Radical initiators and chain extenders for converting methane gas into methane-sulfonic acid
View Patent ↗Improved initiators, solvents, and SO3 mixtures are disclosed which can increase the yields and efficiency of a process which converts methane gas into methane-sulfonic acid (MSA). MSA is valuable in its own right, or it can be processed to create desulfured fuels and other chemicals. Preferred initiators have been identified, comprising at least one “primary” initiator, and at least one “extender” (or secondary, supplemental, enhancing, tuning, tweaking, or similar terms) initiator. “Primary” initiator(s) include (unmethylated) Marshall's acid, mono-methyl-Marshall's acid, and di-methyl-Marshall's acid, while a secondary/extender initiator comprises methyl-Caro's acid, which can oxidize sulfur DI-oxide (an unwanted chain terminator) into sulfur TRI-oxide (an essential reagent). Other enhancements to the MSA manufacturing process also are described.
1. A method for producing methane-sulfonic acid from methane and sulfur trioxide using methane sulfonic acid, sulfuric acid or a combination thereof as a solvent which comprises performing a radical chain reaction by introducing a first gas/liquid mixture comprising sulfur trioxide reagent and methane into a reactor vessel continuously with a second mixture comprising:
(i) at least one primary initiator compound having a peroxide bond which when broken will release radical species capable of efficiently removing hydrogen atoms from at least one hydrocarbon or carbohydrate reagent, wherein said primary initiator compound is selected from the group consisting of methyl-Marshall's acid (methyl-sulfonyl-peroxo-sulfuric acid), and dimethyl-Marshall's acid (dimethyl-sulfonyl-peroxide), and combinations thereof; and,
(ii) methyl-Caro's acid (methyl-sulfonyl-peroxy-acid) as an extender initiator having a peroxide bond which, when broken apart, will release at least one radical species that will oxidize sulfur dioxide molecules into sulfur trioxide molecules wherein the quantity of said extender initiator is in the range of from 2% to 10% of the total initiator weight, and wherein said reactor vessel comprises a tube enclosure with at least one internal static mixing baffle configured for processing the gas/liquid mixture that flows through said tube enclosure at a pressure in the range of from 470 psi to 1500 psi and a temperature in the range of from 60° C. to 90° C. under plug flow conditions with the result that methane-sulfonic acid in liquid form is recovered from the reactor vessel.
2. The method of claim 1 wherein said reactor vessel comprises multiple linear segments of tubing, coupled together to create a continuous flow path through multiple tubing segments.
3. The method of claim 1 or claim 2 wherein (i) said extender initiator is injected separately into the reactor vessel but continuously while said primary initiator is introduced into the reactor vessel or (ii) said extender initiator is injected intermittently into the reactor vessel while said primary initiator is introduced into the reactor vessel.
4. The method of claim 1 or claim 2 wherein said first gas/liquid mixture comprising sulfur trioxide reagent and methane is introduced into said reactor vessel continuously with:
(i) the at least one primary initiator compound, and
(ii) the extender initiator is generated within the reactor vessel.
5. The method of claim 1 or claim 2 wherein said second mixture comprises:
(i) methyl-Marshall's acid (methyl-sulfonyl-peroxo-sulfuric acid), and
(ii) methyl-Caro's acid (methyl-sulfonyl-peroxy-acid) that is formed by mixing H 2 O 2 with methane sulfonic acid and then adding SO 3 to the resulting mixture wherein the SO 3 is added at no more than a molar equivalent of the amount of methyl-Marshall's acid in the mixture.