Patent Application
20170313637
The invention relates to oxygen transfer agents and the reactor systems and processes that utilize the oxygen transfer agents for the oxidative dehydrogenation (ODH) of hydrocarbons.
Ethylene and propylene are important building blocks for the petrochemical industry. These olefins are used in the manufacturing of polymers such as polyethylene, polypropylene, polystyrene and many more chemicals of commercial interest. Over 90% of the global olefin production comes from the high temperature steam cracking of naphtha or ethane and propane. The steam cracking process, which utilizes furnaces, is highly energy intensive, and 1.5 to 2 tons of carbon dioxide is produced for every ton of olefin product.
Natural gas production from shale deposits has dramatically increased supply in recent years. As a result of the continued global demand for olefins and the potential for a new growing supply of ethane and propane available in natural gas liquids from shale deposits, a significant amount of interest and investment is currently centered around expanding the capacity of ethylene and propylene derived from these new sources. Numerous olefin grass root and expansion projects are either under contract or in the planning stages to take advantage of the relative low cost liquids from wet shale gas. However, there are many environmental and cost challenges to bringing on this level of new capacity.
Olefin production is the largest emitter of CO2 and NOx in the organic chemical industry. With worldwide ethylene production at ˜150 MT/yr, the industry emits 150-300 MT/yr of CO2 and roughly 1.4 MT/yr of NOx. Projects located in severe EPA non-attainment zones are challenged by the increase cost of NOx control. The total greenhouse gas (GHG) emission profile, reported in CO2 equivalents, is another critical part of the permitting for all production expansions.
The industry continues to push for production technology that: (1) generates higher overall yield of ethylene and propylene; (2) increases the run length between furnace turnarounds (e.g. inspections, repairs, improvements, etc.); (3) lowers steam and energy utilization; (4) lowers all GHGs including carbon dioxide and NOx. ODH of ethane and propane offers a potential solution for these needs.
The ODH of ethane and propane to olefins offers a production route that can significantly reduce CO2 emissions and virtually eliminate NOx emissions from world scale plants. ODH is a selective catalytic process that produces primarily ethylene and water as products, and is thereby an exothermic reaction (reaction 1).
CH3CH3+½O2→CH2CH2+H2O ΔHo=−105 kJ/mol (1)
The per pass yield of the ODH reaction is not limited by thermodynamic equilibrium, as it is in pyrolysis, (reaction 2).
CH3CH3+Heat⇄CH2CH2+H2 ΔHo=+137 kJ/mol (2)
ODH provides an opportunity to achieve some of the objectives to improve the efficiency of olefin production. While a significant amount of research has been done in ODH over the last 25 years, most reported processes involve highly exothermic catalytic reactions with co-fed oxygen and hydrocarbon over platinum group metal catalysts, which are expensive materials. Therefore, there is a need for improved materials for facilitating ODH, as well as reactors and processes that include these improved materials.
In a first aspect of the present invention, an oxygen transfer agent is provided that comprises a mixed oxide having a cubic crystal lattice structure and a chemical formula of:
R6R′O8
wherein R is a first element, R′ is a second element that is different than the first element, and O is oxygen, and the oxygen transfer agent preferably further comprises a promoter.
In a second aspect of the present invention, a reactor vessel is provided that comprises:
a reactor defining an inner volume at least partially filled with an oxygen transfer agent according to the present invention;
an inlet stream attached to the reactor, the inlet stream configured to deliver at least one of a saturated hydrocarbon and an oxygen-containing gas to the reactor; and
an effluent stream attached to the reactor, the effluent stream configured to allow the removal of at least one of unsaturated hydrocarbons, water, and an oxygen-depleted gas from the reactor,
wherein the reactor is configured to enable the contact of the oxygen transfer agent with at least one of the saturated hydrocarbons and the oxygen-containing gas.
In a third aspect of the invention, a process is provided comprising providing a saturated hydrocarbon to a reactor at least partially filled with an oxygen transfer agent according to the present invention, removing an effluent from the reactor containing the unsaturated hydrocarbon, and supplying oxygen to the oxygen transfer agent such that the oxygen transfer agent is oxidized.
In order that the invention may be more fully understood, the following figures are provided by way of illustration, in which:
Although the invention is illustrated and described herein with reference to specific embodiments, the invention is not intended to be limited to the details shown. Rather, various modifications may be made in the details within the scope and range of equivalents of the claims and without departing from the invention.
According to various embodiments of the present invention, oxygen transfer agents are provided that are useful for the ODH of hydrocarbons following the generalized formula of Equation 1:
zCnH2n+2−2β+(z−1+δ)“O”→C(z×n)H2(z×n)+2−2β−2δ+(z−1+δ)H2O (Eq. 1.)
where z=the number of reacting molecules; n=the number of atomic units in the reacting molecule; β=the degree of unsaturation where the value is zero for single bonds, one for double bonds and molecular rings, and two for triple bonds; and δ=the change in the degree of unsaturation. The oxygen, “O” in Equation 1 may be supplied by the reduction of a metal oxide or via the catalytic use of molecular oxygen.
The oxygen transfer agents according to the present invention may also be useful for the case of Equation 1, where the carbon number, n, is equal to one. In this case the useful reaction promoted by these agents is called the oxidative coupling of methane (OCM) to higher hydrocarbons.
A few examples of the reactions described by Equation 1 that may be promoted using an oxygen transfer agent according to the present invention are shown in Table 1.
While promoting the conversion of hydrocarbons according to any of the reactions of Equation 1, the oxygen transfer agent according to the present invention is reduced from an oxidized state to a less oxidized, reduced, state. In order to regenerate the agent, oxygen may be used to re-oxidize the reduced agent. This re-oxidation process may occur concurrent with the reduction of the oxygen transfer agent in the presence of one or more oxidation agent(s) such as oxygen, air, carbon dioxide, steam, NOx, and/or oxides of sulfur. A preferred embodiment of this invention is the re-oxidation of the oxygen transfer agents in a separate step. This reduction/oxidation of the oxygen transfer agent with concurrent formation of useful products, which is schematically illustrated in
There are many benefits of processing the ODH reaction in a chemical looping mode which include:
According to a first embodiment of the present invention, the oxygen transfer agent comprises an alkali metal or a compound thereof and at least one of
According to a second embodiment of the present invention, the oxygen transfer agent comprises an alkali metal or a compound thereof, boron or a compound thereof, and at least one of
According to a third embodiment of the present invention, the oxygen transfer agent comprises:
The mixed oxides included in the oxygen transfer agents useful for the present invention are prepared from materials that come from a family of cubic crystal lattice, R6R′O8, wherein R and R′ are different elements and O is oxygen. These materials are solid solutions of R′ in R and have been observed to show very little crystal lattice parameter change upon reduction or re-oxidation, thus making them dimensionally stable as oxygen transfer agents. Examples of materials include Mg6MnO8, Cu6PbO8 and Ni6MnO8, with Mg6MnO8 being particularly preferred.
In addition to stable crystal structures upon redox cycles, these R6R′O8 materials may be prepared in a way that yields very dense, hard, substrates. The addition of small amounts of boron greatly increases their particle toughness.
To date, the highest reported yield via chemical looping using known catalysts is about 60%. However, the oxygen transfer agents according to various embodiments of the present invention when used to convert ethane to ethylene and higher olefins via chemical looping have exhibited yields at 70-80% (see
The challenge for chemical looping, or “redox”, ODH systems is to minimize the thermodynamically-favored, non-selective production of carbon dioxide. Table 2 shows thermodynamic values for pertinent reactions at 1,100 K.
Systems that include oxygen transfer agents according to the present invention have been found to not only exhibit higher yields of unsaturated hydrocarbons, but also exhibit reduced CO2 production. The oxygen transfer agents according to the present invention promote the oxidation of hydrocarbons to more oxidized hydrocarbons in preference to the formation of carbon dioxide, carbon monoxide, or solid carbon products commonly known as coke.
The materials can promote the selective oxidation of compounds, as long as the oxygen transfer agents are at least partially oxidized, and thereby would also react with hydrogen to form water. Hydrogen may also be produced from the dehydrogenation of hydrocarbons in the reactor. As explained above, the oxygen transfer agents are reduced by the reaction with hydrogen and/or hydrocarbons in the feed stream and reoxidized by reaction with oxygen.
The oxygen transfer agents according the various embodiments of the present invention may further include a promoter that serve to promote higher selectivity to specific desired products. While not wishing to be bound to theory, it is believed that active oxygen is drawn to the promoter sites within the oxygen transfer agent. This enables the oxygen transfer agents to act as a selective promoter of Equation 1 and as an oxygen reservoir to the selective promoting agent.
Promoters that may be included in the oxygen transfer agent according to various embodiments of the present invention include, but are not limited to,
Other promoters may include silicates or aluminates of alkaline metals or alkaline earth metals, such as silicates and aluminates of sodium, lithium, calcium, and barium. In addition, silicates and aluminates of manganese (braunite), iron, zirconium, copper or ruthenium may be used. Another class of oxygen flux promoters that may be used includes oxides with hole structures that promote oxygen anion transport such as cerium oxide, zinc oxide, zirconium oxide (with or without additives such as yttrium), praseodymium oxide, or barium oxide.
The oxygen transfer agents may be conveniently prepared by any methods known by those skilled in the art which include precipitation, co-precipitation, impregnation, granulation, spray drying, dry mixing or others. Precursors may be transformed into the active agents according to the present invention by calcination at temperatures suitable for the formation of the active components, typically in the range of 400° to 1,100° C. The calcination may be performed under any atmosphere, such as air, inert gases, hydrogen, carbon monoxide, and hydrocarbon gases, so as to form the active oxygen transfer agents of the present invention.
According to another embodiment of the present invention, a system is provided comprising a reactor containing an oxygen transfer agent useful for the ODH of hydrocarbons as described above. The system may include any reactor type known to be useful for the selective oxidation or dehydrogenation of hydrocarbons. In the instance where the conversions of Equation 1 are run in a co-feed mode with a mixture of hydrocarbon and oxidant, it will be useful to use reactors that can effectively remove the heat of reaction, such as shell and tube reactors.
The oxygen transfer agents according to various embodiments of the present invention may be used in a chemical looping system to promote an ODH reaction via a Mars-van Krevelen-like mechanism, as illustrated in
In
The preferred embodiment of the current invention would be a system that includes a reactor that circulates oxygen transfer agent from a hydrocarbon reactor zone to a regeneration zone, such as the system illustrated in
In
The systems according to the present invention may be run in lean phase, dense phase particle transport, or include a free-falling bed, for example. The reactors in the systems according to various embodiments of the present invention are not limited by the fluidization regime employed in either the hydrocarbon oxidation or re-oxidation reactors.
The physical shape of the reactor is not important as long as the unit can effectively contact the reactants with the oxygen transfer agent, have effective control of the reaction contact times, have suitable mechanical stability under reaction conditions, and can be manufactured at reasonable costs.
The oxygen transfer agents according to the present invention may be porous, or dense, in so much as effective mass transport of reactants is maintained. The contact time of the feed hydrocarbons or the feed oxidant, typically air, with the oxygen transfer agent may be 0.01 seconds to 60 seconds, when calculated at reaction conditions of temperature and pressure. More typically, the contact time will be in the range of 0.1 to 20 seconds. The reaction contact times are optimized to produce the highest yield of the desired product of oxidation.
The reaction pressure in the reactors should be optimized to produce the highest is yield of the desired oxidation products. Typical pressures of operation are between 0.1 and 20 atmospheres and more preferably between 1 and 15 atmospheres. The preferred temperature for reaction in the reactor is 400° to 1,000° C. A more narrow operating range of 500-950° C. may be effective depending on the type and amount of promoters included with the oxygen transfer agent. In addition, it may be beneficial to run the process at elevated pressures depending on the promoter material. The temperature and pressure should also be selected to allow for safe operation.
In yet another embodiment of the present invention, methods of using the above-described systems include the step of introducing gas phase promoters into the reactors that facilitate the desired reactions of Equation 1. The addition of gas phase promoters may greatly enhance the selectivity of the desired ODH products when used with oxygen transfer agents of the present invention. The gas phase promoters may also result in higher activity and extend the useful life of the oxygen transfer agents. Various gas phase promoters include, but are not limited to, gas phase water, steam, CO2, halide gases (such as chlorine, bromine, or fluorine), hydrogen halides (such as HCl, HBr, and HF), and sulfur containing gases such as hydrogen sulfide, oxides of sulfur, and organo-sulfur compounds.
The oxygen transfer agents of the present invention may be used to convert various forms of sulfur containing natural gas which includes, but is not limited to biogas, shale gas, associated gas from oil & gas production, coal gas, or any other form of methane containing gas that also contains some form of sulfur, either organic or inorganic sulfur, to higher hydrocarbons. The oxidation of H2S contained in the natural gas into SO2 and SO3 has been found to be synergistically beneficial for CO2 sequestration, selectivity to C2+ products, and useful life of the oxygen transfer agent. Generally, all sulfur in the feed provided to a reactor according to an embodiment of the present invention is converted to SO2, SO3, or a mixture of the two sulfur gases.
Compared to current systems that utilize platinum-based materials to produce unsaturated hydrocarbons, systems according to various embodiments of the present invention advantageously generate low amounts of NOx. Systems that utilize platinum-based catalysts generally require high temperature fuel combustion or de-coking to promote the generation of unsaturated hydrocarbons. High temperatures often lead to NOx production, unless the nitrogen is removed from the feed gases used to maintain combustion in the furnaces. NOx production in these platinum-based systems may be avoided, but only by using expensive pure oxygen feed streams. The ODH reactions performed using oxygen transfer agent according to the present invention are exothermic reactions; however, the temperatures of the exotherm are relatively low compared to furnace temperatures and therefore, generate little NOx. Thus, systems and methods according to the present invention offer more environmentally friendly and less expensive alternatives to present day processes.
The effluent produced by the reactor of the present invention may comprise unconverted hydrocarbons as well as some lower value products, such as carbon dioxide and carbon monoxide that may also be formed at low concentrations. Additional components of the effluent may include oxygenated hydrocarbons, such as alcohols, which are formed in preference to the production of carbon monoxide or carbon dioxide, resulting in an effluent from the reactor with a higher molar concentration of oxygenated hydrocarbons than carbon monoxide or carbon dioxide. It is within the scope of the present invention to recycle the effluent. Similarly, lower value products, such as carbon oxides and water, may be removed from the effluent prior to further treatment.
Preferably, further downstream processes include separation methods in order to isolate polymer grade olefins. For example, ethylene fractionation may include one or more driers in order to remove water prior to feeding the dried product to a distillation column. The distillation column preferably includes several stages to provide a highly pure polymer grade ethylene product. The polymer grade olefins may then be sold as raw materials for the production of higher molecular weight products by oligomerization.
Numerous catalysts and processes are known for the oligomerization of olefins generally, and of ethylene particularly, all of which may be employed for converting the polymer grade olefins made according to the various methods of the present invention to higher molecular weight products. For example, phosphoric acid supported on a kieselguhr base has been widely used for making polymer gasoline (i.e., olefinic hydrocarbon liquids within the gasoline boiling range) from refinery gases. Other catalysts which have been employed for similar purposes include the oxides of cobalt, nickel, chromium, molybdenum and tungsten on supports such as alumina, silica-alumina, kieselguhr, carbon and the like. Higher hydrocarbon products of interest may include aviation fuels, kerosene, or intermediate refining streams.
Without intending to limit the scope of the claimed invention, most oligomerization catalysts may be classified in one of two general categories: metal catalysts and acid catalysts. They may also be classified as heterogeneous (solid) catalysts or homogeneous (liquid-phase) catalysts. Examples of metal catalysts that may be used in a process according to the present invention for oligomerization of unsaturated hydrocarbons, include nickel (note that these catalysts require a donor ligand and a Lewis acid), palladium, chromium, cobalt, titanium, tungsten, and rhenium. Examples of acid catalysts include phosphoric acid and acid catalysts based on alumina.
Other acid catalysts that may be used in the present invention are silaceous, crystalline molecular sieves. Such silica-containing crystalline materials include materials which contain, in addition to silica, significant amounts of alumina, and generally known as “zeolites”, i.e., crystalline aluminosilicates. Silica-containing crystalline materials also include essentially aluminum-free silicates. These crystalline materials are exemplified by crystalline silica polymorphs (e.g., silicalite and organosilicates), chromia silicates (e.g., CZM), ferrosilicates and galliosilicates, and borosilicates. Crystalline aluminosilicate zeolites are best exemplified by ZSM-5, ZSM-11, ZSM-12, ZSM-21, ZSM-38, ZSM-23, and ZSM-35.
Metal oligomerization catalysts in general are more sensitive to feed impurities, (e.g., water, carbon monoxide, dienes, etc.) than are the acid catalysts. Although homogeneous, metal catalysts are quite active, the need for dry feeds, solvents, and other measures to prevent catalyst deactivation and precipitation is disadvantageous and suggests an obvious advantage to supported, heterogeneous, metal catalyst.
Homogeneous acid catalysts are effective but, are also corrosive and tend to form two liquid-phase systems with the non-polar hydrocarbon oligomerization products. Considering the foregoing observations, heterogeneous acid catalysts are the preferred catalyst for use in the oligomerization step of the process according to the present invention. Of the heterogeneous acid catalysts, acid zeolites are especially preferred, particularly zeolites of the ZSM-type and borosilicates.
In order that the invention may be more fully understood, the following Examples are provided by way of illustration only.
The following is an evaluation and comparison of catalysts used for the oxidative coupling of methane (OCM) and an oxygen transfer agent of the present invention when the materials are used for ethane conversion.
Ethane was fed at 4,500 hr−1 GHSV, 850° C., through four 0.5 mL beds in a quartz U-tube reactor. Each bed contained a different material. The effluent from the bed was connected directly to a mass spectrometer, and the reaction continuously monitored over an 8 second pulse of 80% ethane. Ethane pulses were followed by a nitrogen purge and air regeneration to simulate redox cycles.
The material of Bed A was a low surface area alpha alumina inert support. The material of Bed B was a 15% manganese on magnesia. The material of Bed C was a first oxygen transfer agent according to the present invention comprising Li/Mn/B/MgO. The material of Bed D was a second oxygen transfer agent according to the present invention comprising W/P/Li/Mn/B/MgO.
The material in Bed C was prepared by ball milling manganese dioxide (32.2 grams), boric acid (11.3 grams), magnesia (42.3 grams) and lithium hydroxide (4.5 grams) with water. The milled mixture was calcined in air at 900° C. for 8 hours.
The material used in Bed D was prepared by ball milling manganese dioxide (32.2 grams), boric acid (11.3 grams), magnesia (42.3 grams) and lithium hydroxide (4.5 grams). The milled mixture was calcined in air at 900° C. for 8 hours. The resulting material was treated with phosphotungstic acid via incipient wetness technique to yield 5% W and calcined again at 900° C. for 8 hours.
The ethane reaction profile of each of Beds A-D is provided in
The data demonstrates that oxygen transfer agents according to the present invention provide high C2+ olefin selectivity and that the use of a promoter is particularly advantageous. This suggests that simply changing the composition of the oxygen transfer agent enables adjustment of the amount of hydrocarbon production, thereby allowing the tuning of hydrocarbon yields based on the market needs of each specific ODH installation.
To determine the effect of various promoters on oxygen transfer agent according to the present invention various ethane conversions were performed in a temperature range of 825-850° C. and at atmospheric pressure. The cumulative yields of the first 15 seconds of ethane conversions are provided in Table 3.
Product profiles interpolated from example 2 were incorporated into standard industrial process simulation software. The simulation was used to project the productivity of a commercial scale reactor. The projections suggest that one or two large circulating bed units consisting of one ODH reactor and one regeneration unit could convert all the gas feed for a 1,000 kT/a ethylene plant. This process intensity is consistent with typical modern FCC units.
For a single, two reactor unit, a capital estimate and process economics were developed for an ODH system using an oxygen transfer agent according to the present invention. The results are provided in Table 4. The downstream recovery sections were approximated to be similar to conventional steam cracking. However, heat recovery and compression systems were factored relative to steam cracking to match the reduced load of the ODH system. In addition, the steam cracking and ODH systems were compared to an estimate for a catalytic partial oxidation route (POx).
While the direct POx process has the potential for lower overall capital costs, pure oxygen is required for the catalytic reaction. The cost of oxygen adds about 1-2 ¢/lb. to the cost of ethylene. Using the ODH technology, one large scale fluid bed reactor may be able to convert the same ethane feed rate as 6-8 steam cracking furnaces. This will save on capital and reduce the turnaround schedule for the plant. A steam cracker requires multiple turnarounds each year. In comparison, an FCC unit may go 2-3 years before a turnaround, as the circulating material is continuously regenerated and replenished. The same extended turnaround schedule for the ODH process is expected.
One of the biggest benefits of ODH is the more than 90% reduction in production of CO2. The exothermic ODH reaction generates excess heat that is used for downstream processing. In addition, since no high temperature furnace is required, NOx production will be extremely low. These environmental benefits may not only save capital and lower operating costs, but they may allow for a quicker permitting process.
While preferred embodiments of the invention have been shown and described herein, it will be understood that such embodiments are provided by way of example only. Numerous variations, changes, and substitutions will occur to those skilled in the art without departing from the spirit of the invention. Accordingly, it is intended that the appended claims cover all such variations as fall within the spirit and scope of the invention.
The present application claims priority to and benefit of U.S. Provisional Patent Application No. 62/054,424, filed Sep. 24, 2014, the disclosure of which is incorporated herein by reference in its entirety for all purposes.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2015/051661 | 9/23/2015 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 62054424 | Sep 2014 | US |
