EP1720831A1 - Fabrication d'hydrocarbures superieurs a partir du methane, via l'acide sulfonique de methane, le sulfene, et d'autres voies - Google Patents

Fabrication d'hydrocarbures superieurs a partir du methane, via l'acide sulfonique de methane, le sulfene, et d'autres voies

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Publication number
EP1720831A1
EP1720831A1 EP04810350A EP04810350A EP1720831A1 EP 1720831 A1 EP1720831 A1 EP 1720831A1 EP 04810350 A EP04810350 A EP 04810350A EP 04810350 A EP04810350 A EP 04810350A EP 1720831 A1 EP1720831 A1 EP 1720831A1
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EP
European Patent Office
Prior art keywords
sulfene
msa
methane
catalysts
reaction
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EP04810350A
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German (de)
English (en)
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EP1720831A4 (fr
Inventor
Alan K. Richards
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Individual
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Individual
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Priority claimed from PCT/US2003/035396 external-priority patent/WO2004041399A2/fr
Priority claimed from PCT/US2004/019977 external-priority patent/WO2005069751A2/fr
Application filed by Individual filed Critical Individual
Publication of EP1720831A1 publication Critical patent/EP1720831A1/fr
Publication of EP1720831A4 publication Critical patent/EP1720831A4/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/868—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains sulfur as hetero-atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
    • C07C1/322—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom the hetero-atom being a sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
    • C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/22—Higher olefins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • This invention relates to organic chemistry, hydrocarbon chemistry, and processing of methane gas. Because there have been no adequate methods for converting methane gas into liquids that can be transported efficienty to commercial markets, huge volumes of methane are wasted every day, mainly by flaring or reinjection, at fields that produce crude oil. In addition, numerous gas fields are simply shut in, at numerous locations around the world. Skilled chemists have tried for at least 100 years to develop methods for converting methane gas into various types of liquids. While various efforts in the prior art could produce relatively small quantities and low yields of methanol or other liquids, none of those efforts ever created yields that were sufficient to support commercial use at oil- producing sites.
  • LNG processing burns about 40% of a methane stream, to refrigerate the remainder to somewhere between -260 and -330°F, causing it to liquefy so it can be loaded into specialized ocean-going tankers. After a tanker reaches its destination, another large portion of the methane must be burned, to warm the remainder back up to temperatures that allow it to be handled by normal pipes and pumps. Therefore, LNG wastes roughly half of a methane stream. Nevertheless, as of mid 2004, oil companies had committed an estimated $30 billion to build LNG facilities. Fischer-Tropsch processing burns about 30% of a methane stream, to convert the remainder into a carbon monoxide and hydrogen mix called "synthetic gas" or "syngas".
  • the syngas is then converted (using expensive catalysts) into heavy oils and paraffins, which then must be cracked and/or distilled to convert them into diesel fuel, heating oil, and other products.
  • the syngas conversion, the catalyst costs, and the requirement for cracking thick and heavy oils and waxes all create inefficiencies, but as of mid 2004, companies have committed tens of billions of dollars to Fischer-Tropsch facilities.
  • the wastes and inefficiencies of LNG and Fischer-Tropsch systems prove the assertion that any methane-to-methanol systems previously proposed, based on small-scale laboratory work, have not been regarded as commercially practical, by any major companies.
  • most methanol conversion systems proposed to date generate large quantities of acidic and hazardous byproducts and toxic wastes.
  • MSA methane-sulfonic acid
  • FIGURES 1 and 2 The methane-to-methanol conversion system disclosed in those two applications is illustrated in FIGURES 1 and 2 herein, and can be briefly summarized as follows: (1) An "initiator” compound is used to trigger a reaction that will become a chain reaction that will continue indefinitely. This is accomplished by creating and using a "strong radical” that can efficiently remove a complete hydrogen atom (both a proton, and an electron) from methane, thereby creating a methane radical with an unpaired electonr, represented herein as H 3 C*, where * represents the unpaired electron.
  • H 3 C* an unpaired electonr
  • * represents the unpaired electron.
  • Various methods and compounds for creating methyl radicals are known, and several are illustrated in FIG. 1, and described in PCT/US2004/019977.
  • hydroxy radicals are much stronger than conventional hydroxy radicals (HO*) from compounds such as hydrogen peroxide.
  • sulfuric acid radicals will remove hydrogen atoms from methane, to create stabilized sulfuric acid while converting the methane into methyl radicals. Because a small quantity of Marshall's acid will trigger a chain reaction that will keep going and convert a large quantity of methane into MSA and/or methanol, the amount of sulfuric acid waste will be small, if Marshall's acid is used as a radical initiator.
  • the unstable methyl radicals are mixed with sulfur trioxide.
  • methyl radicals are not strong enough to remove anything from SO 3 , they will bond to it, thereby forming radicals of methane-sulfonic acid.
  • the MSA radicals which are quite strong, will attack fresh methane that is being continuously pumped into the reactor vessel. Each MSA radical will remove a single hydrogen atom (both proton and electron) from a methane molecule. This creates stabilized MSA, in liquid form. It also creates new methyl radicals, which will keep the chain reaction going, as long as proper quantities of methane and SO 3 continue to be added to the reactor vessel.
  • liquid MSA in the reactor vessel also acts as an "amphoteric" solvent (i.e., a solvent having two domains with different traits).
  • the methyl domain of MSA helps methane gas dissolve and mix rapidly in the solution, while the sulfonic domain helps liquid SO 3 mix rapidly in the solution.
  • Liquid MSA, which is being formed in the reactor is continuously removed from the outlet of the reactor. It is then passed through a "cracking" vessel, which breaks it apart (this process can also be called thermolysis, since it is carried out at elevated temperatures).
  • the "cracking" operation causes a rearrangement of the molecule, in a way that causes the hydroxy group of the SO 3 H sulfonic domain of MSA to leave with the methyl group.
  • This allows the cracking operation to release methanol (H 3 COH) and sulfur dioxide (SO 2 ).
  • SO 3 is pumped into the reactor, and it combines with methane gas to form MSA.
  • the MSA is cracked, in a way that transfers a hydroxy group to the methyl carbon, to form methanol while releasing SO 2 .
  • the SO 2 is then passed through a separate reactor, which oxidizes it back to SO 3 , using oxygen from the atmosphere.
  • the SO 3 is then returned to the MSA reactor, to complete the cycle.
  • the reaction shown on the left side of FIG. 2 is not an endless cycle. Instead, methane (a gas) is pumped into the system, and methanol (a liquid) is pumped out. That reaction pathway is described in more detail in the two above-cited PCT applications. It should be noted that MSA does not need to be cracked, to release methanol, to accomplish the goal of converting methane gas into a stable and transportable liquid.
  • MSA intermediate is regarded as the dividing point between "upstream” and “downstream” processing. Any steps, reactors, or devices used to make or purify MSA (or its precursors, such as Marshall's acid or any other radical initiator), or to keep an MSA-forming reactor running properly, are regarded as being on the upstream side of an operation. By contrast, any steps, reactors, or devices that receive MSA as a feedstock, intermediate, or product are on the "downstream" side of an operation.
  • the MSA-forming reactor is analogous to a dam on a river; it is neither upstream nor downstream, and instead is what creates and defines the different upstream and downstream zones.
  • the oxidation of SO 2 to SO 3 also is neither upstream nor downstream; in most cases, it will be carried out in a separate and isolated reactor system that will not receive or process any organic compounds at all (although it may contain organic catalysts to speed up the SO 2 to SO 3 oxidation).
  • Catalytic Surfaces, Zeolites, and Monoliths Many chemical reactions involved in this invention use catalysts that are coated onto the surfaces of hard supporting materials, such as wire meshes, particulates in packed or fluidized beds, Zeolites or other porous solids, etc.
  • "Supported” (or immobilized) catalysts are widely used in petroleum and chemical processing, since they allow expensive catalysts to be held and retained inside a reactor while large volumes of gas and/or liquid are pumped through the reactor.
  • supported catalysts are well known, and are described in numerous books (such as Hayes et al 1997), articles (such as Raja et al 2000), and patents (various examples are cited below, most of which briefly mention one or more types of support and then focus on the catalysts that are coated onto the support surface).
  • This section contains a brief overview of three major types of catalysts, which are zeolite, SAPO, and monolith materials. This is followed by a discussion of how "ketene” compounds have been created by catalytic surfaces, which can help explain some of the principles that arise in creating a compound called "sulfene", which is important in this invention.
  • Zero-silicon is the common name that has been given to porous "aluminosilicate” materials that contain silicon, aluminum, and oxygen, in crystalline lattices.
  • the lattices have molecular-sized cavities (also called cages) that are connected to each other by smaller tunnels (channels), in repeating geometric formations.
  • the sizes of the cavities can be modified, in controlled ways, by varying the formulation of a zeolite, thereby providing a certain zeolite formulation with cavities that are an optimal size to hold a particular type of molecule that will be processed by that zeolite.
  • the narrow tunnels between cavities are small enough to force molecules being treated to line up in certain orientations, before they can pass from one cavity to the next, driven by pressure from a gas or liquid.
  • the crystalline lattice that forms the cavities and tunnels can be embedded (or "doped") with catalytic atoms, ions, or molecules. Because of these factors, zeolites and other porous catalysts can cause organic molecules to react in controllable ways that cannot be easily achieved by other materials.
  • MTO Methanol-to-olefin
  • zeolite or SAPO beds usually require periodic cleaning and regeneration, usually at high temperatures.
  • many types of zeolites and similar catalytic materials have been developed that are designed to have surface activity only. Some of these materials have microscopic pores, comparable to pits, which encourage certain molecules to nestle into those pits in certain orientations, causing a certain atom or domain of the molecule to remain exposed to gases or liquids that are passed over the surface of the "charged” or “loaded” material.
  • Other materials may be chemically treated, to bond positively- or negatively-charged atoms or groups to their surfaces, usually at a controlled density or spacing.
  • monoliths can provide higher and faster flow rates, lower pressure drops, and fewer clogging and fouling problems, compared to zeolites or other materials having non-linear flow channels. Therefore, catalytic monoliths are often used in devices that cannot be easily or periodically shut down and cleaned out (such as catalytic converters that remove pollutant gases from automobile exhausts).
  • Monoliths can be prepared with various channel sizes and densities, usually expressed as channels per square inch (cpsi).
  • Monoliths that handle gases usually have cpsi values ranging from about 400 to over 1000.
  • Monoliths that handle liquids or foams require larger channels, with correspondingly lower cpsi numbers, to achieve an optimal balance between (i) reasonable and acceptably low "pressure drops" across the material, and (ii) desirably high levels of contact between the solid surfaces and the liquids flowing through the channels. Because thousands of flow channels pass through a monolith of any substantial size, very large total surface areas, inside the thousands of tiny flow channels, will be contacted by a gas or liquid that passes through a monolith.
  • the material that provides the porous supporting structure of a catalytic monolith is usually called the "support”.
  • substrate it is sometimes referred to as the "substrate", to distinguish it from the catalytic coating material, but that term is confusing and should be avoided, since “substrate” also refers to a chemical compound that is acted upon by a catalyst, enzyme, or other chemical reagent.
  • monolith supports must be able to withstand strong acids (which eliminates most metals and alloys) and high temperatures (which eliminates most plastics and starch-type polymers) . These requirements usually lead to the use of minerals and/or ceramics, which frequently contain silicon and oxygen (often referred to as "silicate” materials), which are comparable to quartz but with porous lattices that provide flow channels.
  • Support compounds such as cordierite, mullite, or silicon carbide are widely used, and are sold by companies such as Corning Inc. (www.corning.com) and Rauschert Process Technologies (www.rauschertus.com).
  • Various types of surfaces can be provided on a hard support material.
  • One class of such surfaces is called “porous” supports, which implies irregular and uneven surfaces, which may be created by the material itself, or by surface treatment processes such as anodic or acidic etching.
  • "abraded" supports usually provide smoother surfaces, formed by processes comparable to sanding. The suitability of any such porous, abraded, or other support surface, for hydrocarbon or chemical processing as disclosed herein, can be evaluated through routine testing.
  • the surface of a hard and presumably inert support material is coated with catalytic atoms, ions, or groups; the term "coating” is used broadly herein, and involves plating, liquid immersion, sputter coating or other gaseous diffusion, or any other process that creates a surface layer that is somehow different from an underlying support material).
  • the second approach involves incorporating the catalytic atoms, ions, or groups into the reagents used to form a supported catalyst, in some manner that distributes the catalytic atoms, ions, or groups throughout the resulting material.
  • This second method is conventionally used to make zeolite, SAPO, and monolith materials that require catalytic "dopant" atoms to be positioned at regular intervals in a crystalline lattice.
  • Either of those two approaches can be regarded as "functionalizing" a catalyst, in a way that turns an inert supporting material into a chemically active material that can help trigger, drive, and control valuable reactions.
  • This is a brief and simplified overview, intended to help readers who do not specialize in these types of materials develop a basic understanding of how these types of materials are made and used. Any reader who wants more information on supported catalysts can locate numerous articles and books on the subject, and in websites that provide lecture and course notes for chemistry courses at various universities.
  • the IZA has been designated by the IUPAC (the International Union of Pure and Applied Chemists) as having official responsibility for nomenclature and other matters relating to zeolites and other compounds with structural lattices that enable them to function as molecular sieves and/or catalysts.
  • the IZA has three major working groups, devoted to structures, synthesis, and catalysis.
  • At least one professional journal, Microporous and Mesoporous Materials is entirely devoted to zeolite and similar materials, and several other journals (including the Journal of Molecular Catalysis, the Journal of Physical Chemistry, and Fuel Processing Technology) frequently publish articles on processing and research using porous catalysts. Accordingly, experts who specialize in particular formulations, or in processing certain classes of chemicals on porous catalysts, can be located by contacting an editor who works with one of those journals, or by reviewing the titles of articles that have been published in such journals. Also, methods and machines have been developed for screening large numbers of candidate catalyst formulations, in a rapid and automated manner. These methods and machines are described in articles such as Muller et al 2003, and other articles cited therein.
  • Such devices use, for example: (i) reactors with multiple parallel tubes, each tube containing a different candidate catalyst, or (ii) titer plates with multiple wells, each well containing a candidate catalyst.
  • a certain reagent is passed through or loaded into all of the tubes or wells, the product generated by each individual tube or well (and therefore by each candidate catalyst) is collected separately, and delivered to an automated analytical device, such as a mass spectrometer or chromatograph.
  • the tubes or wells that created the highest yields of the desired compound can be identified, and the exact content of the catalysts in any tubes or wells that resulted in good and desirable yields can be identified and studied more closely.
  • the best-performing candidate catalyst from one round of tests can be used as a "baseline” or "centerpoint” material, in a subsequent round of tests that will use variants that resemble the best-performing catalyst from the previous round of screening.
  • Those variants can include known and controlled compounds, having exact compositions; alterately or additionally, "combinatorial chemistry" methods and reagents can be used, to generate random or semi-random variants of a material that provided good results in an earlier screening test. Accordingly, these types of automated screening systems offer powerful and useful tools for rapidly identifying and/or improving porous catalyst formulations that can efficiently promote any particular desired reaction.
  • MSA has two very different domains, methyl and sulfonic.
  • the silicate support merely uses hydroxy groups to attract and interact with MSA.
  • More potent and efficient catalysts might be developed, by providing a catalytic surface with two different types of functional agents, allowing one type of catalytic group to attract and interact with the sulfonic portion of MSA, while the second type of catalytic group attracts and interacts with the methyl portion.
  • this "close association” will last only very brief time (typically measured in milliseconds), and it will occur solely during the transition from one state to a different state (especially in reactions that run at high temperatures).
  • This association usually is initiated by some form of charged (positive- to-negative) attraction, in which hydrogen protons or other positively-charged ions or atoms are attracted to localized negative charges (such as unshared electron pairs, on the surfaces of exposed oxygen atoms) .
  • This charge attraction draws a liquid or gaseous compound into close proximity with certain molecules on the surface of the support material.
  • any reference to any transitional or intermediate state of any particular atom, ion, or radical can be regarded as merely a convenient reference term, comparable to an estimate or approximation, intended to provide a map or narrative description of the relevant terrain, for the use of experts who wish to analyze these types of reactions in greater detail.
  • this invention resides in the recognition and disclosure of several practical and useful results (including but not limited to the realization that MSA, which can be formed from "waste” methane, can be pushed into forming a sulfene intermediate, and the sulfene will then react in ways that will form ethene or other valuable compounds).
  • MSA which can be formed from "waste” methane
  • sulfene will then react in ways that will form ethene or other valuable compounds.
  • Those and other practical teachings herein form the essence of this invention, and any discussion of postulated, hypothesized, probable, or modeled atomic or molecular interactions or transition states is offered merely as additional commentary, in the hope that such commentary might be useful to experts who wish to study and analyze these or similar reactions in greater detail.
  • R and R 2 are variables.
  • the suffix (ad) was used to indicate a compound that was temporarily "adsorbed" to the surface of a solid catalytic material.
  • the suffix (g) referred to a compound that was released, from the catalytic surface, as a gas (in the case of water, this will be steam, since these reactions are carried out at high temperatures).
  • the suffix "O(/)” referred to "surface oxide anions" (i.e.
  • a second molecule of acetic acid ionizes, and transfers its hydrogen proton to an adsorbed hydroxy group on the support surface. This causes the hydroxy group to be converted into a full molecule of water, which leaves the support surface, in the form of steam.
  • the second acetate anion becomes adsorbed onto the support, which continues to have positive charges on it due to other hydrogen protons that are being donated to it by the acetic acid solution that continues to contact the support.
  • One object of this invention is to disclose various enhancements and options that can be used to expand and improve upon various teachings of two previous PCT applications (serial numbers PCT/US03/035396, published as WO 2004/041399, and PCT/US2004/019977) that were previously filed by the same Applicant.
  • Another object of this invention is to disclose various processing pathways and options, using methane-sulfonic acid (from methane gas) as a feedstock or intermediate, to create various types of valuable organic chemicals.
  • Another object of this invention is to disclose enhanced methods for oxidizing SO 2 into SO 3 , so that the cycling of sulfur compounds, as part of a larger processing system that converts methane into methanol or other compounds, can be carried out more efficiently and economically.
  • Another object of this invention is to disclose methods and catalysts for causing methyl radicals to react with carbon dioxide, to form acetic acid, thereby forming a valuable chemical while also reducing carbon dioxide emissions into the atmosphere.
  • Enhancements and options are disclosed for chemical processing methods described previously by the Applicant, for converting methane into methanol or other organic compounds, via methyl radicals and methane-sulfonic acid (MSA).
  • MSA methane-sulfonic acid
  • a major set of options and enhancements, which are the primary focus of the claims herein, relate to converting MSA into an unstable and highly reactive anhydride intermediate called sulfene, H 2 C SO 2 .
  • This compound is a potent and useful donor of methylene groups (-CH 2 -), which can be used for purposes such as creating heavier liquid fuels or olefin compounds, or for creating plastic or polymeric compounds in particulate or other form.
  • FIGURE 1 depicts several known chemical reactions that can "activate" methane (CH 4 ) by removing a hydrogen atom (both a proton and an electron), to convert the methane into a methyl radical (H 3 C*, where the asterisk represents an unpaired electron).
  • FIGURE 2 depicts a reaction system that combines methyl radicals (H 3 C*) and sulfur trioxide, to form methane-sulfonic acid (MSA) by a multi-step process that creates a new methyl radical. This establishes a chain reaction, and the newly-created methyl radicals will react with newly-added SO 3 .
  • FIGURE 3 depicts transitional intermediates that are likely to be formed if MSA is dewatered with the assistance of a silicate monolith material having hydroxy groups on its surface.
  • FIGURE 5 depicts an alternate candidate pathway for dewatering MSA to form sulfene, using tungsto-phosphoric acid (also called phospho-tungstic acid).
  • FIGURE 6 depicts an alternate candidate pathway for making sulfene, using a methyl-MSA compound that is reacted with methanol, which is recovered and recycled.
  • FIGURE 7 depicts a pathway for using sulfene to convert ethene into cyclopropane, which can be converted into propene (propylene), propanol (propyl alcohol), or other products.
  • FIGURE 8 depicts a reaction pathway that proceeds through an "outer" anhydride form of MSA, formed by condensing two molecules of MSA while removing a water molecule.
  • FIGURE 9 depicts a potential polymerization pathway, in which sulfene will insert multiple methylene groups into a growing alkane molecule or derivative, which may be a branched alkane or derivative if certain types of diimine or other catalysts are used.
  • FIGURE 10 shows a pathway that enables a vandaium diformate catalyst to convert SO 2 into SO 3 , using pathways that appear from computer modeling to be thermodynamically favorable.
  • FIGURE 11 is a schematic depiction of a system for converting SO 2 to SO 3 , which uses heat from the SO 2 oxidation reaction to heat MSA from its relatively cool formation temperature, up to a much higher cracking temperature.
  • MSA methanesulfonic acid
  • H 2 C SO 2 (also called thioformaldehyde dioxide).
  • ethylene also called ethene
  • the SO 2 group in sulfene will act as a leaving group in most types of reactions, causing most sulfene reactions to release SO 2 in gaseous form. This gas can be collected, oxidized back into SO 3 , and returned to the reactor vessel that is being used to convert methane into MSA, in a recycling operation that minimizes wastes and unwanted byproducts.
  • sulfene can be used as a "methylene transfer agent", which can insert methylene groups (which can be represented as -CH 2 - or as H 2 C:) into other compounds, qas discussed in more detail below.
  • This reaction can be used to convert various hydrocarbon compounds (include gaseous or other relatively light or “thin" hydrocarbons, such as short-chain hydrocarbons with 2 to 5 carbon atoms) into larger and heavier compounds, which generally will be easier to handle (since they will be less volatile) and more valuable (since they will have higher energy density) .
  • the methylene group from sulfene will convert the ethylene into cyclopropane, which can be (1) used as a chemical feedstock, which will be highly reactive due to its stressed bond angles, (2) isomerized to form propylene (also called propene), another valuable olefin, or (3) hydrated to form propyl alcohol, a valuable chemical and a gasoline additive or substitute.
  • propylene also called propene
  • transfer of methylene groups into most types of gaseous and/or volatile hydrocarbons will decrease their volatility, making them easier to store, transport, and handle, and will also increase their energy density, utility, and value.
  • each water molecule that is released during a dewatering process typically will contain a hydroxy group from the sulfate domain of one MSA molecule, and a hydrogen proton from the methyl domain of a different molecule of MSA.
  • an "outer” anhydride of MSA H 3 CSO 2 -O-SO 2 CH 3 , formed by condensing two molecules of MSA while removing a single molecule of water.
  • this intermediate can rearrange to form sulfene, while releasing MSA.
  • Outer anhydrides of MSA can be useful, and are discussed below.
  • Several candidate methods for converting MSA into sulfene are disclosed herein. Preferred methods for different manufacturing sites may depend on various factors, such as flow rates and flow rate consistency levels at that site, the purity levels and contaminant loads in the methane stream as well as the MSA intermediate, the ability of other equipment at a site to handle any wastes or unwanted byproducts that may be created by the various candidate methods, and the targeted purity levels for sulfene or downstream products that will enable operations at a particular site to be optimized on an economic basis.
  • any candidate method disclosed herein can be evaluated, both in batch-processing and continuous-flow modes of operation, to determine its suitability and economics for use at any particular site. It should be recognized that until this point in time, sulfene has received little attention from chemical researchers, mainly because of two reasons: (i) it is unstable, and will not last long even when created; and, (ii) the only prior art methods for preparing it are difficult and tedious, and generate too much toxic and hazardous waste to enable sulfene manufacture to be used as a practical and economic route toward creating other valuable products.
  • water may be removed from certain components prior to the creation of sulfene.
  • This can provide benefits in various types of downstream processing.
  • Three main categories of candidate pathways are described below, for synthesizing sulfene. Each candidate pathway is discussed under its own subsection.
  • CANDIDATE PATHWAY #1 SOLID-SUPPORTED CATALYSTS
  • the first candidate pathway disclosed herein for dewatering MSA to form sulfene uses catalytic materials on the surfaces of solid supports. Catalysts that are coated onto (or otherwise made accessible on) the surfaces of solid support materials are widely used in the petroleum and chemical industries, because they allow expensive catalytic materials to be retained inside a reactor while large volumes of gas or liquid are pumped through the reactor.
  • the types of solid-support catalysts disclosed herein can be provided in any of several candidate forms, such as: (i) "monolith” materials, with essentially linear and parallel flow channels passing through a highly porous material that can be manufactured in a "cake” or similar form that can be placed inside a reactor device, or (ii) particulate materials, which can be loaded into a packed bed, fluidized bed, stirred reactor, or comparable device.
  • one of the double-bonded oxygens of the sulfate portion of MSA is attracted to one of the hydrogen protons on the silicate support, and the hydrogen proton on the hydroxy group of the sulfate portion of MSA is attracted to one of the oxygen atoms in one of the hydroxy groups on the silicate support.
  • a coordinate bond between the two silicon atoms is also disrupted or reconfigured.
  • This combination of steps forms an adsorbate, in which MSA has become closely associated with the silicate surface. This attraction and affiliation is an exothermic reaction that occurs spontaneously, with a A E value of -10.72 kcal/mol (kilocalories per mole).
  • a E refers to bonding energies, which correspond to ⁇ H (enthalpy) values when certain "zero point energy” (ZPE) corrections are made, as known to those skilled in the art.
  • ZPE zero point energy
  • the MSA residue will pivot and swing around an "axle" that is provided by the silicon-oxygen-sulfur linkage, until one of the positively- charged hydrogen protons, on the methyl group of the MSA residue, approaches a negatively-charged hydroxy group, which might be bonded to the same silicon atom that the sulfur is bonded to, but which more likely will be bonded to some other nearby silicon atom in the matrix of the silicate support.
  • three proton and electron shifts take place, which function together to set the stage for the disengagement of sulfene from the substrate.
  • the hydrogen proton that formed the bridge between the methyl group of MSA, and the hydroxy group of the substrate shifts toward the hydroxy group of the substrate, thereby weakening its bond and its attraction to the carbon atom of the MSA.
  • the electron pair that previously formed the carbon-hydrogen bond (which has now become weakened because of the hydrogen proton's attraction to the hydroxy group on the substrate) will be pulled toward the electronegative sulfur atom. This sets up the formation of a double bond between the carbon atom and the sulfur atom.
  • this formation of the double bond between the sulfur and the carbon will weaken the single bond between the sulfur atom, and the oxygen atom that forms the sulfur-oxygen-silicon linkage.
  • the fifth step can occur, in which the MSA residue will detach from the silicate support, in a way that creates a double bond between the carbon and the sulfur.
  • the hydrogen proton from the methyl group, and the oxygen atom from the sulfate group, will both be left behind, adsorbed on the solid support material.
  • the H 2 C SO 2 molecule that remains from the original MSA has become sulfene.
  • Table 1 provides the AH (change in enthalpy) values and the *G (change in Gibbs free energy) values for the formation of ethene via either of two routes: (1) from acetic acid via ketene, as described in Barteau 1996, for comparative purposes; and, (2) from MSA via sulfene, as disclosed herein. These units are in kilocalories per mole, but since two moles of sulfene make only one mole of ethene, attention needs to be paid to whether the one- mole compound is on the left or the right side of the reaction arrow, as discussed in more detail following the table.
  • Both sets of values were calculated at 3 different temperatures, which are 300, 600, and 900 Kelvin.
  • the Kelvin scale begins at theoretical absolute zero, at which all atomic motion completely stops.
  • a Kelvin temperature can be converted into centigrade by subtracting 273.15; therefore, the modeling temperatures were equal to 26.85, 326.85, and 626.85°C.
  • Those temperatures are equal to 80, 620, and 1130°, in the Fahrenheit scale, which is mentioned to emphasize the range they cover, and to point out that the lowest modeled temperature (which is close to room temperature) would not be useful or practical for manufacturing ethene from MSA, since the initial barrier to reach sulfene is too high.
  • bifunctional catalysts can be regarded as "two-handed" catalysts.
  • most people cannot securely grip and hold a basketball with just one hand; however, nearly anyone can do it, using two hands.
  • two-handed catalysts can attract, grasp, and manipulate some types of molecules more rapidly, efficiently, and securely than catalysts having only one type of active site or group. This is especially true with a molecule such as MSA, which has methyl and sulfonic domains that are very different from each other. Therefore, rather than using a silicate support that only has hydroxy groups as the active sites (as described in the first candidate pathway, above), more efficient catalysts can be developed by providing a catalytic surface with two or more types of functional groups, allowing one type of group to attract and interact with the sulfonic domain of MSA, while a different group attracts and interacts with the methyl domain.
  • bi-functional catalysts use either or both of the following: (1) two distinct mechanisms that occur in sequence, usually quite rapidly (such as within nano-, micro-, or milliseconds); and/or, (2) anchimeric, symphoric, or neighboring group effects, in which a partial shift in one part of a molecule enables and promotes a secondary shift in another part of the molecule.
  • an initial reaction or shift usually avoids or minimizes some type of transitional barrier that otherwise would hinder or block the second part of the desired reaction.
  • Hetero-polyacid compounds such as tungsto-phosphoric acid (also called phospho-tungstic acid) can function in a desired manner, in a liquid solution.
  • This teaching can then be adapted for use with immobilized catalysts on solid supports.
  • Hetero-polyacid compounds usually are formed by combining two or more types of salts, then using a strong acid to acidify the salt mixture.
  • tungsto-phosphoric acid can be created by: (1) mixing a tungsten salt such as sodium tungstate dihydrate, Na 2 WO 4 2H 2 , with a sodium phosphate hydrate such as Na 2 HPO 12H 2 O, in distilled water; (2) adding concentrated hydrochloric acid, slowly and with vigorous stirring; (3) evaporating the water under a vacuum; (4) extracting tungsto-phosphoric acid from the residue, using a solvent such as ethyl alcohol; and, (5) removing the solvent under a vacuum, to provide a crystalline acid.
  • a tungsten salt such as sodium tungstate dihydrate, Na 2 WO 4 2H 2
  • a sodium phosphate hydrate such as Na 2 HPO 12H 2 O
  • This mixture will contains various species that can be represented as WO x (W is the symbol for tungsten) and H y PO 2 , where x, y, and z are variable numbers (usually but not always represented as integers).
  • the acid mixture can be represented by one or more dominant species, such as WO 3 H 3 PO 3 .
  • This compound is sold by Alfa-Aesar (www.alfa.com).
  • phosphoric acid will donate a hydrogen to the sulfate group on the MSA, causing it to become an ionic group with an extra hydrogen proton, -SO 2 OH 2 + .
  • the -OH 2 group will then leave, as water (i.e. , as steam, if the reaction is carried out at high temperature), leaving behind an ionic sulfate group, -SO 2 + .
  • This generates a transitional MSA ion that is likely to rearrange into sulfene, while releasing water, as shown in FIG. 5.
  • bifunctional catalysts can be immobilized on solid supports, to prevent the catalyst from being washed out of a reactor by the gas or liquid flowing through the reactor.
  • Immobilization of a bi-functional catalysts can be accomplished by using and/or adapting various synthesis routes that are already known to skilled experts who specialize in creating and testing new types of zeolites and other semi-permeable catalysts.
  • the "SAPO" class of zeolite catalysts already contains phosphorus atoms, in an aluminosilicate matrix. Therefore, an activating agent can be used to donate tungsten atoms or groups in a manner that will coat the accessible surfaces of a SAPO material, in a manner that will create immobilized groups that are similar to tungsto-phosphoric acid mixtures as described above.
  • a donor compound can be added to a reagent mixture that is being used to synthesize a porous catalyst.
  • this approach tends to make less efficient use of an expensive "dopant" compound, since much of the dopant is likely to be inaccessible, inside the final material, rather than merely coated onto accessible surfaces.
  • Examples of hydrocarbon processing using bi-functional catalysts are provided in numerous published articles. As one example, scheme III shown on page 427 of Olah 1987 represents two sequential reactions that are triggered, first, by an acidic domain of a catalyst, and second, by an alkaline domain of the same catalyst material. Olah et al 1984 (entitled, "Onium Ylide Chemistry: 1.
  • Bifunctional Acid-Base-Catalyzed Conversion of ... contains more information on this subject.
  • metal oxide catalysts such as vanadium oxide catalysts, platinum oxide catalysts, etc.
  • act as bi-functional catalysts in which a vanadium, platinum, or other metal atom interacts with one domain of a compound being treated, while one or more oxygen atoms bonded to the metal atom interact with a different domain of the compound being treated.
  • bi-functional catalysts hold exceptionally good promise for converting MSA into sulfene, in ways that adapt and extend the teachings set forth above, concerning solid-supported catalysts in general.
  • CANDIDATE PATHWAY #3 MSA METHYL ESTER PATHWAY
  • MSA METHYL ESTER PATHWAY a question arose as to whether the MSA was (or might be, under certain conditions) contaminated by a methyl-methanesulfonate ester, with a structure shown at the top of FIG. 6. That question triggered some additional analysis and computer modeling, as well as a careful rereading of every patent issued to Snyder and Grosse in the early 1950' s. That work eventually resulted in a postulated pathway that (according to the computer modeling results) appears to offer an improved pathway to sulfene, with lower thermodynamic hurdles than candidate pathway 1, above. This candidate pathway is illustrated in FIG. 6.
  • the MMS ester compound is then treated with a highly polarized metallic salt, such as a zinc halide, such as zinc chloride, ZnCl 2 , which can act as a "Friedel-Crafts" catalyst.
  • a highly polarized metallic salt such as a zinc halide, such as zinc chloride, ZnCl 2 , which can act as a "Friedel-Crafts" catalyst.
  • the reaction of the methoxy group with a hydrogen proton completes the re-formation and release of methanol, which is recycled back into the dehydration reactor.
  • the release of methanol, from the the MMS ester leaves behind an "ylide" form of sulfene, as the residue.
  • Various candidate solvents can be tested, to deterine which solvent(s) can maximize the yields of this reaction
  • Tetrahydrofuran, dimethylsulfoxide, and other candidate solvents can provide a range of polarity levels, which will merit evaluation for such use.
  • the preferred solvent selected for a particular manufacturing facility is likely to depend on the operating temperature that is used, at that site.
  • Solvents with lower polarity levels can be used to slow down SO 2 removal, in ways that can be used to control reaction kinetics, to maximize desired yields.
  • the sulfene ylide compound will react with sulfene to form ethylene, a valuable olefin used to make plastics and polymers. These reactions are complex, involving various types of pi and sigma bonds.
  • various options can be evaluated for controlling the levels of sulfene reactivity, including, for example: (i) carrying out such reactions at low temperatures, under reduced pressures, and/or in the presence of various solvents that will help sustain reactions at lower rates; and, (ii) modifying MSA, prior to dewatering it, in ways that may, for example, modify one or more of the oxygen atoms on the sulfonic group. If the ethylene remains in solution while additional sulfene is being formed, at least some of the ethylene is likely to react with sulfene, to form cyclopropane.
  • cyclopropane can be isomerized by steps such as mild heating, to form propylene (a valuable olefin that is easier to handle and transport than ethylene), or it can be reacted with water to convert it into propyl alcohol, which makes a very good gasoline additive or substitute, with an energy density higher than methanol or ethanol.
  • this invention discloses a useful pathway for converting methane or MSA into olefins or other valuable and useful products, by passing through sulfene, an intermediate that effectively provides a pathway for making olefins and other materials, with lower thermodynamic barriers than other alternative pathways.
  • candidate pathways described above are not regarded as exhaustive or exclusive. Instead, other candidate pathways for reaching sulfene, or for reaching other useful intermediates that can be converted into olefins or other valuable products, are likely to be recognized by those skilled in the art, after the chemical pathways and commercial prospects for converting stranded and wasted methane into MSA, then sulfene, and then ethylene, have been disclosed.
  • sulfene may be potentially useful as a "methylene transfer agent" (MTA) in various other situations.
  • MTA methylene transfer agent
  • This potential utility will be limited by the tendency of sulfene to react with itself, rapidly and exothermically, to form ethylene; nevertheless, by controlling reaction conditions such as temperatures, pressures, and ratios of reagents, it may be possible and practical to induce sulfene to react with various other compounds, in various ways and at commercial levels.
  • Cyclopropane offers a good example, since it can be formed by reacting ethylene (formed by condensing sulfene, or by any other known method) with additional sulfene. If a fixed quantity of sulfene is placed or created in a closed reactor, much of the sulfene is likely to form ethylene, fairly rapidly; then, as the ratio of ethylene to sulfene in the reactor rises, the remaining sulfene will become more likely to react with the growing quantity of ethylene, than with the dwindling quantity of remaining sulfene.
  • FIG. 7 depicts a reaction pathway for using sulfene to convert ethylene into cyclopropane.
  • a reaction pathway for using sulfene to convert ethylene into cyclopropane when a molecule of sulfene contacts a compound having a double bond, the sulfur dioxide group from the sulfene will leave, and the methylene group (which has two unshared electrons, and which can be represented as either H 2 C: or -CH 2 -) will react with the double bond, in a way that generates a triangular structure, as shown in FIG. 7.
  • the triangular product will be cyclopropane, which is useful and valuable because it is highly reactive, due to the fact that its bonds are stressed at 60 degree angles in a planar structure (by contrast, the conventional bond angle in alkane molecules is 109.5 degrees).
  • propylene Since propylene is larger and heavier than ethylene, it is less volatile, and more inclined to behave as a liquid rather than a gas, at temperatures and pressures that can be achieved more easily and at less expense than required for ethylene. Propylene can be stored and transported as a liquid, using tanks that can operate at lower operating pressures and/or warmer temperatures than required to store or transport ethylene as a liquid. Therefore, ethylene-to-propylene conversion, using sulfene as shown in FIG. 7, may have important commercial implications. Alternately, cyclopropane can be reacted with water, in a manner that breaks one of the stressed triangular bonds, in a way that creates propyl alcohol (also called propanol).
  • propyl alcohol also called propanol
  • This reaction can be referred to either as hydrolysis (since one of the carbon-carbon bonds is broken), or as hydration (since the components of a water molecule are being added to the cyclopropane).
  • Propyl alcohol is a clean-burning fuel, which can be used as a gasoline additive or substitute with higher energy content than methanol or ethanol, and it has other valuable uses as a chemical feedstock, skin disinfectant, etc.
  • sulfene can be regarded and used as a dipolar compound that has both " super- nucleophile” and "super-electrophile” traits. This gives it an exceptionally potent ability to react with double bonds, in ways that can avoid the destruction and elimination of the double bonds.
  • a methylene radical by itself, can be regarded as a dipolar and bi-functional agent that is both a super-nucleophile, and a super-electrophile.
  • a methylene radical On one level, a methylene radical has two extra and unpaired electrons exposed on its surface, and those electrons will aggressively seek out and bind to the positively-charged nucleus of another carbon atom. That makes methylene radicals highly potent nucleophiles. However, at the same time, a methylene radical is missing two electrons from its valence shell, and it will aggressively seek out and bind to an electron- rich structure which can help it fill those gaps (such as a double bond, in an olefin molecule). That makes methylene radicals highly potent electrophiles. These combined traits are believed to make sulfene a highly potent "methylene transfer agent", which can insert -CH 2 - groups into various types of compounds.
  • sulfene will be able to insert methylene groups into olefins, without destroying the double-bonded constituents of the targeted olefins.
  • it is believed to be able to convert propene into butene, butene into pentene, pentene into hexene, etc. , by chain-lengthening reactions in which the sulfene is most likely to react with the electron- rich double bond, in each step of the reaction.
  • the initial step in a "methylene insertion" reaction will create a three-membered ring, comparable to a cyclopropane molecule that has a "tail” attached to one of the three carbons.
  • the ring having three carbon atoms (with stressed bonds, having bond angles of 60 degrees) can then be induced (such as by moderate heating) to cross a relatively low transitional energy barrier, in a way that isomerizes the three-member ring to form an "alpha" olefin, with the double bond positioned between the first and second carbon atoms in the chain.
  • This isomerization form is believed to be preferred over a 2,3-olefin formation, because the #3 carbon atom in a three-membered ring (i.e.
  • the carbon atom that has a hydrocarbon "tail” attached to it will be less electron-rich, and less likely to participate in the formation of a double-bond.
  • this approach can be used to manufacture liquid mixtures that will be comparable to "fractions” that can be obtained by distillation or other conventional hydrocarbon processing, with sufficient quality and consistency to enable their use as gasoline or other fuels, or as fuel additives, blending agents, etc.
  • liquid hydrocarbons including straight-chain alkanes, branched alkanes, alkenes (also called olefins), cycloalkanes and cycloalkenes, aromatics, and possibly even substituted hydrocarbons (such as halogenated or oxygenated derivatives, etc.).
  • sulfene-containing preparations can generate solid polymeric materials.
  • plastic and/or polymeric materials when manufactured in this manner at methane-producing sites, have a wide range of uses; for example, they can be stored and transported in particulate form, in ways that allow them to be melted and molded into desired shapes, at a factory. Because of the reactivity of sulfene, it is likely that most commercial-scale reactions involving sulfene will generate a mixture of products, rather than a single relatively pure product.
  • ylides and ylids that are of interest herein will have a "carbanion", a term that combines "carbon” with “anion” .
  • This unshared electron pair is created by positioning the carbon atom next to a positively-charged "hetero-atom” , which will donate one of its electrons to the carbon atom (a more complete description of this electron shift requires an analysis of electron valence shells, "p” and “d” orbitals, pi bonding, etc.).
  • the heteroatom will be sulfur, nitrogen, or phosphorus, although some chemists regard oxygen as also having sufficient strength to form compounds that can behave as ylides under at least some conditions).
  • Ylides and other compounds that contain negatively-charged, electron-rich "carbanions” are relevant to the manufacture of olefins, for the following reason: if two molecules that contain electron-rich "carbanions” react with each other, the electron-rich "carbanions” in the reagent molecules are likely to form an electron-rich double bond, between the two carbon atoms, in a new molecule created by the reaction, while the positively-charged heteroatoms act as leaving groups.
  • the bond between the sulfur atom and the carbon atom can be written in any of three ways (often called “canonical” forms, comparable to a musical piece such as "Pachelbel's Canon", in which the same melody is played repeatedly, but in slightly different ways).
  • a second written version depicts a single bond with charge indicators,
  • resonating structure is often used to describe electron configurations that cannot be cleanly represented as one particular form.
  • resonating (or resonant) electron structures can have either or both of: (i) two distinctly different forms which will shift back and forth, to coexist with each other, in equilibrium; or, (ii) a quasi- stable intermediate form, located somewhere between the two ends of the continuum, and having some combination of mid-point properties.
  • Resonating electron structures are fairly common in chemistry, and are used to explain a wide variety of semi-stable molecules, including carbon monoxide, sulfur dioxide, and molecules that shift back and forth between "tautomeric” forms (such as sugar molecules, which shift back and forth between rings, and straight chains).
  • disclosures herein can be combined with additional disclosures (already published in the art) involving ylides, ylids, and Wittig reactions, in ways that will enable commercial and industrial adaptation of sulfene and sulfene-analog chemistry for use with additional types of ylids and ylides, in ways that will become apparent to those skilled in that particular field of chemistry, after they have analyzed and evaluated the disclosures herein.
  • FIG. 8 shows a condensation step involving two molecules of MSA, which creates an "outer anhydride” of MSA (shown as the starting reagent in Karger's Equation 8) while releasing a molecule of water.
  • the sulfate group on a first molecule of MSA releases a hydrogen proton
  • the sulfate group on a second molecule of MSA releases a hydroxy group.
  • This reaction is postulated to involve: (i) release of a hydrogen proton from the methyl group of the anhydride; (ii) migration of the electrons from the C-H bond over to the C-S bond, thereby forming a double bond; and, (iii) breakage of the S-O linkage, in the presence of protons in the acidic MSA solution. It is possible but not especially likely that the same hydrogen proton from a particular molecule will bond to the oxygen atom from an S-O linkage that is being broken in that same molecule. In addition to generating sulfene, as shown in FIG. 8, the rearrangement in step 2 also regenerates and releases a molecule of MSA.
  • the Applicant herein believes and anticipates that polymeric material can be created by repeated insertions of methylene groups (-CH 2 -) into growing carbon chains, as indicated in FIG. 9. It is possible that methylene groups can be inserted into the carbon- sulfur bond, shown in the MSA molecule that serves as the starting point for the chain- lengthening reaction; however, computer modeling indicates that the more likely point of insertion appears to be at a carbon-hydrogen bond in the methyl group. Regardless of which bond provides the particular insertion site, a hard polymeric compound was indeed observed, when the "outer anhydride" of MSA (purchased in crystalline form, from Aldrich Chemicals) was heated to a temperature higher than 250°C, under nitrogen gas.
  • MSA methylene groups
  • the decomposition created both a clear liquid, and a black solid. Both the liquid and the residue were chemically analyzed.
  • the clear liquid was found to consist mainly of MSA and cycloalkanes.
  • the black solid was found to contain cyclic hydrocarbons, naphthenics, and a relatively high quantity of aromatic structures. Some of the aromatic rings were bridged by sulfonate or methylene bridges, and some of the aromatic rings had cyclopropane rings attached to them.
  • molecules that have some degree of branching are not as long as straight-chain molecules, for a given number of carbon atoms, and there is less chance that the "far end" of some particular molecule will be pushed away, in unburned form, when one of the molecules goes through rapid and explosive but imperfect combustion.
  • the molecule with the gold- standard " 100" octane rating is 2,2,4-trimethyl pentane, rather than straight-chain octane.
  • a carbonyl group located at the end of a carbon chain or into a ketone group (i.e., a carbonyl group located in the middle of a carbon chain)
  • the insertion will create a three-membered oxirane or epoxide ring, which will include the carbon atom that had the carbonyl group.
  • Epoxide and oxirane rings are unstable and reactive, due to their stressed bond angles. This makes them useful reactants in certain types of chemical processing, if they can be used rapidly after they are generated, before they have time to spontaneously decompose. It should also be noted that sulfene may become useful in modifying the surfaces of various types of silicate materials that will have special properties or uses following such treatments.
  • Examples of such candidate uses include semiconductors, and an emerging category of materials that are creating new types of interfaces and interactions between biological materials (such as antibody fragments or other proteins, DNA segments, etc.) and nonbiological materials, for purposes such as diagnostic, therapeutic, or other analytical, processing, medical, or other physico-chemical uses.
  • biological materials such as antibody fragments or other proteins, DNA segments, etc.
  • nonbiological materials for purposes such as diagnostic, therapeutic, or other analytical, processing, medical, or other physico-chemical uses.
  • researchers interested in this category of uses should study Lie et al 2002, including passages such as the first full paragraph on page 116, which discusses the formation of direct silicon-carbon bonds rather than silicon-oxygen-carbon linkages, and the last paragraph in column 1 of page 117, which discusses the possible insertion of methylene groups (-CH 2 -) into silicon-silicon bonds.
  • upstream options and enhancements include the following: (1) It is believed and anticipated that if carbon dioxide (CO 2 ) is pressurized to a point that causes it to become a supercritical liquid, it may be able to increase the solubility of methane gas, in a liquid solution of SO 3 and MSA. If this is confirmed in continuous- flow testing, the use of supercritical liquid CO 2 may be able to increase and improve the mass transfer rates that will transfer gaseous methane into a liquid solution. This may be able to increase the speed and efficiency of the reaction that converts methane into MSA.
  • radicals can be regarded as “double-strong” radicals, since they have not just one, but two unpaired electrons.
  • a methylene radical (with two unpaired electrons) reacts with methane, the "double-strong" methylene radical is likely to remove a single hydrogen atom from methane. This will balance out the two molecules, making them equal, thereby creating two methyl radicals, H 3 C*.
  • Each of these methyl radicals will be able to combine with sulfur trioxide, SO 3 , to form MSA radicals, as shown in FIG. 2, and the MSA radicals will then remove hydrogens from fresh methane, to form stable MSA while creating new methyl radicals that will keep the chain reaction going.
  • sulfene in gaseous, mist, or similar form
  • it may be an effective and useful radical initiator compound, which may eliminate or reduce the need for Marshall's acid, halogen gases, or other compounds that would likely create acidic wastes.
  • an MSA anhydride can be pumped out of a device (which can be called a "radical gun") having a nozzle that contains a very hot electric filament or other heating element (which can be embedded in a quartz tube or other protective device, if desired) that will break apart the radical-releasing molecules as they pass across the heating element.
  • borate compounds such as trimethyl borate, or borate anhydride
  • if properly utilized in the MSA reactor vessel may be able to help promote the synthesis of MSA, mainly by reducing unwanted SO 3 reactions (such as the formation of CH x (SO y ) n H polymers and other species, where x, y, and n are variables).
  • the borate compound can also help maintain SO 3 molecules in their aplha and gamma forms, which can help improve the overall conversion of SO 3 to MSA.
  • Such borate compounds can be coated onto immobilized or particulate surfaces, to ensure that they remain inside the MSA reactor.
  • the mixed liquid and gas streams may be able to react with methane gas, in the liquid/gas mixtures and interfaces that will be present inside the reactor, in ways that will increase the rates of MSA formation.
  • the resulting surface-treated supports may be able to function as efficient removers of hydrogen atoms (both protons and electrons) from lower alkyl molecules such as methane, or from other compounds (such as azomethane, sulfene, ketene, etc.) that can subsequently function as "strong radical initiators” (i.e. , compounds that can efficiently remove hydrogen atoms from methane or other lower alkanes). This would generate methyl radicals, in quantities that may be able to initiate the methane-to-MSA conversion reaction shown in FIG.
  • FIG. 2 IMPROVED CONVERSION OF SO 2 INTO SO 3
  • the process illustrated in FIG. 2 pumps SO 3 into an MSA-forming reactor, and removes SO 2 from an MSA cracker. To keep that sulfur cycle running, SO 2 that emerges from the MSA cracker to be oxidized back into SO 3 . While that is a well-known process, used at numerous facilities aorund the world, the volumes that will be involved, in methane-to-methanol conversion, are likely to dwarf any SO 2 oxidizers that have ever been built. As mentioned in the Background section, roughly $100 million worth of methane is wasted by flaring or reinjection, every day. Those are huge volumes of methane, and correspondingly huge volumes of SO 2 will need to be converted into SO 3 , every day.
  • monoliths are hard but porous materials with essentially linear and parallel flow channels, usually ranging from about 100 channels per square inch (cpsi) for liquids, up to 1000 or more cpsi for gases.
  • SO 2 to SO conversion is described in patents such as US 5,264,200 (Felthouse et al 1993).
  • Other materials that can provide solid supports for catalytic materials include woven glass fibers (e.g. , Bal'zhinimaev et al 2003), and zeolite- type porous materials (e.g. , US patent 6,500,402, Winkler et al 2002).
  • Other relevant patents that address fluid-handling and heat-exchanging machinery include US 6,572,835 (MacArthur et al 2003).
  • the first set of reasons centers on the fact that a large network (or "base") of existing V 2 O 5 systems already exists, and has been running for years. People and companies already know how to keep those systems running, and if a system suffers an upset, local operators and available experts know how to get it running again, quickly. Replacement of those existing systems, and training people not just to run them but also to diagnose and correct any upsets and malfunctions, would be very expensive.
  • the second cluster of reasons centers on the fact that the SO 2 to SO 3 reaction is highly exothermic. Since it releases a lot of heat and energy, which can be captured and used for steam generation or other useful purposes, there has been no motivation or incentive for industrial companies that already own and run V 2 O 5 systems to invest in other systems that might be smaller, faster, or more efficient.
  • a new class of vanadium catalysts including vanadium diformate and halogenated analogs of vanadium diformate (such as vanadium fluoro- or perfluoro- diformate, in which some or all of the hydrogen atoms have been replaced by fluorine atoms), may be able to offer a better catalytic pathway from SO 2 to SO 3 , using steps and intermediates such as illustrated in FIG. 10. Accordingly, it is disclosed herien that vanadium formate catalysts (or any other vanadium catalyst) can be coated onto activated carbon, for use (which may include low temperature use) in converting SO 2 to SO 3 .
  • This type of processing preferably should be carried out in an aprotic medium, where the solvent has a low dielectric constant, such as supercritical CO 2 , to help promote rapid desorption of SO 3 away from catalytic sites, and to prevent the hindrance of vanadium catalytic sites, as can occur with solvents having higher dielectric constants.
  • a low dielectric constant such as supercritical CO 2
  • SO 2 catalytic oxidation reactors that are run at high temepratures can be placed inside tubular structures, which can be surrounded by annular or other flow channels that will carry liquid MSA, preferably in a counterflow direction.
  • This can provide an efficient heat exchange mechanism, allowing heat that is released by SO 2 oxidation, inside the inner reactor tube, to be transferred to the MSA liquid in the annular space, to heat the MSA liquid up to cracking temperatures. Accordingly, FIG.
  • FIG. 11 is a schematic depiction of a system for converting SO 2 to SO 3 , using: (i) an oxidizing reactor that contains a catalyst on a monolithic, fiberglass, or other porous support; (ii) a heat exchanger that allows heat from the SO 2 to SO 3 reaction to heat MSA from its formation temperature (about 50°C) to its cracking temperature (more than 300°C); (iii) an SO 3 condenser, to allow liquid SO 3 to be collected and pumped back into the MSA reactor; and (iv) a device for separating SO 2 from remnants of the air that was used as an oxygen source, allowing purified SO 2 to be returned to the catalytic reactor for another conversion pass.
  • EXAMPLE 1 MAKING AND CRACKING MSA Methods and reagents used to make Marshall's acid and MSA in laboratory conditions, using a batch reactors, have already been described in PCT applications PCT/US03/035396 (published in May 2004 as WO 2004/041399) and PCT/US04/019977, both filed by the same Applicant herein. Therefore, those descriptions will not be repeated herein.
  • nitrogen gas (N 2 ) was passed through a gas bubbler containing 10.0-15.0 g of MSA at 120-140°C.
  • the outlet of the bubbler was connected to a quartz tube with an inner diameter of 2 cm and a length of 20 cm, which (except for short inlet and outlet segments) passed through a furnace
  • the tube was either empty, or a 10 cm length of the tube was loaded with 4 to 8 mesh zeolite beads (Davison Chemicals, code number 54208080237).
  • the outlet of the tube was connected to two bubblers, each containing 5.0 g of D 2 O (i.e. , water containing the heavier deuterium isotope of hydrogen, for analysis using ,H-nuclear magnetic resonance) at 4-6°C, for trapping any emerging liquids.
  • EXAMPLE 3 DECOMPOSITION OF MSA OUTER ANHYDRIDE
  • MSA "outer anhydride” compound, in crystalline form, from Aldrich Chemical. In a reaction beaker, it was heated until the crystals melted and then began to form a clear liquid over a black solid. The liquid and the solid were analyzed, using ⁇ -NMR, 13 C-NMR, and gas chromatography. The results indicated that the clear liquid consisted mainly of MSA and cycloalkanes. The black solid was found to contain cyclic hydrocarbons, naphthenics, and a relatively high quantity of aromatic structures.

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Abstract

La présente invention a trait à la fabrication d'hydrocarbures supérieurs à partir du méthane, via l'acide sulfonique de méthane, le sulfène, et d'autres voies.
EP04810350A 2003-11-05 2004-11-05 Fabrication d'hydrocarbures superieurs a partir du methane, via l'acide sulfonique de methane, le sulfene, et d'autres voies Withdrawn EP1720831A4 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
PCT/US2003/035396 WO2004041399A2 (fr) 2002-11-05 2003-11-05 Conversion anhydre de methane et d'autres alcanes legers en methanol et d'autres derives au moyen de trajets de radicaux et de reactions en chaine produisant un minimum de dechets
US56267504P 2004-04-15 2004-04-15
PCT/US2004/019977 WO2005069751A2 (fr) 2003-06-21 2004-06-21 Traitement anhydre de methane en acide methanesulfonique, methanol, et autres composes
PCT/US2004/036831 WO2005044789A1 (fr) 2003-11-05 2004-11-05 Fabrication d'hydrocarbures superieurs a partir du methane, via l'acide sulfonique de methane, le sulfene, et d'autres voies

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EP1720831A4 EP1720831A4 (fr) 2010-04-07

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WO (1) WO2005044789A1 (fr)

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US20070282151A1 (en) * 2006-05-19 2007-12-06 Richards Alan K Manufacture of higher hydrocarbons from methane, via methanesulfonic acid, sulfene, and other pathways
FR3077817B1 (fr) * 2018-02-14 2020-02-28 Arkema France Procede de synthese industrielle en continu d'acide alcane-sulfonique

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US2553576A (en) * 1947-03-26 1951-05-22 Houdry Process Corp Production of organic compounds from methane sulfonic acid
US5292947A (en) * 1992-09-28 1994-03-08 Eastman Kodak Company Process for preparing alkylsulfonic anhydrides

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CA2586326A1 (fr) 2005-05-19
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MXPA06005141A (es) 2007-01-26
OA13283A (en) 2007-01-31

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