Name of Applicant/s: Actual Inventor/s: Address for Service: The BOC Group, Inc Yongxian Zeng and Ravi Jain and Satish S. Tamhankar and Donald L. MacLean and Narayanan Ramprasad BALDWIN SHELSTON WATERS MARGARET STREET SYDNEY NSW 2000 'HYDROCARBON PARTIAL OXIDATION PROCESS' Invention Title: The following statement is a full description of this invention, including the best method of performing it known to me/us:- File: 25338AUP00 -la- HYDROCARBON PARTIAL OXIDATION PROCESS FIELD OF THE INVENTION This invention relates to the partial oxidation of hydrocarbons, and more particularly to the production of hydrogen and carbon monoxide by the oxidation of hydrocarbons. Specifically, the invention relates to the high temperature adsorption of oxygen onto ceramic adsorbents and partial oxidation of hydrocarbons by contacting the hydrocarbons with the sorbed oxygen at elevated temperatures.
BACKGROUND OF THE INVENTION Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of common general knowledge in the field.
Syngas and its components, hydrogen and carbon monoxide, are conventionally produced by the high temperature partial oxidation of hydrocarbons with controlled amounts of air or oxygen. Although air is less expensive and more convenient to use in 15 partial oxidation reactions, it is less attractive than oxygen for such reactions because the S" large quantities of nitrogen that are produced when air is used as the oxidant must be subsequently separated from the product gas prior to its use. The cost of gas separation and purification equipment required to purify the product gas adds considerably to the cost of syngas production using air.
o 0 00 oo o 0oo 0 0 0:e .0.0 2 Although oxygen is more desirable than air as an oxidant for partial oxidation reactions, its use is not without disadvantage, in that oxygen must be imported into the system, or it must be generated on site, for example, by means of a cryogenic air separation plant or an adsorption system. In either alternative, using oxygen as the oxidant likewise adds considerably to the cost of the process.
More economical methods of on site production of oxygen for applications such as hydrocarbon partial oxidation reactions are continuously sought. U. S. Pat.
No. 5,714,091 discloses an oxygen-based hydrocarbon partial oxidation process 10 in which the oxygen is produced on site by subjecting air to membrane separation using a membrane constructed of perovskite-based ceramic material.
Oxygen, which is permeable to the membrane, passes through the membrane and is made to. react with hydrocarbons on the downstream side of the membrane unit. The disadvantages of this method of oxygen production are the high cost of production of the membrane and the difficulty of producing membrane structures that are leak-proof.
The present invention provides a system and process for the partial oxidation of hydrocarbons with oxygen that is produced from air in the partial oxidation reactor using a relatively inexpensive ceramic-based adsorbent material and a simple reactor design. The method of this invention has the additional advantage that the heat produced by the partial oxidation reaction can be used to increase the overall efficiency of the process by maintaining the adsorbent at the desired adsorption temperature without an external heat source.
SUMMARY OF THE INVENTION According to a first aspect, the present invention provides a process for producing hydrogen and carbon monoxide by the partial oxidation of at least one hydrocarbon comprising the steps: passing an oxygen-containing gas at a temperature in the range of about 300 to about 14000 C through at least one reaction zone containing an oxygen-selective mixed conductor at an absolute pressure in the range of about 0.5 to about bara, thereby preferentially retaining said oxygen in said mixes conductor; and passing said at least one hydrocarbon through said at least one reaction zone at a temperature in the range of about 300 to about 14000 C, thereby containing said mixed conductor retaining oxygen and reacting to produce a product gas comprising hydrogen, carbon monoxide or mixtures of these.
In a preferred embodiment of the invention, the oxygen-selective mixed conductor is selected from: perovskite substances having the structural formula AI.xMxBO3_-, where A is a rare earth ion, M is Sr, Ca, Ba or mixtures of these, B is Co, Mn, Cr, Fe or mixtures of these, x varies from 0 to 1 and 6 is the deviation from stoichiometric composition resulting from the substitution of Sr, Ca and Ba for rare earth ions; (2) ceramic substances selected from Bi 2 0 3 ZrO 2 CeO 2 ThO 2 HfO 2 and mixtures of these, the ceramic substance being doped with CaO, rare earth metal oxides or mixtures of these; brownmillerite oxide; and mixtures of any of these.
In a more preferred embodiment of the invention, the oxygen-selective mixed conductor is a perovskite substance, and in a preferred aspect of this embodiment, x varies from about 0.1 to 1.
r r oo •o o oo*oo^ *oo oo• *oo r oo o•^ oo *oo 4 In another preferred embodiment, the oxygen-selective mixed conductor is a ceramic substance of group above, and the ceramic substance is doped with a rare earth metal oxide selected from Y 2 0 3 Nb 2 0 3 Sm 2 03, Gd 2 0 3 and mixtures of these.
In another preferred embodiment, the oxygen-containing gas is air.
In another preferred embodiment, the process comprises repeatedly performing steps and in sequence in the above-mentioned at least one reaction zone.
In another preferred embodiment, the process further comprises, between steps and the additional step of removing nonadsorbed gas component from oo 10 the adsorption vessel(s): by purging the at least one reaction zone with gas that is compatible with the partial oxidation reaction product gas, by 00 •depressurizing the at least one reaction zone or by both purging the at least one reaction zone with gas that is compatible with the partial oxidation reaction product gas and depressurizing the at least one reaction zone. In a preferred aspect of this preferred embodiment, the gas that is used to purge the at least one reaction zone is oxygen, steam, carbon dioxide or mixtures of these *In another preferred embodiment, the process further comprises, after step removing residual product gas from the at least one adsorption zone: by purging the at least one reaction zone with steam, carbon dioxide, nitrogen, argon, helium or mixtures of these, by depressurizing the at least one reaction zone or by both purging the at least one reaction zone with steam, carbon dioxide, nitrogen, argon, helium or mixtures of these and depressurizing the at least one reaction zone.
In another preferred embodiment, the at least one hydrocarbon has an aliphatic, cycloaliphatic or aromatic structure and it contains 1 to 12 carbon atoms.
In another preferred embodiment, the process is carried out at a temperature in the range of about 600 to about 12000 C.
In another preferred embodiment, step of the process is carried out at an absolute pressure in the range of about 0.5 to 20 bara.
In a more preferred embodiment, the at least one hydrocarbon contains 1 to 6 carbon atoms.
In other preferred embodiments, the oxygen-selective mixed conductor is a •perovskite substance and A is La, Y or mixtures of these and/or M is Sr, Ca or mixtures of these and/or B is Co, Fe or mixtures of these. More preferably, A is La, Y or mixtures of these, and/or M is Sr, Ca or mixtures of these and/or B is Co, Fe or mixtures of these.
In another preferred embodiment of the invention the oxygen-selective mixed conductor is a perovskite substance and x is 0.2 to 1.
o* 4 In a most preferred embodiment, the process is carried out at a temperature in the range of about 750 to about 11000 C.
In a more preferred embodiment, the at least one hydrocarbon comprises 1 to 4 carbon atoms, and in one most preferred embodiment, it is methane. In another most preferred embodiment, the hydrocarbon feed gas is natural gas.
In another preferred embodiment, the at least one hydrocarbon comprises a petroleum derivative. In a more preferred embodiment, the petroleum derivative is naphtha, gasoline or mixtures thereof.
In another preferred embodiment, the at least one reaction zone contains particulate material having a thermal conductivity greater than that of the oxygenselective mixed conductor. In one preferred aspect of this preferred embodiment, the high thermal conductivity particulate material is mixed with the oxygen-selective mixed conductor, and in another preferred aspect, the high thermal conductivity particulate is placed, upstream, downstream or both upstream and downstream of the oxygen-selective mixed conductor.
In another preferred embodiment, the at least one reaction zone additionally contains one or more catalysts for partial oxidation reactions. In a more preferred embodiment, the additional catalyst is deposited on the oxygen-selective mixed conductor.
In another preferred embodiment, the process of the invention further comprises, during step passing a moderating agent selected from steam, carbon dioxide and mixtures of these through the at least one reaction zone. In a preferred aspect of this embodiment, the moderating agent is steam.
According to a second, the present invention provides apparatus for the partial oxidation of hydrocarbons comprising: at least one reaction zone containing an oxygen-selective mixed conductor; sequential means for introducing oxygen-containing gas into said at least one reaction zone; sequential means for introducing hydrocarbon feed into said at least one reaction zone; sequential means for removing a product stream from said at least one reaction .zone.
According to a third aspect, the present invention provides hydrogen and carbon monoxide when produced by a process according to the first aspect.
:Unless the context clearly requires otherwise, throughout the description and the 1 25 claims, the words 'comprise', 'comprising', and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of "including, but not limited to".
BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic representation of a two-reaction vessel system for practice of 30 the process of the invention.
DETAILED DESCRIPTION OF THE INVENTION The process of the invention is useful for carrying out partial oxidation processes that produce hydrogen and/or carbon monoxide and perhaps other products using as the 6aoxidant substantially pure oxygen produced in the partial oxidation reaction chamber.
The process of the invention is particularly useful for economically conducting partial oxidation processes in systems of any desired size. The oxygen adsorption step is carried out at high temperatures; accordingly, the adsorption step provides a high temperature environment for the partial oxidation process.
The oxygen is produced by adsorbing it from an oxygen-containing gas onto a ceramic substance which serves as the site of the partial oxidation reaction. By "oxygen-containing gas" is meant a gas that contains elemental oxygen. The Oxygen-containing gas may be substantially pure oxygen or oxygen-gas mixtures, such as oxygen-nitrogen mixtures, oxygen-argon mixtures, oxygennitrogen-argon mixtures, such as air, oxygen-carbon dioxide mixtures, oxygencarbon monoxide mixtures, etc. The preferred oxygen-containing gas is air, particularly ambient air, because of its low cost and ready availability.
The adsorption/partial oxidation process of the invention is preferably carried out on a cyclical basis. It comprises a high temperature oxygen adsorption step and a partial oxidation reaction step using the adsorbed oxygen as the oxidant. The process can be carried out in a system comprising a single adsorption/reaction 15 unit or a battery of adsorption/reaction units operated in phase, or a plurality of adsorption/reactor units or batteries of adsorption/reaction units operated out of phase, whichever is desired. When a system comprising a single unit or a battery .i of units all of which are operated in phase is used, the adsorption and partial oxidation steps are necessarily intermittent, whereas when a plurality of units are employed in parallel and operated out of phase, one or more units can be in oxygen adsorption service while the partial oxidation reaction is being carried out in one or more other units. In preferred embodiments of the invention, adsorption/partial oxidation cycles are repeatedly carried out in a manner such that production of the desired partial oxidation products is substantially continuous.
The adsorbent/catalyst used in the process of this invention is an oxygenselective mixed conductor. By "oxygen-selective mixed conductor" is meant a iO II 8 ceramic material that exhibits both oxygen ion conductivity and electronic conductivity. Properties of oxygen-selective mixed conductors are set forth in Lin et al., "Oxygen Permeation through Thin Mixed Conducting Solid Oxide Membranes", AIChE Joumal, May 1994, Vol. 40, No. 5, pp. 786-798, the text of which is incorporated herein by reference.
Preferred oxygen-selective mixed conductors include ceramic materials selected from: perovskite substances having the structural formula Ai MxBO,, where A is a rare earth ion, M is Sr, Ca, Ba or mixtures of these, B is Co, Mn, Cr, Fe or mixtures of these, x varies from >0 to 1 and 6 is the deviation from stoichiometric composition resulting from the substitution of Sr, Ca and Ba for rare earth ions; ceramic materials selected from compounds such as Bi 2 0 3 ZrO 2 CeO 2 ThO 2 HfO 2 and mixtures of these, wherein the ceramic material is doped with CaO, a rare earth metal oxides, such as, for example, Y 2 0 3 NbO 3 Sm 2 0 3 Gd 2 03 and mixtures of these; a brownmillerite oxide; and mixtures of any of these.
In a preferred embodiment the ceramic oxygen-adsorbing material is a ceramic substance having the perovskite structure. When the ceramic material is a perovskite, the maximum oxygen adsorbing capability is attained when x, in the formula above, has a value of 1. Although oxygen adsorption can occur when the value of x in the perovskite compound used in the process is 0, it is generally not commercially feasible to use perovskite compounds having a value of x less than about 0.01 in the process of the invention. Preferably x has a value of about 0.1 to 1, and most preferably it has a value of about 0.2 to 1. Details of the adsorption step of the process are set forth in the copending U. S. patent application entitled High Temperature Adsorption Process, filed of even date herewith, the specification of which is incorporated herein by reference.
When the ceramic material is perovskite, the preferred rare earth ions for use in the process of the invention are La and Y, and the preferred divalent cations are Sr and Ca. Also, B is preferably Co or Fe. Typical of perovskite adsorbents suitable for use in the invention are La,,SrxBO,, YlxSrxBO,, Y,.CaxBO, and combinations of these, wherein B is Co, Mn, Cr or Fe. Specific useful perovskite adsorbents are materials having the structural formulas: Lao.
7 Cao.3FeOs, Yo.Sro.CrOu, SrCoO 3 etc. In the last compound, SrCoO 3 x has a value of 1.
The minimum temperature at which the adsorption step of the process of the o invention is carried out is generally at least about 3000 C. This step is preferably carried out at temperatures of at least about 6000 C, and most preferably carried out at temperatures of at least about 7500 C. The upper temperature limit for carrying out the adsorption step is below the temperature at which the oxygenselective adsorbent begins to melt. Generally the maximum upper temperature is not in excess of about 14000 C. Preferably, the adsorption step is carried out at temperatures not exceeding about 12000 C, and this step is most preferably carried out at temperatures not in excess of about 11000 C. The partial oxidation step of the process is generally carried out at or near the temperature at which the adsorption step is carried out.
Since the partial oxidation step of the process is highly exothermic, the temperature in the reaction zone tends to rise as the reaction step of the cycle proceeds. It is often desirable to recover the significant quantity of heat generated during the process. This can be conveniently accomplished by including thermal ballast in the system. The ballast may be, for example, in the form of particles of materials having high thermal conductivities. The high thermal conductivity material may be mixed with the oxygen-selective-adsorbent, or it may comprise an independent layer upstream and/or downstream of the layer of the oxygen-selective adsorbent material. In the latter alternative it is often desirable to position the layer of high thermal conductivity material on the downstream side of the oxygen-selective-adsorbent with respect to the direction of flow of gas through the reaction vessel during the partial oxidation step of the process. The reason for this is that heat can be captured from the hot gases leaving the reaction zone after the partial oxidation reaction. This serves the dual purpose of cooling the product gas stream and storing heat for use in heating air being fed into the reaction zone during the following adsorption step of the process. To this end it may be preferable to operate the system in a manner such that fresh air feed and hot product gas flow through the reaction vessel in 10 opposite directions relative to each other. When this counterflow arrangement is loll employed it may be preferable to position the layer of high thermal conductivity :material at the air inlet end (hot reaction gas outlet end) of the reaction vessel so that the hot gases exiting the reaction zone heat the high conductivity material just prior to the passage of feed air through the high thermal conductivity material 15 during the next succeeding adsorption step of the process.
The pressure at which the adsorption step of the process is carried out is a matter of choice and not critical. In general, this step is usually carried out at a pressure at or above about 1 bar, absolute (bara). High pressures are generally preferred over low pressures because the adsorbent has a greater capacity for oxygen at high pressures. The minimum pressure at which the adsorption step is carried out is preferably about 0.5 bara and is most preferably about 5 bara. The upper pressure limit of the adsorption step of the process is determined by economics and limitations of the reaction system and, in general, this step is desirably carried out at absolute pressures not in excess of about 50 bara, is preferably carried out at pressures not in excess of about 20 bara, and is most preferably carried out at pressures not in excess of about 15 bara.
11 The pressure at which the partial oxidation step is carried out is likewise a matter of choice and not critical. It is convenient to carry out the partial oxidation step at or below the pressure at which the adsorption step is carried out.
It may be desirable to include a purge or evacuation step between the adsorption step and the partial oxidation step to remove from the reaction vessel any residual gas components that it is not desired to include in the partial oxidation step product stream. For instance, when the oxidant feed to the system is air, it may be desirable to discharge residual nitrogen from the reaction chamber to avoid diluting the partial oxidation reaction gas product stream with nitrogen. This 10 can be accomplished, for example, by purging the reaction chamber with a gaseous substance that is compatible with the partial oxidation product gas. By "compatible" is meant that the purge gas will be consumed during the partial oxidation reaction, or that it is easily separable from the product gas or that the presence of the purge gas in the reaction product gas is not objectionable with respect to the intended use or further processing of the product gas. Suitable purge gases include substantially pure oxygen, steam and carbon dioxide. When oxygen is used as the purge gas, it may be obtained from, for example, another adsorption/reaction vessel of the system that is undergoing its adsorption step, or from storage.
As an alternative to purging, or in addition to purging, the reaction chamber can be evacuated upon completion of the adsorption step of the process. If the reaction chamber is evacuated between the oxygen adsorption step and the partial oxidation reaction step, it is preferred to avoid conducting the evacuation step to the extent that significant quantities of sorbed oxygen are desorbed from the adsorbent, since this reduces the overall efficiency of the process. When evacuation is carried out at this stage of the process, the pressure in the reaction chamber is preferably not reduced to below about 0.5 bara, and is most preferably not reduced to pressures below about 1 bara. Any suitable gas pumping means, such as a vacuum pump can be used for this step of the process.
It may also be desirable to include an evacuation step and/or a purge step after the partial oxidation step of the process but before the adsorption step of the next succeeding cycle to recover or remove any product gas remaining in the reaction chamber after the partial oxidation step. This can be accomplished by evacuating the reaction chamber with the same or different gas pumping means that is used for the post adsorption step evacuation step. This evacuation step can be carried out to any desired pressure. For example, the pressure can be 10 reduced to about 0.1 bara or lower, but, for economic purposes, it is preferably .ooo 0 not reduced to below about 0.2 bara at this stage of the process. Alternatively to, or in addition to, evacuation, residual product gas remaining in the reaction vessel upon completion of the partial oxidation reaction step can be at least partially removed from the vessel by purging the reaction vessel with a suitable gaseous substance, such as carbon dioxide or steam.
In a variation of the partial oxidation reaction described above, water, preferably in the form of steam, carbon dioxide or both of these can be passed through the reaction zone with the hydrocarbon. In this variation, steam- or carbon dioxidereforming of the hydrocarbon occurs in addition to partial oxidation of the hydrocarbon. The steam and/or carbon dioxide reforming reaction can take place even after substantially all of the sorbed oxygen is consumed by the partial oxidation reaction. Since the partial oxidation reaction is highly exothermic and the reforming reaction is endothermic, the reforming reaction may also serve the useful function of moderating the temperature in the reaction zone. On the other hand, it may be desirable or necessary in some cases to provide supplemental heat to the reaction zone to compensate for heat consumed in the reforming reaction. Supplemental heat can be provided by any suitable means, such as by the use of heaters.
13 If desired, the partial oxidation step of the process can be used to produce partial oxidation products other than carbon monoxide and hydrogen. This can be accomplished by including in the reaction chamber a catalyst which promotes the desired partial oxidation reaction and using the appropriate hydrocarbon as the feed stream. Typical of such partial oxidation product manufacturing processes are: 1. The manufacture of cyclic anhydrides by the reaction of aromatic compounds or straight-chained C4 hydrocarbons with oxygen in the presence of a vanadium-based catalyst. Examples include the production of maleic anhydride 10 by the reaction of benzene or a saturated or unsaturated C4 hydrocarbon such as butane or butene with oxygen and the manufacture of phthalic anhydride by the reaction of p-xylene or naphthalene with oxygen.
2. The manufacture of alkylene oxides by the reaction of lower alkanes or alkenes with oxygen in the presence of a silver oxide catalyst supported on silica .is 15 or alumina or mixed molten nitrate salts. An example is the reaction of propane or propylene with oxygen in the presence of molten sodium and potassium nitrates to produce propylene oxide.
so 3. The manufacture of chlorinated hydrocarbons by the reaction of lower alkanes or alkenes with oxygen and hydrogen chloride or chlorine in the presence of a copper chloride catalyst supported on silica or alumina. Examples include the reaction of ethylene or ethane with oxygen and hydrogen chloride or chlorine to produce vinyl chloride or ethylene dichloride.
4. The manufacture of aldehydes by the reaction of lower alkanes or alkenes with oxygen in the presence of various metal halides or metal oxide catalysts.
Examples include the production of acetaldehyde by the reaction of ethylene with oxygen in the presence of copper chloride and palladium chloride, and the 14 manufacture of acrolein by the reaction of propane or propylene with oxygen over a molybdenum-bismuth-iron catalyst.
The manufacture of olefinically unsaturated nitriles by the reaction of lower alkanes or alkenes with oxygen and ammonia in the presence of a bismuth molybdenum oxide catalyst or an iron antimony oxide catalyst supported on silica or alumina. Examples of this type of process include the production of acrylonitrile by the reaction of propane or propylene with oxygen and ammonia and the production of methacrylonitrile by the reaction of i-butane or i-butylene with oxygen and ammonia.
o 10 The oxygen-containing gas may be air, oxygen-enriched air, or other oxygeninert gas mixtures. By oxygen-enriched air is meant air that contains more oxygen than is naturally present in air. Oxygen-inert gas mixtures include 0 oxygen-nitrogen mixtures, oxygen-argon mixtures, oxygen-carbon dioxide mixtures, etc. The most preferred oxidant for use in the invention is air.
15 The particular hydrocarbon or hydrocarbons used as reactant in the hydrocarbon partial oxidation step of the process of the invention is a matter of choice. When the partial oxidation process is used to simply produce hydrogen and carbon monoxide, the hydrocarbon used as feed may be any aliphatic, cycloaliphatic or aromatic hydrocarbon having 1 to 12 or more carbon atoms, and it may be saturated or ethylenically unsaturated and straight chain or branched chain.
Preferred hydrocarbons are the aliphatic hydrocarbons having 1 to 6 carbon atoms, and more preferred hydrocarbon feeds are comprised of one or more hydrocarbons having 1 to 4 carbon atoms. Typical of suitable hydrocarbon feed substances are methane, ethane, propane, the butanes, benzene, the xylenes, refined petroleum fractions, such as naphtha and gasoline, etc. Preferred hydrocarbon feeds include methane, ethane, ethene, propane, propene and the C4 hydrocarbons. Most preferred hydrocarbon feeds for the production of hydrogen and carbon monoxide by the process of the invention are methane and natural gas.
When the partial oxidation process is used to produce compounds other than hydrogen and carbon monoxide, the feed hydrocarbon may be one or more aromatic, aliphatic or cycloaliphatic compounds, and it may be saturated or ethylenically unsaturated and straight chain or branched. Suitable aromatic hydrocarbons include those having up to twelve or more carbon atoms and suitable aliphatic and cycloaliphatic hydrocarbons include those having two to twelve or more carbon atoms. Preferred aromatic hydrocarbons are those o having six to ten carbon atoms, such as benzene, the xylenes and naphthalene, and preferred aliphatic hydrocarbons are the saturated or ethylenically unsaturated straight-chain hydrocarbons having two to six hydrocarbon atoms, such as ethane, ethene, propane, propylene, n-butane, i-butane, n-butylene, Ibutylene, butadiene,.and the pentanes, pentenes, hexanes and hexenes.
15 The invention can be more easily understood by reference to the appended drawing, considered in conjunction with the following description. Equipment that is not necessary for an understanding of the invention, such as auxiliary valves, pumps, storage vessels and pumps, have not been included in the illustrated system.
Turning now to the drawing, illustrated therein is a two vessel partial oxidation system containing a pair of reaction vessels, A and B, arranged in parallel.
Vessels A and B are packed with a particulate adsorbent of the type described above, for example a perovskite ceramic material of the type described above. At the inlet end, the system is provided with air feed line 2, which is connected to manifold 4. Manifold 4 can be put into fluid communication with reaction vessel feed lines 10 and 12 via valves 6 and 8, respectively. Lines 10 and 12 are connected to the inlet end of reaction vessels A and B, respectively. The inlet 16 end of the system is also provided with hydrocarbon feed line 14, which is attached to manifold 16 at a point between valves 18 and 20, also provided in manifold 16. Manifold 16 can be put into fluid communication with lines 10 and 12 via valves 18 and 20, respectively. Purge gas inlet line 22 is connected to manifold 24, which, in turn, communicates with lines 10 and 12 via valves 26 and 28, which are located in manifold 24.
On their outlet ends, vessels A and B are connected to lines 30 and 32, **respectively. Lines 30 and 32 are connected to manifold 34, and flow to manifold 34 from lines 30 and 32 is provided by valves 36 and 38, which are attached to go.
o. 10 manifold 34. Also attached to manifold 34, at a point between valves 36 and 38, eig.
is nitrogen gas discharge line 40. Lines 30 and 32 can be put into fluid go: communication with manifold 42 through valves 44 and 46, respectively, which are positioned in manifold 48. Manifold 48 is connected to partial oxidation reaction product gas line 48 at a point between valves 44 and 46. Additionally go.
attached to lines 30 and 32 is manifold 50. Flow to manifold 50 from lines 30 and 32 is provided by valves 52 and 54, respectively, which are positioned in manifold 50. Purge gas discharge line 56 is connected to manifold 50 at a point between valves 52 and 54.
g The system illustrated in the drawing is designed to be operated in semicontinuous fashion, with reactors A and B being operated 1800 out of phase, so that reactor A is in oxygen adsorption service while reactor B is in partial oxidation reaction service, and vice versa. The process of the invention, as carried out in the system illustrated in the drawing, will be described as a twostage process comprising a first stage, in which reactor A is in oxygen adsorption mode and reactor B is in partial oxidation reaction mode, and a second stage, in which reactor B is in adsorption mode and reactor A is in partial oxidation mode.
17 At the beginning of the first stage, valves 6, 20, 36 and 46 are open and all other valves are closed. Air, introduced into the system through line 2, passes through line 10 and enters vessel A. The air may be blown into the system by means of a compressor, a blower, or other gas pumping means positioned in line 2. An air drying step is not ordinarily necessary or desirable in the process of the invention, since only oxygen will be adsorbed by the oxygen-selective adsorbent.
Moisture and other impurities, such as carbon dioxide, will be discharged from the system with the nonadsorbed waste gas stream.
During the adsorption stage of the process the adsorbent in vessel A is maintained at a temperature in the range of about 600 to about 14000 C. Initial .**.*heating of the adsorbent can be accomplished by heating the feed air before it .enters vessel A or by heating the adsorbent in vessel A. Heating of the feed air or adsorbent can be accomplished by any suitable means, such as by means of .extemal heating devices. When it is desired to heat the adsorbent in addition to or instead of heating the incoming air, this can be accomplished by suitable method, such as by use of electric heating means, by incorporating the reaction zone in a furnace zone or by combusting fuel and passing the hot combustion gases through the reaction zone prior to introduction of air thereinto. The method used to heat the adsorbent in reaction vessels A and B is a matter of choice and forms no part of this invention.
Once the adsorbent in vessels A and B reaches the desired reaction temperature, it is generally not necessary to continue applying heat to the reaction zone to maintain the adsorbent at the desired adsorption and partial oxidation reaction temperature since the heat of adsorption during the oxygen adsorption step and the heat of combustion during the partial oxidation step is adequate to accomplish this. Distribution of heat in the reaction zone can, if desired, be facilitated by incorporating a material having a high thermal conductivity into the reaction zone. As mentioned above, this can be 18 accomplished mixing or sandwiching, i. e. layering, the oxygen-selective adsorbent with a high temperature stable material, such as a heat conducting ceramic material or a particulate metal material. Heat flow in the reaction zone can also be accomplished by inserting strips or rods of metallic material in, upstream or downstream of the reaction zones. If it is desirable or necessary to remove heat from the reaction zone to prevent excessive heating of the adsorbent contained therein, this can be accomplished by means of the abovedescribed heat transmission means.
•*oo In any event, the air feedstream entering vessel A passes upwardly through the adsorbent contained therein, and as it does so oxygen is adsorbed by the adsorbent. Nonadsorbed gas, comprised substantially of nitrogen and argon when air is the feed, leaves vessel A through line 30 and passes out of the system through manifold 34 and line 40. The nitrogen may be collected as a •byproduct gas stream, or it can be discharged to the atmosphere. As the adsorption step proceeds in vessel A, the adsorbed oxygen forms a front which advances through the bed of adsorbent toward the nonadsorbed product outlet S• end of vessel A.
While the oxygen adsorption step is taking place in vessel A the partial oxidation step is initiated and carried on in vessel B. During this stage of the cycle, a hydrocarbon gas, such as methane or natural gas, is introduced into vessel B through lines 14 and 12. If desired, the hydrocarbon feed may be compressed to the desired-pressure by any suitable means, such as by a compressor or gas blower, or the gas may be provided from its source as a pressurized gas stream.
As the hydrocarbon gas contacts the hot adsorbent in vessel B, it reacts with the oxygen sorbed onto the adsorbent to produce the desired partial oxidation gas product, which is generally a mixture of hydrogen and carbon monoxide. The product gas stream may also contain other gaseous by-products, such as carbon dioxide and moisture, but the concentration of these by-products can be 19 minimized by maintaining optimum reaction conditions in the reaction vessel. The hot reaction gases pass out of vessel B through lines 32 and 48 and they pass, for example, to storage or downstream processing units. As the partial oxidation reaction progresses in vessel B, the adsorbent in this vessel is regenerated by removal of the sorbed oxygen therefrom.
At a predetermined point in the first stage of the process, such as when the adsorbed oxygen front reaches a desired point in vessel A, or when all of the oxygen in vessel B is reacted with hydrocarbon, the first stage of the cycle is •Oil terminated and the second stage begins. By proper sizing of the reaction vessels and careful control of the reactant gas flow rates, etc., the process. can be designed so that the adsorption step in vessel A reaches its desired end point at substantially the same time that all of the sorbed oxygen in vessel B is reacted.
Alternatively, if the adsorption step in vessel A reaches its desired end point •before the oxygen in vessel B is completely reacted, or vice versa, the completed part of the first stage of the process can be terminated and further activity in that vessel can be suspended until the other part of the first stage reaches its desired end point.
Upon completion of the first stage of the process, the second stage is begun.
During the second stage valves 8, 18, 38 and 44 are open and all other valves are closed. Air, introduced into the system through line 2, now passes through line 12 and enters vessel B. As the air passes through vessel B, oxygen is adsorbed by the regenerated perovskite adsorbent in this vessel. Nonadsorbed gas now passes out of vessel B through line 32 and leaves the system through line 40. Meanwhile, the partial oxidation step is initiated and carried on in vessel A. During this stage of the cycle, hydrocarbon gas is introduced into vessel A through lines 14 and 10. As the hydrocarbon gas contacts the hot adsorbent in vessel A, it reacts with the oxygen sorbed onto the perovskite adsorbent to produce the desired partial oxidation gas product The hot reaction gases pass out of vessel A through line 30 and passes out of the system through line 48.
When the desired stage 2 end point is reached, the second stage of the process (and the current cycle) ends and the next cycle begins with vessel A in oxygen adsorption mode and vessel B in partial oxidation reaction mode.
To increase the overall efficiency of the process of the invention, it may be .**desirable to include a step for removing residual nonadsorbed gas component from the vessel undergoing oxygen following completion of this step. This can be accomplished in the manner described above, by purging the vessel completing its adsorption step with a gas that is compatible with the partial oxidation reaction product gas, such as oxygen, steam or carbon dioxide, or by evacuating the vessel to desired extent without significantly desorbing oxygen from the adsorbent. It can be appreciated that evacuating the vessel and/or purging the vessel with steam and/or carbon dioxide is usually preferable to purging the 15 vessel with oxygen, since these methods avoid the necessity of supplying pure .oxygen to the system.
In any event, if it is desired to purge the reaction vessel completing its adsorption step, this can be accomplished by closing the relevant valves in manifolds 4 and 34 and opening the relevant valves in manifolds 24 and 50. For example, when it is desired to purge vessel A upon completion of its oxygen adsorption step, purging of vessel A can be accomplished by closing valves 6 and 36 and opening valves 26 and 44; and when it is desired to purge vessel B upon completion of its oxygen adsorption step, purging of vessel B can be accomplished by closing valves 8 and 38 and opening valves 28 and 46. The duration of the cycle can be adjusted as necessary or desired to balance operation of the steps taking place in each reaction vessel.
When it is desired to evacuate the vessel completing its adsorption step, this can be accomplished by providing a gas pumping means, such as a vacuum pump, in line 40 to remove residual nonadsorbed gas from that vessel. As indicated above, this is the desired alternative. As an alternative, both oxygen purging and vessel evacuation can be carried out, if desired. When only evacuation of the vessel completing its oxygen adsorption step is to be carried out, manifolds 24 and 50 and the valves associated with these manifolds can be eliminated from •the system.
l* *I It may also be desirable to conduct evacuation of the vessel completing its partial oxidation step of the process. This can be accomplished by providing a gas pumping means, such as a vacuum pump, in line 48. Evacuation of the vessel in which the partial oxidation step is taking place can be carried out during and/or upon completion of the partial oxidation step.
"In a more preferred embodiment of the invention, both evacuation of the vessel 15 undergoing or completing its adsorption step and evacuation of the vessel undergoing or completing its partial oxidation step are carried out. This can be conveniently carried out by evacuating both vessels simultaneously during or upon completion of the adsorption step and partial oxidation step taking place in the vessels. In this case, when a two vessel system is used for practice of the process, two gas pumping means are required.
It will be appreciated that it is within the scope of the present invention to utilize conventional equipment to monitor and automatically regulate the flow of gases within the system so that it can be fully automated to run continuously in an efficient manner.
The invention is further illustrated by the following example in which, unless otherwise indicated, parts, percentages and ratios are on a volume basis.
An alumina tube reactor 22 inches long and having an outside diameter of 0.25 was packed with 1.67 g of La 08 Sr0.2Co0.
5 Fe0.50 perovskite particulate ceramic material having a particle size of about 50 microns. The reactor was heated to 900 C by means of a tubular electric furnace. Air was then passed through the -o.reactor at a flow rate of 50 ml/min(STP) for about 10 minutes. Oxygen S adsorption was monitored during this step by recording oxygen breakthrough.
Following this step, a gas stream containing 20% methane and 80% nitrogen was passed through the reactor for a period of 20 minutes at a flow rate of o ml(STP)/min while maintaining the temperature in the reactor at about 9000 C.
Some carbon dioxide was produced during the first 2 minutes of the reaction period; however, over the entire reaction period, the average methane conversion was greater than 95% and the selectivity for hydrogen and carbon monoxide was greater than 80%. The average formation rates for hydrogen 15 and carbon monoxide were respectively 526 Lmol/min/g and 235 Vmol/min/g.
Carbon dioxide and higher hydrocarbons were produced in relatively small amounts.
This example illustrates that methane can be reacted with adsorbed oxygen on a perovskite adsorbent at an elevated temperature to produce hydrogen and carbon monoxide as principal reaction products.
Although the invention has been described with particular reference to specific equipment arrangements and to a specific experiment, these features are merely exemplary of the invention and variations are contemplated. For example, the process can be carried out in multiple vessel systems comprising three or more vessels operated, for example, out of phase. Additionally, as noted above, the direction of hydrocarbon flow through the reaction vessels can be countercurrent 23 to the direction of flow of air through the vessels. For instance, in the system illustrated in the appended drawing, hydrocarbon gas can be introduced into the system through line 48, flow downwardly through vessels A and B, and exit the system through line 14 As another alternative to the above-described process, the invention can be practiced by conducting the hydrocarbon partial oxidation step in the liquid phase. The scope of the invention is limited only by the breadth of the appended claims.
1. A process for producing hydrogen and carbon monoxide by the partial oxidation of at least one hydrocarbon comprising the steps: passing an oxygen-containing gas at a temperature in the range of about 300 to about 14000 C through at least one reaction zone containing an oxygen-selective mixed conductor at an absolute pressure in the range of about 0.5 to about 50 bara, thereby preferentially retaining said oxygen in said mixed conductor; and passing said at least one hydrocarbon through said at least one reaction zone at a temperature in the range of about 300 to 1400' C, thereby contacting said mixed conductor retaining oxygen and reacting to produce a product gas comprising hydrogen, carbon monoxide or mixtures of these.
4. The process of claim 3, wherein x varies from about 0.1 to 1. oooo o.o The process of claim 3, wherein A is La, Y or mixtures of these.
6. The process of claim 3, wherein M is Sr, Ca or mixtures of these.
8. The process of claim 4, wherein A is La, Y or mixtures of these, M is Sr, 5 Ca or mixtures of these and B is Co, Fe or mixtures of these.
9. The process of claim 8, wherein xis 0.2 to 1 loll The process of claim 2, wherein said oxygen-selective mixed conductor is V *a ceramic substance of said ceramic substance being doped with a rare earth metal oxide selected from the group consisting of Y203, Nb 2 0 3 Sm 2 0 3 Gd 2 0 3 and mixtures of these.
11. The process of claim 1, claim 2 or claim 3, wherein said oxygen- containing gas is air.
12. The process of claim 11, further comprising, between steps and the additional step comprising: purging said at least one reaction zone with gas that is compatible with said product gas, depressurizing said at least one reaction zone, or both purging said at least one reaction zone with gas that is compatible with said product gas and depressurizing said at least one reaction zone.
13. The process of claim 12, wherein the purge gas is oxygen, steam, carbon dioxide or mixtures of these.
14. The process of claim 11, further comprising, after step removing said product gas from said at least one reaction zone by: purging said at least one reaction zone with steam, carbon dioxide, nitrogen, argon, helium or mixtures of p a these, depressurizing said at least one reaction zone, or both purging said at least one reaction zone with steam, carbon dioxide, nitrogen, argon, helium or mixtures of these and depressurizing said at least one reaction zone. The process of claim 11, wherein said at least one hydrocarbon has an aliphatic, cycloaliphatic or aromatic structure and it contains 1 to 12 carbon atoms.
16. The process of claim 15, carried out at a temperature in the range of about 600 to about 12000 C.
17. The process of claim 16, wherein step is carried out at an absolute pressure in the range of about 0.5 to 20 bara.
18. The process of claim 17, wherein said at least one hydrocarbon contains 1 to 6 carbon atoms.
19. The process of claim 18, carried out about 750 to about 11000 C.
20. The process of claim 19, wherein comprises methane.
21. The process of claim 20, wherein comprises natural gas.
24. The process of claim 11, wherein said at least one reaction zone contains particulate material having a thermal conductivity greater than that of said oxygen- selective mixed conductor. The process of claim 24, wherein said particulate material is mixed with said oxygen-selective mixed conductor.
26. The process of claim 24, wherein said particulate material is placed upstream, downstream or both upstream and downstream of said oxygen-selective mixed conductor.
27. The process of claim 11, wherein said reaction zone additionally contains a catalyst selective for partial oxidation reactions.
28. The process of claim 27, wherein said catalyst is deposited on said oxygen- selective mixed conductor.
29. The process of claim 11, further comprising, during step passing a moderating agent selected from stream, carbon dioxide and mixtures thereof through said at least one reaction zone. The process of claim 29, wherein said moderating agent is stream.
31. The process of claim 11, further comprising repeatedly performing steps (a) and in sequence in said at least one reaction zone. 000. 00° 32. Apparatus for the partial oxidation of hydrocarbons comprising: at least one reaction zone containing an oxygen-selective mixed conductor; sequential means for introducing oxygen-containing gas into said at least one reaction zone; °°°oo sequential means for introducing hydrocarbon feed into said at lest one reaction zone; -28- sequential means for removing a product stream from said at least one reaction zone.
34. The apparatus of claim 33, further comprising: means of heating said oxygen-containing gas: means for heating said at least one reaction zone; or (c) means for heating said oxygen-containing gas and said at least one reaction zone. The apparatus of claim 34, wherein said oxygen-selective mixed conductor is a S perovskite substance.
36. The apparatus of claim 35, wherein x varies from about 0.1 to 1. i 37. The apparatus of claim 36, wherein A is the La, Y or mixtures of these.
38. The apparatus of claim 36, wherein M is Sr, Ca or mixtures of these.
39. The apparatus of claim 36, wherein B is Co, Fe or mixtures of these. o -29- The apparatus of claim 36, wherein A is La, Y or mixtures of these, M is Sr, Ca or mixtures of these and B is Co, Fe or mixtures of these.
41. The apparatus of claim 40, wherein x is 0.2 to 1.
42. The apparatus of claim 34, wherein said oxygen-selective mixed conductor is a ceramic substance of said ceramic substance being doped with a rare earth metal oxide selected from the group consisting of Y 2 0 3 Nb 2 0 3 Sm 2 0 3 Gd 2 03 and mixtures ofthese.
43. The apparatus of any one of claims 32 to 34, wherein said oxygen-containing gas is air.
44. The apparatus of claim 43, wherein said hydrocarbon contains 1-12 carbon atoms. The apparatus of claim 44, wherein said hydrocarbon is gaseous.
46. Hydrogen and carbon monoxide when produced by a process according to any one of claims 1 to 31.
47. A process for producing hydrogen and carbon monoxide, substantially as herein 15 described with reference to any one of the embodiments of the invention illustrated in the accompanying example.
MX2016005700A (en) 2013-11-06 2016-08-12 WATT Fuel Cell Corp Chemical reactor with manifold for management of a flow of gaseous reaction medium thereto.
FR3020356A1 (en) * 2014-04-29 2015-10-30 Univ Lille Sciences Tech dry reforming process of at least one alkane.


This is my tree. There are many like it, but this one is mine.
There are certain things that you learn to live without in my line of work. I miss some of them more than others. I love art, live music, and the feeling of my gigantic bed with my down comforter on top of it. But of all the things that are kept from me in this wonderful country, I miss great food the most. Don't get me wrong an MRE (Meals Ready to Eat) is delicious cuisine. Still, after being on a mission for a week, then killing myself in a two hour workout that results in bleeding shins and locals running away from me because they think I am a white American demon brought to Earth to throw anything he can pick up and jump on anything he MIGHT be able to clear…well…a huge pile of Penang Curry would go a long way.
This leads me to the latest instance where everyone I'm co-located with reaffirmed their already pre-existing belief that I am truly insane. We had just finished a three-day firefight that, in short, sucked worse than that movie where John Travolta plays a girl.
However, as we were leaving this God forsaken valley I looked over and saw what I can only describe as one of the most beautiful things my eyes had ever beheld. There before me was a pomegranate tree. This wasn't just any tree, this tree was green – really green – and let's just say there aren't a whole lot of living plants where I am working right now.
So there it is, in all its splendor, looking at me with its little green eyes, pretty much just pleading for someone to love it – to enjoy the fruit already waiting on it's branches. There was no other course of action. I had to have it. I decided we (as in my entire team) were going to stop and transplant this gift from God away from this valley of murderers to my FOB (forward operating base). And that is exactly what we did. Yes, I was berated by my fellow soldiers who thought getting out of our vehicles at this juncture was near suicide, but I kept my eye on the prize. I knew that there was a greater good that had to be accomplished.
It didn't take long for the story of my tree to spread. I wake up every morning, I walk over to MY pomegranate tree, water it, and check the fruits of my labor (pun intended). I have in the past few weeks enjoyed some of the most delicious arils my mouth has ever tasted. In case you don't know, I'm from CA. The pomegranate is not indigenous to CA, but has been there long enough for me to claim it as a CA fruit. They're a little taste of home. MY tree is outside my hut, and the unspoken rule is very clear – no one gets near it. I'm a pretty amicable guy outside the cage, but touch my tree and it will bring you a certain and painful death.
I don't have a nutritionist. I don't have a physical trainer. I don't have a million dollar MMA facility. So I make up for it with extreme violence (sometimes taken out on inanimate objects), some creative workout plans, and now a pomegranate or two. My tree is just the latest of my eccentricities that concern my fellow mates. On most missions I wear a hat with a big fat peace sign emblazoned on it. I'm not trying to do the Full Metal Jacket "duality of man" thing – seriously, you can ask my wife. I just like the hat. The pomegranate tree, the peace sign hat, and my love of "classic" 80s tunes is the trifecta that makes me the weirdest guy in country. We might be rolling onto a target, and out of my vehicle someone just might hear some classic Prince, or perhaps even Madonna.
If I were a bad guy and I looked out my window and beheld a bunch of dudes who look like I look (220lbs, beard, way too many guns for a single person, and one of them in a peace sign hat) rolling into my hood, and they were listening to Duran Duran while they ate pomegranates, I would pretty much surrender right there and then. Either that, or I would decide that this group of infidels wasn't worth the effort and explosives it would take to blow up…plus then I'd have to run away before more of them showed up…and its hot outside today…I really don't want to get all sweaty and sandy for these guys do I?
Anyway, assuming I don't get blown up, shot, or otherwise made dead, I will be back in the good old USA soon, and I am fired up about it. For the first time since 2001, I will be fighting full time. Being a special operations soldier and being a professional fighter at the same time might sound like an easy gig, but I assure you it isn't. Now I have my green light. I have been told to get as good as I can and win every title I can.
My new mission is to be the best fighter in the world. You've heard this from a lot of guys, so I know it might ring hollow, but I now have total clarity and total focus on the task ahead of me, and I'm not big on failure.
My future opponents have something to fear. I will be spending every waking moment with the best guys in the industry. They are going to have to lock me out of the gym. I'm not going to be taking for granted the fact that I now have real mats and rings to train with. I won't be taking a fight only days after graduating Ranger School. I'll be 100% ready and focused. Even worse for that next opponent, he will have to deal with me imagining that he just stole my last pomegranate. It might seem funny to some of you, but when you have been deployed where I've been and seen what I've seen you realize a single piece of fruit is a really big deal…and that guy across the cage just took mine.


MINSK, 4 August (BelTA) – Belarus' Council of Ministers approved the national export promotion program for 2016-2020 and a roadmap for its implementation. It is envisaged in Decree No.604 of 1 August 2016, BelTA learnt from the press service of the Belarusian government.
"The national program does not provide a detailed forecast for external trade in 2016-2020 but spells out concrete measures to promote exports with an ultimate target to diversify and increase the export turnover," the press service explained.
The program is aimed at the growth, development and diversification of the national export, first of all, innovative and high-technology exports, enhancement of the efficiency of the government support for export promotion. The implementation of the roadmap events will increase the volume of high-value exports, modern materials and complete products with improved features, further develop the export of technically and technologically-intensive products, and also increase the export of high-tech and intellectual services (engineering, technical, computer and education).
The achievement of the main targets of the program as well as the creation of favorable conditions for the implementation of the second stage (2021-2030) of Belarus' sustainable social and economic development strategy through 2030 will help secure systemic export diversification for an equal distribution of exports between third markets: EEU, EU and other states, including the countries of Asia and Oceania, Africa and Middle East, Latin America (by 2020 it should represent a one third-one third-one third correlation).
The exports of goods to new promising markets are expected to account for 10% of the total exports by 2020.
Among the main goals of the program is the diversification of trade and economic ties with various countries and regions alongside with preserving and strengthening positions on traditional markets; optimization of laws in the export promotion area taking into account the world's best practices and the operation of the Belarusian economic model; improvement of approaches to the work with small and medium-sized enterprises in the exports matter; encouragement of goods and services producers to expand their product and service portfolio. The program also envisages the development of conditions to stimulate non-primary exports as well as high-technology and innovative exports of goods and services; further economic integration within the EEU which envisages the removal of barriers, restrictions and withdrawals in the trade of certain products and services, first of all in respect to energy resources, goods for assembly plants, liberalization of highway transportation operations and other matters. The program also stipulates the development of cooperation with regional associations, international economic organizations, export culture promotion.
Under the program, in 2016-2020 the export of goods and services is expected to increase 1.21-1.25 times, while the growth of exports shall outpace the growth of imports by at least 65% of produced industrial products. The export of goods to new promising markets is to go up from 5.8% of the total exports in 2015 to 10% in 2020. The export of services will account for 25% of the total exports in goods and services in 2020.
In order to strengthen the export potential of the country more efforts will be put in for further development of areas important for Belarus' economic integration with the world economy such as the development of the common restriction and withdrawal-free market in the EEU, liberalization of services and capital markets, development of the common financial market, harmonization of the national legislation of the EEU member states and the improvement of the EEU general legislation. Besides, the program envisages further work on Belarus' accession to the World Trade Organization with the observance of the national economic interests and expansion of cooperation within other international organizations; expansion of multilateral cooperation with the countries of the EU and the USA; further intensification of trade and economic ties with promising countries, and also with the states of Southeast Asia, Middle East, Africa and Latin America. Measures will be taken to boost the export of services; advance the national capital to world markets, inclusion to international transnational corporations and development of new transnational corporations to secure a new level of labor productivity and environmental security.
The program is coordinated by the Belarusian Ministry of Foreign Affairs. Among the program executors are national government bodies and other state organizations, local executive and regulatory bodies.


text:
Home English Indian Sugar News India will continue to export about 60-70 lakh tonnes of sugar during...
India will continue to export about 60-70 lakh tonnes of sugar during 2020-21 season: ISMA
According to the Indian Sugar Mills Association (ISMA), with an opening balance as on 1st Oct. 2019 of 145 lakh tonnes, estimated sugar production for the current season 2019-20 of around 272 lakh tonnes, expected domestic sales of around 250 lakh tonnes and exports of around 52 lakh tonnes during the season, the opening stocks as on 1st Oct, 2020, is estimated to be around 115 lakh tonnes.
The OB of about 115 lakh tonnes on 1st Oct. 2020, will be 30 lakh tonnes less than the opening stock as on 1st Oct 2019. The OB for 2020-21 of the 115 lakh tonnes is however, about 65 lakh tonnes more than the domestic requirement for the initial months of next season, till when new season's sugar does not get fully available in the market. Since we expect much higher production in 2020-21 SS, India will continue to export about 60-70 lakh tonnes of the surplus sugar out of the country during 2020-21 SS. With Thailand's sugar production to further fall in next season, beyond the 60 lakh tonnes fall in current season, there is an opportunity for India to export sugar to Asian countries.
The ex-mill sugar prices which had fallen to around Rs.31-31.50 per kilo during the lockdown due to drop in domestic sales, have improved quite significantly to close to the levels seen before the lockdown was announced, at around Rs.32-33.50 per kilo now.
Demand for sugar had also fallen during the lockdown from end of March, but as was expected the demand has picked up again from end of May. Thanks to the major relaxations in the lockdown and the summer demand coming up, the sugar offtake seems to have reached normal levels.
Similarly, thanks to the pro-active steps taken by the OMCs and cooperation extended by ethanol suppliers during the last 2-3 months, the ethanol offtake, which could have been majorly impacted due to drop in sales of petrol and lakh of storage capacities in some depots of OMCs, has been almost normal. The OMCs took prompt action to relocate the supplies to alternate depots in other States, to ensure smooth ethanol offtake from the distilleries. As a result, against an annual supply contract of 170 crore litres for 2019-20 (Dec-Nov), 88 crore litres have already been supplied till 15th June 2020, i.e. almost 52% of contracted quantity has been supplied in the 6.5 months of the contract period. Ethanol blending in petrol for the country as a whole has therefore at 4.97% as upto 15th June 2020. This is despite the lower production of sugarcane and molasses due to drought in Maharashtra and Karnataka. The 3rd tender was floated for more ethanol on 1st June 2020, at the same prices decided by Government in July 2019, and the bids are expected to be opened soon, which will increase supplies.
https://storage.googleapis.com/stateless-chinimandi-com/2020/06/55d247eb-india-will-continue-to-export-about-60-70-lakh-tonnes.dom_.eng_.25.06.2020.02.34.mp3
To Listen to this News click on the play button.
Ethanol blending in Petrol
India sugar export
Indian Sugar Mills Association
Sugar Export
sugar export from india
Sugar season 2020-21

redpajama_set_name: RedPajamaCommonCrawl


text:
Q: Cant document enum with Doxygen I have the following code:
/**
 * \enum compare_str_stat
 * \brief String Comparison Member Function status.
 *
 * \var no_match explanation 1
 * \var match explanation 2
 * \var partial_match explanation 3
 */
enum compare_str_stat {
    no_match,       //!< String is not found
    match,          //!< Match has been found
    partial_match   //!< partial part
};

I am using Doxygen 1.8.6 and for some reason doxygen is not documenting the enum anywhere.  I cannot even find a mention of it.  I am trying to link to it with no luck.
Thanks...

A: Maybe you need to check your doxygen configuration: the Doxyfile
In Doxyfile, there is a tag:
EXTRACT_ALL            = YES

Check if you set it as NO.

redpajama_set_name: RedPajamaStackExchange


Providing support & encouragement for musical opportunities!
Welcome to the 2018-2019 Choir Year!
It was great to meet so many of you recently at Open House, and we hope it is only the beginning of your involvement this year in your students' musical lives. As promised, here's a grab bag of important info relevant to students in the choral program.
Boosters: Our choir boosters support the program through funding scholarships, organizing fundraisers, serving concessions at performances, and distributing spirit wear. The first booster meeting is tonight, Monday, September 10 at 7pm in the choir room, and all are welcome. We are actively seeking to grow the boosters, particularly with parents of freshmen and sophomores. Even if you choose not to attend monthly meetings regularly, support the boosters and the choirs by returning the attached membership form. Commitment is scalable, and we love keeping you in the loop.
Communication: Join our Choir Remind group by texting @dgsch to the number 81010. Here, we'll remind parents and students about concerts and call times and direct you to any important long-form communication (like this email!).
Concert Attire – Curricular Choirs (Freshman Girls Choir, Concert Choir, Treble Choir, A Cappella Choir): Start prepping now! For our October 11 concert students will wear robes – these hit about mid-calf. Under their robes, students should wear something presentable but cool – dress slacks and dress shirt, a dress, etc. The guideline here is that we should be able to tell you were in the concert even after you remove the robe. Students also need to wear black shoes. No sneakers, no boots, short or no heel. Any hair accessories (headbands, ribbons, etc.) should be neutral colors.
Concert Attire – Select Ensembles (Chamber Singers, Treble Ensemble, Madrigals): Students should be looking for information coming from their director soon, as some elements of attire vary with each group. That being said, we are moving to one ensemble dress for women this year (the same for each ensemble), which is $65, and students will also need black character shoes, which we purchase for $40. Madrigals and Chamber Singers guys will purchase attire through the school as well (tuxes and ties, respectively) – details and costs on these coming soon. Payment for all ensemble wear is due September 30. (Checks payable to DGS.) Scholarship is available for families in need; please let us know soon if this might be the case for you.
Voice Lessons: Your student has the opportunity to take voice lessons at school once each week during their choir class at a rate of $20-25, depending on the teacher. Spots are filling up very quickly, so if you meant to turn in the form and haven't yet, it is attached!
Thanks, always, for supporting your singer in the fine arts at DGS!
This entry was posted in Uncategorized by dgschoralboosters. Bookmark the permalink.


text:
In August 2019, an Oklahoma City area Burger King restaurant refused service to a customer because she is deaf. According to KFOR-TV, the customer, Rachel Hollis, complained that a Burger King employee told her that staff was "too busy" to fill her order. Burger King has fired the employee involved, according to Oklahoma City media reports.
A restaurant's refusal to provide service to a person with a disability because of the disability is discrimination pursuant to Title III of the Americans with Disabilities Act (ADA).
As KFOR-TV reports:
"Rachel Hollis says she was stopping to get food after taking her two sons to hockey practice.
'I had my order ready, I had it typed on my phone. I do that often when I go through drive-thrus, it hasn't ever been an issue,' Hollis told News 4 through an interpreter. 'I show him my order, and he gives me this face of frustration.'
Hollis says she started taking a video of the incident because she was feeling uneasy, then in the video you can see the employee hand her a note that says, 'Can't do a full order at the window. Too busy.'
Eventually, the employee comes back to the window and starts arguing with Hollis. 'You have to come inside. It's too busy. Too busy ma'am, I can't do a full order at the window I'm sorry,' the employee says to Hollis. 'It has nothing to do with your disability, I have a disability too.
After that, he slams the window shut.
Hollis says one of the worst parts about the whole experience was that it happened with her kids in the car. 'I could tell they knew something was going on, I was just trying to keep them calm,' Hollis said. 'I said I'll explain it to you when we get home. But they knew something was going on.'
Hollis says she tries to stay calm in that moment, but she's tired of people being treated that way.
'When I got home, that was when I really broke down. I was very upset, I was crying, I was very tired. I'm tired of discrimination,' Hollis told News 4 through an interpreter. 'I've never experienced anything like that, for someone to call the police. That's crazy, it just doesn't seem right.'"
After the incident, KFOR contacted Burger King's corporate offices for comments. Seeming to concede the truth of Hollis's complaint, Burger King provided a statement to the Oklahoma City television station. As KFOR reported:
"All guests should be treated with respect and provided with a high level of service at our restaurants. The restaurant owner has reached out to the guest and her family to apologize, the employee was terminated and all employees at the location will undergo additional sensitivity training to ensure our customers always feel welcomed."
KFOR posted online Hollis's recording of her interaction with the employee. In the recorded video, Hollis had a brief exchange with the employee. After the employee refused service, he closed the Burger King's drive through window and walked away.
Just days after her Burger King experience, Hollis announced that she would be suing Burger King for disability discrimination. A check of the docket for the U.S. District Court for the Western District of Oklahoma in Oklahoma City at the end of August revealed that a federal Americans with Disabilities Act had not yet been filed by Hollis.
According to Fox 6 News:
"Hollis, her attorney Cameron Spradling, and the Oklahoma Disability Law Center say the excuse was both unacceptable and illegal.
'You can't make them do something different in order to get those services,' Joy Turner from the Oklahoma Disability Law Center said.
They're now starting the process of filing a lawsuit, claiming the restaurant is 'failing the deaf community and ignoring the Americans with Disabilities Act…"
Fox added further reporting that the local Burger King employee called the police as Hollis waited for service in the drive through lane.
According to Fox6's reporting:
"Meanwhile, another employee calls the police.
'I have a lady that's stuck – sitting in my drive-thru and won't move,' the employee tells the 911 dispatcher. "She just pulled up to the window and my drive-thru is all the way wrapped around."
Later, the [Burger King employee] motions for Hollis to come inside… If this is a multibillion dollar international company how come they do not know better? Spradling said.
That's exactly what this pending litigation asks, pointing out that this particular location was part of the franchise's 'Burger King of Tomorrow' plan. Through this plan, the restaurant added a 'simplified ordering journey."
The [attorney's] letter also mentions the McDonald's across the street, which has a sign telling 'customers with speech or hearing difficulties to pull up for assistance.'
As for Hollis and her legal team, they're just hoping to serve justice. 'It's complete thoughtlessness,' Spradling said. Burger King told KFOR the employee in the video was fired and that specific restaurant is going through sensitivity training."
What does the law say?
Under ADA Title III, restaurants, hotels, and other public businesses are legally required to provide effective communicate for customers. Title III affords businesses some flexibility in deciding the type of communication to offer in given situations. The complexity of the transaction will inform the type of accommodation needed. For example, simply ordering food at a restaurant or cashing a check at a bank are typically not viewed as necessitating sign language interpretation, as determined by the federal courts and the U.S. Department of Justice.
According to U.S. Department of Justice Title III Guidance:
"Communicating successfully with customers is an essential part of doing business. When dealing with customers who are blind or have low vision, those who are deaf or hard of hearing, or those who have speech disabilities, many business owners and employees are not sure what to do. The ADA requires businesses to take steps necessary to communicate effectively with customers with vision, hearing, and speech disabilities.
Because the nature of communications differs from business to business, the rules allow for flexibility in determining effective communication solutions…. For example, a restaurant can put its menu on an audio cassette or a waiter can read it to a patron…. Usually a customer will tell you which format he or she needs. If not, it is appropriate to ask.
In-person sign language interpreters or Video Remote Interpreting typically will not be required in restaurant settings. In this case, Hollis attempted to communicate with Burger King by written note. If the employee had responded appropriately, in writing, without refusing service to Hollis, the written communication would likely have been legally appropriate here.
However, without such an appropriate interaction, Burger King now faces disability discrimination litigation in federal court.
The only probable "crime" was speaking Spanish	Bromberg & Associates: Celebrating 20 Years of Language Access in Metro Detroit and Beyond


Teens used to fill those jobs,college kids. In my little town there are next to no illegals, thank goodness. In other towns & cities all the fast food places are nearly all run by Mexicans, but here the teens & moms w/ kids in school do it for a few extra bucks, just as they always have.
If the costs to enforce our current immigration laws would be substantial, how will we enforce the proposed CIR which requires securing the border, biometrics for all illegals, thorough background checks, payment of back taxes (unless they affirm they owe none), and English skills? At least that's what the proponents of CIR would have us believe.
The Arizona law proves enforcement is indeed effective. We can't have laws that effectively reduce illegal immigration, now can we?
Data on health care costs for illegal immigrants are sketchy because hospitals and community health centers don't ask about patients' legal status. In California, a 2004 study by the Federation for American Immigration Reform put the state's annual cost at $1.4 billion. Similar studies in Colorado and Minnesota in 2005 came up with much smaller estimates: $31 million and $17 million, respectively.
Illegal immigrants make up less than 5% of the cost in most states, but closer to 10% in some California counties. In 2000, counties along the Mexican border lost more than $800 million in health care services for which they were not paid; about 25% of that went to care for illegal immigrants, according to a report by the United States/Mexico Border Counties Coalition.