CATALYSIS: THE SERIES (Part 1)

If you are reading this blog post, it is likely that you are a catalysis expert, with a deep understanding of the subject.  As important as catalysis is to modern life, however, it is often difficult to describe catalysis to the layman in terms he/she can understand.

Bridging the understanding gap becomes critical when trying to convince managers, corporate sponsors, or venture capitalists of the significance of your particular approach.

I believe that Wikipedia can help.  The Wikipedia article on catalysis, for example, explains the basic concepts in a way that most people can understand.  Reading the article, or something like it, can help you organize your thoughts in a way that helps you connect with your audience. 

Once connected, it will be easier to explain the value of your contribution.

Here is a snippet from the article …

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Catalysis: Wikipedia
source: https://en.wikipedia.org/wiki/Catalysis

Catalysis (/kəˈtælᵻsᵻs/) is the increase in the rate of a chemical reaction due to the participation of an additional substance called a catalyst^[1] (/ˈkætəlᵻst/). In most cases, reactions occur faster with a catalyst because they require less activation energy. Furthermore, since they are not consumed in the catalyzed reaction, catalysts can continue to act repeatedly. Often only tiny amounts are required in principle.^[2]

Technical perspective[edit]
In the presence of a catalyst, less free energy is required to reach the transition state, but the total free energy from reactants to products does not change.^[1] A catalyst may participate in multiple chemical transformations. The effect of a catalyst may vary due to the presence of other substances known as inhibitors or poisons (which reduce the catalytic activity) or promoters (which increase the activity).^[1]
Catalyzed reactions have a lower activation energy (rate-limiting free energy of activation) than the corresponding uncatalyzed reaction, resulting in a higher reaction rate at the same temperature and for the same reactant concentrations. However, the detailed mechanics of catalysis is complex. Catalysts may affect the reaction environment favorably^[how?], or bind to the reagents to polarize bonds, e.g. acid catalysts for reactions of carbonyl compounds, or form specific intermediates that are not produced naturally, such as osmate esters in osmium tetroxide-catalyzed dihydroxylation of alkenes, or cause dissociation of reagents to reactive forms, such as chemisorbed hydrogen in catalytic hydrogenation.
Kinetically, catalytic reactions are typical chemical reactions; i.e. the reaction rate depends on the frequency of contact of the reactants in the rate-determining step. Usually, the catalyst participates in this slowest step, and rates are limited by amount of catalyst and its "activity". In heterogeneous catalysis, the diffusion of reagents to the surface and diffusion of products from the surface can be rate determining. A nanomaterial-based catalyst is an example of a heterogeneous catalyst. Analogous events associated with substrate binding and product dissociation apply to homogeneous catalysts.
Although catalysts are not consumed by the reaction itself, they may be inhibited, deactivated, or destroyed by secondary processes. In heterogeneous catalysis, typical secondary processes include coking where the catalyst becomes covered by polymeric side products. Additionally, heterogeneous catalysts can dissolve into the solution in a solid–liquid system or sublimate in a solid–gas system.
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Here’s another TIP: read the Background section of a patent that describes a novel catalyst.  The inventor often provides relatively clear statements as to the significance and benefits of the invention.  For example …

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CATALYSTS FOR PETROCHEMICAL CATALYSIS
United States Patent Application 20160340272
Cizeron; Joel M. ;   et al.   November 24, 2016
Abstract
Metal oxide catalysts comprising various dopants are provided. The catalysts are useful as heterogenous catalysts in a variety of catalytic reactions, for example, the oxidative coupling of methane to C2 hydrocarbons such as ethane and ethylene. Related methods for use and manufacture of the same are also disclosed.
Inventors: Cizeron; Joel M.; (Redwood City, CA) ; Scher; Erik C.; (San Francisco, CA) ; Zurcher; Fabio R.; (Brisbane, CA) ; Schammel; Wayne P.; (Brisbane, CA) ; Nyce; Greg; (Pleasanton, CA) ; Rumplecker; Anja; (San Francisco, CA) ; McCormick; Jarod; (San Carlos, CA) ; Alcid; Marian; (Sunnyvale, CA) ; Gamoras; Joel; (Vallejo, CA) ; Rosenberg; Daniel; (San Francisco, CA) ; Ras; Erik-Jan; (Amsterdam, NL)
Siluria Technologies, Inc., San Francisco, CA
BACKGROUND
[0001] Technical Field
[0002] This invention is generally related to novel catalysts and, more specifically, to doped metal oxide catalysts useful as heterogeneous catalysts in a variety of catalytic reactions, such as the oxidative coupling of methane to C2 hydrocarbons.
[0003] Description of the Related Art
[0004] Catalysis is the process in which the rate of a chemical reaction is either increased or decreased by means of a catalyst. Positive catalysts increase the speed of a chemical reaction, while negative catalysts slow it down. Substances that increase the activity of a catalyst are referred to as promoters or activators, and substances that deactivate a catalyst are referred to as catalytic poisons or deactivators. Unlike other reagents, a catalyst is not consumed by the chemical reaction, but instead participates in multiple chemical transformations. In the case of positive catalysts, the catalytic reaction generally has a lower rate-limiting free energy change to the transition state than the corresponding uncatalyzed reaction, resulting in an increased reaction rate at the same temperature. Thus, at a given temperature, a positive catalyst tends to increase the yield of desired product while decreasing the yield of undesired side products. Although catalysts are not consumed by the reaction itself, they may be inhibited, deactivated or destroyed by secondary processes, resulting in loss of catalytic activity.
[0005] Catalysts are generally characterized as either heterogeneous or homogeneous. Heterogeneous catalysts exist in a different phase than the reactants (e.g. a solid metal catalyst and gas phase reactants), and the catalytic reaction generally occurs on the surface of the heterogeneous catalyst. Thus, for the catalytic reaction to occur, the reactants must diffuse to and/or adsorb onto the catalyst surface. This transport and adsorption of reactants is often the rate limiting step in a heterogeneous catalysis reaction. Heterogeneous catalysts are also generally easily separable from the reaction mixture by common techniques such as filtration or distillation.
[0006] In contrast to a heterogeneous catalyst, a homogenous catalyst exists in the same phase as the reactants (e.g., a soluble organometallic catalyst and solvent-dissolved reactants). Accordingly, reactions catalyzed by a homogeneous catalyst are controlled by different kinetics than a heterogeneously catalyzed reaction. In addition, homogeneous catalysts can be difficult to separate from the reaction mixture.
[0007] While catalysis is involved in any number of technologies, one particular area of importance is the petrochemical industry. At the foundation of the modern petrochemical industry is the energy-intensive endothermic steam cracking of crude oil. Cracking is used to produce nearly all the fundamental chemical intermediates in use today. The amount of oil used for cracking and the volume of green house gases (GHG) emitted in the process are quite large: cracking consumes nearly 10% of the total oil extracted globally and produces 200M metric tons of CO.sub.2 equivalent every year (Ren, T, Patel, M. Res. Conserv. Recycl. 53:513, 2009). There remains a significant need in this field for new technology directed to the conversion of unreactive petrochemical feedstocks (e.g. paraffins, methane, ethane, etc.) into reactive chemical intermediates (e.g. olefins), particularly with regard to highly selective heterogeneous catalysts for the direct oxidation of hydrocarbons.
[0008] While there are multistep paths to convert methane to certain specific chemicals using first; high temperature steam reforming to syngas (a mixture of H.sub.2 and CO), followed by stochiometry adjustment and conversion to either methanol or, via the Fischer-Tropsch (F-T) synthesis, to liquid hydrocarbon fuels such as diesel or gasoline, this does not allow for the formation of certain high value chemical intermediates. This multi-step indirect method also requires a large capital investment in facilities and is expensive to operate, in part due to the energy intensive endothermic reforming step. For instance, in methane reforming, nearly 40% of methane is consumed as fuel for the reaction. It is also inefficient in that a substantial part of the carbon fed into the process ends up as the GHG CO.sub.2, both directly from the reaction and indirectly by burning fossil fuels to heat the reaction. Thus, to better exploit the natural gas resource, direct methods that are more efficient, economical and environmentally responsible are required.
[0009] One of the reactions for direct natural gas activation and its conversion into a useful high value chemical, is the oxidative coupling of methane ("OCM") to ethylene: 2CH.sub.4+O.sub.2.fwdarw.C.sub.2H.sub.4+2H.sub.2O. See, e.g., Zhang, Q., Journal of Natural Gas Chem., 12:81, 2003; Olah, G. "Hydrocarbon Chemistry", Ed. 2, John Wiley & Sons (2003). This reaction is exothermic (.DELTA.H=-67 kcals/mole) and has typically been shown to occur at very high temperatures (>700.degree. C.). Although the detailed reaction mechanism is not fully characterized, experimental evidence suggests that free radical chemistry is involved. (Lunsford, J. Chem. Soc., Chem. Comm., 1991; H. Lunsford, Angew. Chem., Int. Ed. Engl., 34:970, 1995). In the reaction, methane (CH.sub.4) is activated on the catalyst surface, forming methyl radicals which then couple in the gas phase to form ethane (C.sub.2H.sub.6), followed by dehydrogenation to ethylene (C.sub.2H.sub.4). Several catalysts have shown activity for OCM, including various forms of iron oxide, V.sub.2O.sub.5, MoO.sub.3, Co.sub.3O.sub.4, Pt--Rh, Li/ZrO.sub.2, Ag--Au, Au/Co.sub.3O.sub.4, Co/Mn, CeO.sub.2, MgO, La.sub.2O.sub.3, Mn.sub.3O.sub.4, Na.sub.2WO.sub.4, MnO, ZnO, and combinations thereof, on various supports. A number of doping elements have also proven to be useful in combination with the above catalysts.
[0010] Since the OCM reaction was first reported over thirty years ago, it has been the target of intense scientific and commercial interest, but the fundamental limitations of the conventional approach to C--H bond activation appear to limit the yield of this attractive reaction. Specifically, numerous publications from industrial and academic labs have consistently demonstrated characteristic performance of high selectivity at low conversion of methane, or low selectivity at high conversion (J. A. Labinger, Cat. Left., 1:371, 1988). Limited by this conversion/selectivity threshold, no OCM catalyst has been able to exceed 20-25% combined C.sub.2 yield (i.e. ethane and ethylene), and more importantly, all such reported yields operate at extremely high temperatures (>800 C).
[0011] In this regard, it is believed that the low yield of desired products (i.e. C.sub.2H.sub.4 and C.sub.2H.sub.6) is caused by the unique homogeneous/heterogeneous nature of the reaction. Specifically, due to the high reaction temperature, a majority of methyl radicals escape the catalyst surface and enter the gas phase. There, in the presence of oxygen and hydrogen, multiple side reactions are known to take place (J. A. Labinger, Cat. Lett., 1:371, 1988). The non-selective over-oxidation of hydrocarbons to CO and CO.sub.2 (e.g., complete oxidation) is the principal competing fast side reaction. Other undesirable products (e.g. methanol, formaldehyde) have also been observed and rapidly react to form CO and CO.sub.2.
[0012] In order to result in a commercially viable OCM process, a catalyst optimized for the activation of the C--H bond of methane at lower temperatures (e.g. 500-800.degree. C.) higher activities, and higher pressures are required. While the above discussion has focused on the OCM reaction, numerous other catalytic reactions (as discussed in greater detail below) would significantly benefit from catalytic optimization. Accordingly, there remains a need in the art for improved catalysts and, more specifically, catalysts for improving the yield, selectivity and conversion of, for example, the OCM reaction and other catalyzed reactions. The present invention fulfills these needs and provides further related advantages.
BRIEF SUMMARY
[0013] In brief, heterogeneous metal oxide catalysts and related methods are disclosed. For example, catalysts comprising oxides of magnesium, manganese, tungsten and/or rare earth elements are provided. The disclosed catalysts find utility in any number of catalytic reactions, for example in the OCM reaction. In some embodiments, the catalysts are advantageously doped with one or more doping elements. The doping elements may be promoters such that the catalyst comprises an improved catalytic activity. For example, in certain embodiments, the catalytic activity is such that the C2 selectivity is 50% or greater and the methane conversion is 20% or greater when the catalyst is employed as a heterogenous catalyst in the oxidative coupling of methane at a temperature of 850.degree. C. or less, 800.degree. C. or less, for example 750.degree. C. or less or 700.degree. C. or less.
[0014] In one embodiment, the disclosure provides a catalyst comprising a mixed oxide of magnesium and manganese, wherein the catalyst further comprises lithium and boron dopants and at least one doping element from groups 4, 9, 12, 13 or combinations thereof, wherein the catalyst comprises a C.sub.2 selectivity of greater than 50% and a methane conversion of greater than 20% when the catalyst is employed as a heterogenous catalyst in the oxidative coupling of methane at a temperature of 750.degree. C. or less.
[0015] In another embodiment, a catalyst comprising a mixed oxide of manganese and tungsten, wherein the catalyst further comprises a sodium dopant and at least one doping element from groups 2, 16 or combinations thereof is provided.
[0016] In still another embodiment, the disclosure is directed to a catalyst comprising an oxide of a rare earth element, wherein the catalyst further comprises at least one doping element from groups 1-16, lanthanides, actinides or combinations thereof, wherein the catalyst comprises a C.sub.2 selectivity of greater than 50% and a methane conversion of greater than 20% when the catalyst is employed as a heterogenous catalyst in the oxidative coupling of methane at a temperature of 750.degree. C. or less.
[0017] In another embodiment, a catalyst comprising a mixed oxide of manganese and tungsten, wherein the catalyst further comprises a sodium dopant and at least one doping element from groups 2, 4-6, 8-15, lanthanides or combinations thereof, wherein the catalyst comprises a C.sub.2 selectivity of greater than 50% and a methane conversion of greater than 20% when the catalyst is employed as a heterogenous catalyst in the oxidative coupling of methane at a temperature of 750.degree. C. or less is provided.
[0018] In yet other embodiments, the disclosure provides a catalyst comprising a mixed oxide of a lanthanide and tungsten, wherein the catalyst further comprises a sodium dopant and at least one doping element from groups 2, 4-15, lanthanides or combinations thereof, wherein the catalyst comprises a C.sub.2 selectivity of greater than 50% and a methane conversion of greater than 20% when the catalyst is employed as a heterogenous catalyst in the oxidative coupling of methane at a temperature of 750.degree. C. or less.
[0019] Other embodiments are directed to a catalyst comprising a rare earth oxide and one or more dopants, wherein the catalyst comprises a C.sub.2 selectivity of greater than 50% and a methane conversion of greater than 20% when the catalyst is employed as a heterogenous catalyst in the oxidative coupling of methane at a temperature of 750.degree. C. or less, and wherein the dopant comprises Eu/Na, Sr/Na, Na/Zr/Eu/Ca, Mg/Na, Sr/Sm/Ho/Tm, Sr/W, Mg/La/K, Na/K/Mg/Tm, Na/Dy/K, Na/La/Dy, Na/La/Eu, Na/La/Eu/In, Na/La/K, Na/La/Li/Cs, K/La, K/La/S, K/Na, Li/Cs, Li/Cs/La, Li/Cs/La/Tm, Li/Cs/Sr/Tm, Li/Sr/Cs, Li/Sr/Zn/K, Li/Ga/Cs, Li/K/Sr/La, Li/Na, Li/Na/Rb/Ga, Li/Na/Sr, Li/Na/Sr/La, Li/Sm/Cs, Ba/Sm/Yb/S, Ba/Tm/K/La, Ba/Tm/Zn/K, Cs/K/La, Cs/La/Tm/Na, Cs/Li/K/La, Sm/Li/Sr/Cs, Sr/Cs/La, Sr/Tm/Li/Cs, Zn/K, Zr/Cs/K/La, Rb/Ca/In/Ni, Sr/Ho/Tm, La/Nd/S, Li/Rb/Ca, Li/K, Tm/Lu/Ta/P, Rb/Ca/Dy/P, Mg/La/Yb/Zn, Rb/Sr/Lu, Na/Sr/Lu/Nb, Na/Eu/Hf, Dy/Rb/Gd, Na/Pt/Bi, Rb/Hf, Ca/Cs, Ca/Mg/Na, Hf/Bi, Sr/Sn, Sr/W, Sr/Nb, Zr/W, Y/W, Na/W, Bi/W, Bi/Cs, Bi/Ca, Bi/Sn, Bi/Sb, Ge/Hf, Hf/Sm, Sb/Ag, Sb/Bi, Sb/Au, Sb/Sm, Sb/Sr, Sb/W, Sb/Hf, Sb/Yb, Sb/Sn, Yb/Au, Yb/Ta, Yb/W, Yb/Sr, Yb/Pb, Yb/W, Yb/Ag, Au/Sr, W/Ge, Ta/Hf, W/Au, Ca/W, Au/Re, Sm/Li, La/K, Zn/Cs, Na/K/Mg, Zr/Cs, Ca/Ce, Na/Li/Cs, Li/Sr, Cs/Zn, La/Dy/K, Dy/K, La/Mg, Na/Nd/In/K, In/Sr, Sr/Cs, Rb/Ga/Tm/Cs, Ga/Cs, K/La/Zr/Ag, Lu/Fe, Sr/Tm, La/Dy, Sm/Li/Sr, Mg/K, Li/Rb/Ga, Li/Cs/Tm, Zr/K, Li/Cs, Li/K/La, Ce/Zr/La, Ca/Al/La, Sr/Zn/La, Sr/Cs/Zn, Sm/Cs, In/K, Ho/Cs/Li/La, Cs/La/Na, La/S/Sr, K/La/Zr/Ag, Lu/Tl, Pr/Zn, Rb/Sr/La, Na/Sr/Eu/Ca, K/Cs/Sr/La, Na/Sr/Lu, Sr/Eu/Dy, Lu/Nb, La/Dy/Gd, Na/Mg/Tl/P, Na/Pt, Gd/Li/K, Rb/K/Lu, Sr/La/Dy/S, Na/Ce/Co, Na/Ce, Na/Ga/Gd/Al, Ba/Rh/Ta, Ba/Ta, Na/Al/Bi, Cs/Eu/S, Sm/Tm/Yb/Fe, Sm/Tm/Yb, Hf/Zr/Ta, Rb/Gd/Li/K, Gd/Ho/Al/P, Na/Ca/Lu, Cu/Sn, Ag/Au, Al/Bi, Al/Mo, Al/Nb, Au/Pt, Ga/Bi, Mg/W, Pb/Au, Sn/Mg, Zn/Bi, Gd/Ho, Zr/Bi, Ho/Sr, Gd/Ho/Sr, Ca/Sr, Ca/Sr/W, Na/Zr/Eu/Tm, Sr/Ho/Tm/Na, Sr/Pb, Ca, Sr/W/Li, Ca/Sr/W, Sr/Hf or combinations thereof.
[0020] Still other catalysts of the present invention include a catalyst comprising a mixed oxide of a rare earth element and a Group 13 element, wherein the catalyst further comprises one or more Group 2 elements.
[0021] Other embodiments of the present invention are directed to a catalyst comprising a lanthanide oxide doped with an alkali metal, an alkaline earth metal or combinations thereof, and at least one other dopant from groups 3-16.
[0022] Methods for use of the disclosed catalysts in catalytic reactions, for example OCM, are also provided. Furthermore, the present disclosure also provides for the preparation of downstream products of ethylene, wherein the ethylene has been prepared via a reaction employing a catalyst disclosed herein.
[0023] These and other aspects of the invention will be apparent upon reference to the following detailed description. To this end, various references are set forth herein which describe in more detail certain background information, procedures, compounds and/or compositions, and are each hereby incorporated by reference in their entirety.
source: http://appft.uspto.gov/netacgi/nph-Parser?Sect1=PTO2&Sect2=HITOFF&p=1&u=%2Fnetahtml%2FPTO%2Fsearch-bool.html&r=4&f=G&l=50&co1=AND&d=PG01&s1=catalysis.TTL.&s2=sulfur&OS=TTL/catalysis+AND+sulfur&RS=TTL/catalysis+AND+sulfur
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A final HINT: Google® the following:

how to pitch a patent

One of the search results I found particularly interesting was this one …

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How a patent helped the pitch for a million dollar research start-up
Dr Sheila Donnelly
4 November 2016
When Dr Sheila Donnelly and her team at the University of Technology Sydney (UTS) created a novel technology with commercial potential, they worked with the Technology Transfer Office to secure patent protection, and then used their IP position to gain a 1.25 million dollar investment.
The investment, from Australia’s Medical Research Commercialisation Fund (MRCF), meant that Sheila and her team were able to form start-up, Helmedix. Helmedix, named from medicines derived from Helminth parasites, is developing new therapies for autoimmune diseases, such as rheumatoid arthritis, colitis, psoriasis and multiple sclerosis.
These therapies are all based on the technology first developed by Sheila and her team. Their research was concentrated on how worm parasites change their host immune response and if this process could be used as a therapeutic for autoimmune disease. This approach had never previously been explored but Sheila and her team were confident it could lead to something bigger, something tangible, and importantly, something commercial, so they approached the Technology Transfer Office at UTS very early on.
‘When we met with the commercialisation officer, we only had some preliminary data, only one graph and one sequence. We didn’t have a final draft of a paper, and we certainly didn’t have the idea fleshed out, but we had a notion of what it might lead to’, explained Sheila, ‘but because it was so early into the research project, we were able to keep working while the Tech Transfer Office worked with the patent attorneys to develop the patent application’.
The ability to continue researching at the same time the paperwork was being prepared meant the team weren't delayed by the patent application process, ‘We applied for a Patent Cooperation Treaty (PCT) in 2011 and a few months after that we published our paper. We weren't delayed in anyway by the patent application process because we disclosed our idea at an early stage’.
Sheila believes this is an important point for researchers who are concerned about the potential impact commercialisation has on their ability to publish, ‘If you think you may have the ability to commercialise your findings, you need to address that early on, that way you don’t delay your ability to publish. No matter how little data you think you have, the tech transfer office can assess the commercial possibilities; they do not need a fully developed research project. It is important that you communicate with them regularly’
Once the team had their patent filed with IP Australia they had to think about how they were going to execute their commercialisation plan, which Sheila believes is the most challenging part for academics, ‘execution for research academics is the real difficulty. Making that jump from the research lab and innovation to product is where we need collaboration with commercial partners’.
Finding these partners meant that Sheila and her team had to spend two years pitching, ‘We did hundreds of pitches, we pitched to venture capitalists, to small companies, to funding agencies, and eventually in 2013 the MRCF invested in our company and Helmedix was born’.
Sheila believes having IP protection was a critical factor to securing funding for their start-up. ‘We unashamedly advertised our IP position. We really used it to leverage our position. Certainly the feedback we got from a lot of the people we pitched to was that the IP position was quite important. It gave us more strength in the power of our pitches.’
Since receiving funding from MRCF, Helmedix has been able to progress the pre-clinical development of the immune modulating peptides. The plan moving forward is to seek further investment or industry partnerships, and eventually take the technology through clinical development as a treatment for autoimmune disease.
Sheila’s commercialisation journey has taken many years of research, pitching and collaborating, and has been full of challenges and rewards. She urges researchers thinking about commercialisation to consider their IP.
‘I would encourage all research academics to consider their commercialisation options and IP. Having IP protection does create impact, there’s no doubt about it. It almost gives a stamp of approval to your idea and illustrates that your research is innovative and potentially translatable; an important addition to your track record.’
source: https://www.ipaustralia.gov.au/tools-resources/case-studies/how-patent-helped-pitch-million-dollar-research-start
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This is the first in a series on CATALYSIS. Each post offers TIPS and HINTS on how to make your online search process more effective.