecanedioic acid is present up to about 5 wt %, if present tridecanedioic acid is present up to about 4 wt %, if present tetradecanedioic acid is present up to about 2 wt %, and if present pentadecanedioic acid is present up to about 0.4 wt %, or an equivalent amount of the salts or esters thereof.
20. The method of claim 1 , wherein the conditions effective further comprise the presence of a zeolite catalyst.
21. The method of claim 1 , further comprising isolating the decomposition products.
22. The method of claim 21 , wherein the decomposition products are isolated by removal of insoluble products.
23. The method of claim 22 , wherein the removal of insoluble products is by filtration.
24. The method of claim 22 , further comprising evaporation of the aqueous nitric acid.