39 results about "Cryptomelane" patented technology

Cryptomelane-type manganese oxide octahedral molecular sieves (OMS-2) supported Fe and Co catalysts are utilized in a method for producing hydrocarbons by a Fischer-Tropsch mechanism. The hydrocarbon producing method includes providing a catalyst of a manganese oxide-based octahedral molecular sieve nanofibers with an active catalyst component of at least one of iron, cobalt, nickel, copper, manganese, vanadium, zinc, and mixtures thereof, and further containing an alkali metal. The formation of iron carbides and cobalt carbides by exposing the catalyst to conditions sufficient to form those carbides is also taught. After the catalyst has been appropriately treated, a carbon source and a hydrogen source are provided and contacted with the catalyst to thereby form a hydrocarbon containing product. The catalyst have high catalytic activity and selectivity (75%) for C2+ hydrocarbons in both CO hydrogenation and CO2 hydrogenation. Highly selective syntheses of high value jet fuel, C2-C6 alkenes, C2-C6 carboxylic acids; α-hydroxylic acids and their derivatives have been realized by tuning the oxidation ability of OMS-2 supports and by doping with Cu2+ ions.

A metal oxide-loaded molecular sieve catalyst comprises pure cryptomelane type manganese dioxide and transition metal. A method for preparing the molecular sieve catalyst comprises the following steps: 1, preparing solution of potassium permanganate; 2, preparing solution of manganese acetate; 3, adding the solution obtained by the step one into a three-neck flask, and heating, condensing and refluxing the solution; 4, adding the solution obtained by the step two into the three-neck flask of the step three, condensing and refluxing the solution, filtering and drying the obtained black pasty sediment, and roasting the sediment to obtain an octahedral manganese oxide molecular sieve catalyst (OMS-2) solid; 5, adding cerium ammonium nitrate, cobalt nitrate hexahydrate, copper nitrate trihydrate, ferric nitrate nonahydrate or yttrium nitrate into deionized water to form solution; and 6, mixing the solid taken from the step four and the solution in the step five, soaking cerium on the octahedral manganese oxide molecular sieve catalyst (OMS-2) solid, and drying and roasting the obtained solid to obtain the metal oxide-loaded molecular sieve catalyst. The metal oxide-loaded molecular sieve catalyst has the characteristics of high purification efficiency, low price and good thermal stability.

The invention provides a method for treating ammonia nitrogen wastewater, which relates to a method for treating the ammonia nitrogen wastewater by using an adsorption method. The method is characterized in that in the treating process, a natural manganese mineral is used as an adsorbent to perform adsorption reaction with the ammonia nitrogen wastewater so as to remove the ammonia nitrogen in thewastewater. The natural manganese mineral is crushed into a manganese mineral adsorbent of 0-2 millimeters, the pH value of the wastewater containing the ammonia nitrogen is adjusted to be between 2and 12 by using acid or alkali, then the manganese mineral adsorbent contacts and is mixed with the ammonia nitrogen wastewater to perform adsorption, and the adsorption can be performed by adopting afixed bed adsorption column or in a stirring and mixing mode. When the fixed bed adsorption column is adopted for adsorption, the manganese mineral after being crushed is classified to remove fine particles for the best so as to improve the permeability of the adsorption column; and in the same way, when the stirring and mixing mode is adopted, the manganese mineral after being crushed is classified to remove coarse particles for the best so as to reduce the abrasion to equipment. The natural manganese mineral applicable to the method comprises a terrestrial manganese oxide mineral, an oceanpolymetallic nodule, an ocean cobalt-rich incrustation and a terrestrial manganese nodule, the natural manganese minerals usually contain manganese minerals of cryptomelane, todorokite, birnessite, vernadite, rancieite, pyrolusite and the like, have good pore structure and large specific surface area so as to have good adsorption property, and can be used as the adsorbent for treating the ammonianitrogen wastewater after being crushed into certain particle size, and the manganese minerals have the advantages of simple process, easy reproduction and stable performance.

Described herein is a novel, cost effective, stable and recyclable catalyst composition i.e. A-B-OMS, wherein ‘A’ is selected from noble and transition metals; ‘B’ is selected from alkali or alkaline earth metals; and OMS is octahedral molecular sieve which includes synthetic todorokite (OMS-1) and cryptomelane (OMS-2); and characterization thereof. Further the invention provides base free green process for selective aerobic oxidation of 5-hydroxymethylfurfural (HMF) catalysed by said catalyst composition under optimized reaction conditions to obtain high yield of 2,5-furandicarboxylic acid (FDCA) in a shorter span of time. Invention also provides for selective oxidation of glucose to Gluconic Acid, furfural to furoic Acid and glycerol to Glyceric acid. Invention can also applicable for the selective oxidation of hexoses, pentoses, disaccharides to corresponding acids.

The invention provides a cryptomelane-based composite metal element catalyst, and a preparation method and application thereof. The cryptomelane-based composite metal element catalyst is prepared from acryptomelane-containing manganese oxide molecular sieve and a doping metal element, wherein the doping metal element enters a cryptomelane type manganese oxidemolecular sieve framework; the mole ratio of the manganese element in the cryptomelane type manganese oxidemolecular sieve to the doping metal element is (100 to 1) to (10 to 1); the cryptomelane type manganese oxide molecular sieve is obtained through the reaction of septivalence manganese and bivalent manganese; the mole ratio of the septivalence manganese to the bivalent manganese is (2 to 1) to (0.5 to 1). The cryptomelane-based composite metal element catalyst provided by the invention has high catalytic activity, and the usage of precious metal is not needed or reduced, so that the cost of the catalyst is greatly reduced; the catalyst has no need to be activated by utilizing hydrogen reduction, is simple in usage conditions, and can be widely applied in purification treatment of benzene-containing waste gas discharged by fixed sources such as a smelting plant, an oil refinery plant and a chemical plant.

A zinc-air battery having: a cathode, an anode, an electrolyte, a separator between the anode and the cathode, and a housing. The cathode includes: a cathode current collector and a composite having a porous carbon material, a porous cryptomelane-type MnOx material, a porous NiyFe1-yOx material, and a binder. The anode includes: a continuous network having metallic zinc and having metallic zinc bridges connecting metallic zinc particle cores and a continuous network of void space interpenetrating the zinc network. The electrolyte fills the void space in the anode, is in contact with the cathode, and permeates the composite without completely filling or obstructing a majority of the pores. The housing encloses the anode, the cathode, and the separator and exposes the composite to ambient air.

This invention discloses a method for controllable templated synthesis of polyaniline nanotubes. The method comprises: utilizing highly oxidative metal oxide nanowires or nanotubes, such as cryptomelane-type MnO2 nanofibers or beta-MnO2 nanotubes as the template, mixing with aniline monomer in an acidic solution in an ice water bath under stirring, reacting for 4-8 h to obtain a dark green solid product, filtering, washing with deionized water and ethanol to remove residual ions and oligomers on the surface, an drying to obtain polyaniline nanotubes. The ratio of MnO2 template to aniline monomer is 40-50 mg / 0.08-0.1 mL. Aniline monomer is adequately stirrer in the acidic solution, and then rapidly transferred into an aqueous solution dispersed with the MnO2 template, where aniline monomer is polymerized in an ice water bath under stirring.

The invention relates to a full solar spectrum driving cryptomelane nanorod catalyst, and a preparation method and applications thereof. The preparation method comprises following steps: 1) adding 0.01mol of a Mn (II) salt and 0.02mol of KMnO4 into a beaker which is filled with water, and magnetically stirring the mixture so as to obtain a mixed solution of the Mn (II) salt and KMnO4; 2) transforming the mixed solution into a stainless steel reaction vessel, sealing the reaction vessel, and performing hydrothermal oxidation reduction reaction; and 3) when the reaction is complete and the reaction vessel cools to a room temperature, taking sediment out of a Teflon inner container of the stainless steel reaction vessel, and filtering, washing and drying the sediment so as to obtain the full solar spectrum driving cryptomelane nanorod catalyst. Beneficial effects of the invention are that: 1) the OMS-2 nanorod catalyst possesses strong absorption capabilities in ultraviolet light, visible light and infrared light wave bands, and high catalytic activity and stability of ultraviolet light, visible light and infrared light-induced thermo-catalytic degradation of VOCs; and 2) reaction conditions are mild, and technologies are simple.

The invention discloses a yolk-shell-structure cryptomelane-type manganese dioxide catalyst as well as a preparation method and application thereof. The preparation method comprises the following steps: synthesizing manganese carbonate powder from a soluble manganese salt water solution, a ammonium hydrogen carbonate water solution, cyclohexane, n-butyl alcohol and cetyl trimethyl ammonium bromideby virtue of a micro-emulsion method, dissolving manganese carbonate into water, and reacting with potassium permanganate, so as to obtain a precursor; and washing the precursor, drying, and roasting300-500 DEG C, so as to obtain the yolk-shell-structure cryptomelane-type manganese dioxide catalyst. The prepared manganese dioxide catalyst is of a mesoporous material, the process is simple, the cost is relatively low, and a product is uniform in shape, relatively good in repeatability and high in catalytic activity. The prepared catalyst can be applied to the removal of volatile organic pollutants in environmental air, the reaction airspeed is 18000h<-1> when the initial solubility of toluene is 1000pm, and the removal rate at 190 DEG C is more than 90% and is obviously superior to traditional precious metal-loaded catalysts.

The invention discloses a manganese oxide catalyst, and a preparation method and an application thereof, and belongs to the technical field of preparation of manganese oxide catalysts. The morphologyof the manganese oxide catalyst is a nanorod, a nanowire and a nanosheet, and the crystal forms of the manganese oxide catalyst are pyrolusite, cryptomelane and pyrolusite respectively. The catalyst of each crystal form is prepared from different raw materials through hydrothermal reaction and calcination. The used raw materials are cheap and easily available, and are rich in resources, and the preparation method has the advantages of simplicity, quickness, realization of large-scale production, low energy consumption, small pollution and environment friendliness. The catalyst has the advantages of high DOC reaction activity on diesel vehicles, low ignition temperature, and excellent potential in the diesel engine tail gas post-treatment application.

The invention provides cryptomelane-type manganese dioxide and a preparation method and use thereof. The preparation method comprises mixing potassium permanganate and a solvent, mixing the mixture and urea for a reaction to obtain precipitates, and roasting the precipitates to obtain cryptomelane-type manganese dioxide. The use amount of potassium permanganate is greater than the solubility of potassium permanganate in a solvent. The preparation method has simple processes and utilizes easily available raw materials. The cryptomelane-type manganese dioxide has high crystallinity, high yield and high density, can catalyze combustion of volatile organic compounds such as ethyl acetate, benzene and methylene chloride at a high temperature of 200 to 500 DEG C, can decompose ozone at the roomtemperature and high humidity and has good application prospects and wide environmental protection purposes.

The invention discloses a preparation method of a manganese oxide / porous carbon nanofiber composite material. According to the method, the biomass is used a raw material, the cryptomelane nanowire is used for forming a hard film plate, and the surfactant is used as a structural guiding agent; and under the effect of dopamine, hydrothermal reaction and calcining processing are carried out to obtain the manganese oxide / porous carbon nanofiber composite material. According to the preparation method provided by the invention, the biomass is used the raw material, so that the effects of low price and environment protection are realized; the equipment investment is low; the operation is simple; the difference between batches of products is small; and scale production can be realized. The prepared product has advantages of high capacitance, energy density, and power density, good rate capability and cycling stability, and excellent corrosion-resistant performance, so that the product is especially suitable for a super capacitor on the alkaline condition.

The invention relates to a preparation method of a three-dimensional ordered macroporous-mesoporous titanium-silicon composite carrier (3DOM-m TixSi1-xO2) supported cryptomelane-type potassium-manganese composite oxide (K-OMS-2) nanoparticle catalyst and an application in catalytic combustion of soot particles. The three-dimensional ordered macroporous-mesoporous carrier is a composite oxide withdifferent silicon-titanium raios. Three-dimensional ordered macropores have an average pore diameter of 50 nm to 1 micron, and three-dimensional ordered mesopores have an average pore diameter of 2-30nm; a method in combination with soft and hard templates is mainly adopted by the preparation method, wherein polymethyl methacrylate microspheres are adopted as a template of the hard template, andP123 (Polyethylene Oxide-Polypropylene Oxide-Polyethylene Oxide) is adopted as the soft template. Finally, the three-dimensional ordered macroporous-mesoporous titanium-silicon carrier supported highly-dispersed K-OMS-2 nanoparticle catalyst is synthesized by taking low-cost potassium permanganate as a raw material through an equivalent-volume impregnation method with simple operation. The preparation method involved by the invention has the advantages that no special equipment and harsh conditions are needed, the process is simple, the controllability and practicability are high.

A method for producing a mixture of ethylene and carbon monoxide comprises contacting ethane and an oxygen source with a catalyst comprising synthetic cryptomelane or octahedral molecular sieve. The method further comprises reacting ethylene with an alcohol to produce an alkyl propionate, which can further react with formaldehyde to produce an alkyl methacrylate.

The invention relates to a cryptomelane-type K(2-x)CoyNizMn(8-y-z)O16 nanowire, which is prepared by the following steps: mixing and dissolving potassium permanganate, a soluble bivalent cobalt salt and / or soluble bivalent nickel salt into water according to a proper molar ratio to obtain a mixed solution; carrying out heating reaction inside a sealed container under the conditions that the temperature is 150-220 DG C and the pressure is 2-3MPa for 10-24 hours. The data display that the cryptomelane-type K(2-x)CoyNizMn(8-y-z)O16 nanowire is a single compound, and belongs to a tetragonal system. In the cryptomelane-type K(2-x)CoyNizMn(8-y-z)O16 nanowire disclosed by the invention, the structure is stabilized after lattice positions of a part of manganese ions are substituted by cobalt ions and / or nickel ions. Meanwhile, the physical and chemical properties such as catalytic activity, gas adsorption property and the like are improved by the synergistic effects of a few of elements of cobalt, nickel and manganese. Thus, the application prospects of the nanowire in the fields such as catalysis, sensing, a lithium ion battery, a solid fuel battery and the like are expanded.

The invention discloses a multi-effect composite repair material for organic pollution groundwater remediation. The multi-effect composite repair material is characterized by being prepared from the following components in parts by weight based on the total parts by weight being 100 parts: 10-35 parts of natural cryptomelane particles, 20-45 parts of an oxygen-release material, 5-18 parts of additives, 10-25 parts of biochar, 5-20 parts of modified ultrafine zinc oxide, and 15-30 parts of a pH buffer agent. The multi-effect composite repair material prepared by the invention has stable properties, large surface area and better adsorption and catalytic oxidation activity, is long in oxygen release duration and high in release efficiency, and can guarantee the sustainability of a groundwaterbioremediation effect; the multi-effect synergy of adsorption, chemical oxidation, catalytic oxidation and bioremediation is realized, and the problems that the existing groundwater remediation agentis single in treatment function and poor in control of treatment effect, and causes secondary pollution can be solved; therefore, the multi-effect composite repair material for the organic pollutiongroundwater remediation is a multifunctional groundwater remediation agent which is in line with the concept of green and sustainable restoration.

The invention discloses a cryptomelane type manganese dioxide oxidant with a three-dimensional structure as well as a preparation method and application thereof. The preparation method comprises the following steps that a uniformly mixed reaction system containing potassium permanganate, divalent manganese salt, cerium salt, bismuth salt and acid is subjected to a reaction at 50-100 DEG C for 5-24 h, the cryptomelane type manganese dioxide oxidant with a three-dimensional structure is prepared, and the molar ratio of potassium permanganate to cerium salt to bismuth salt is 1: (0.015-0.075): (0.012-0.55). The preparation method disclosed by the invention is simple, high in yield and good in repeatability, the used raw materials are low in toxicity, and large-scale production is facilitated. The cryptomelane type manganese dioxide oxidant prepared by the method has a unique center aggregation type cuboid structure and a single cryptomelane crystal phase, can greatly improve the specific surface area and the surface adsorption energy, and can be used as a solid oxidant to directly oxidize and degrade organic pollutants in a water body under a neutral condition.

The invention relates to the technical field of environmental catalysis, and aims to provide a solid-phase OMS-2 molecular sieve catalyst for room-temperature formaldehyde purification and a preparation method thereof. According to the catalyst, cryptomelane type manganese oxide octahedral molecular sieve is used as a carrier, silver loaded with ions is used as an active component accounting for 0.1-20% of the weight of the catalyst. Non-toxic and harmless components are adopted in the preparation process, so that harm to human health and the ecological environment is avoided, and the preparation method is simple and easy to implement. The catalyst can hold 100% formaldehyde removal rate in a wide temperature operation range and a wide airspeed operation range. Compared with an existing noble metal catalyst for room-temperature catalytic oxidation of formaldehyde, the Ag-loaded solid-phase OMS-2 molecular sieve catalyst is relatively low in price and is more suitable for large-scale popularization and application.

The invention discloses a method for controllably preparing manganese oxide with different structures by taking a manganese terephthalate dihydrate as a precursor. According to the method, manganese oxide with different structure types is obtained by taking the manganese terephthalate dehydrate as the precursor, selecting potassium permanganate as an oxidant, adopting a hot method and regulating the pH value, the temperature and the molar ratio of potassium permanganate to the precursor. The preparation method disclosed by the invention is simple, mild in reaction condition and capable of realizing the controllable preparation of manganese oxide with various structures (such as cryptomelane alpha-MnO2, pyrolusite beta-MnO2, nsutite gramma-MnO2, birnessite delta-MnO2 and black manganese ores) by utilizing an abundant and stable pore structure of a complex so as to be a promising preparation method.

The invention discloses a bifunctional adsorbent as well as a preparation method and application thereof. The preparation method comprises the following step: carrying out modification treatment on a cryptomelane molecular sieve by adopting metal chloride to obtain the bifunctional adsorbent. According to the invention, the chloride is used to modify the cryptomelane molecular sieve to prepare the adsorbent with dual catalysis and adsorption functions, so adsorption capacity is improved, and the cycle service life of the adsorbent is prolonged; and after the bifunctional adsorbent is inactivated due to adsorption saturation, ozone can be converted into active oxygen atoms with higher oxidizing property due to the specific efficient ozone decomposition effect of the cryptomelane molecular sieve, and peculiar smell molecules on the surface of the adsorbent are subjected to oxygenolysis; that is, normal-temperature regeneration of the adsorbent is realized in an ozone atmosphere, deep degradation of peculiar smell gas such as ammonia gas and hydrogen sulfide can be achieved in a regeneration process, and secondary pollution is avoided.

The invention discloses a preparation method of active cryptomelane, which is characterized in that ocean polymetallic nodule ammonia leaching residue is adopted as a raw material, and the active cryptomelane is prepared by heating and modifying through a wet process. The preparation method comprises the following steps that: the ocean polymetallic nodule ammonia leaching residue is dissolved in acid and filtered, the filtrate is uniformly mixed with persulfate, ammonium persulfate, potassium permanganate or potassium chlorate solution, and the pH value is adjusted to 0 to 9 by KOH or H2SO4; and then the mixture is heated and modified through the wet process, aged for 12 to 24h, filtered, washed and dried, and the active cryptomelane is prepared. The preparation method of active cryptomelane takes hydrometallurgy tailing as the main raw material, has far lower preparation cost than that of the preparation method of the traditional active cryptomelane and simple process, and is easy to be operated. The active cryptomelane prepared by the preparation method can serve as a catalyst of oxidation-reduction reaction, an alkali metal ion-sieve and the like.

The invention discloses a method for eliminating formaldehyde at room temperature. A cerium skeleton doped cryptomelane type manganese oxide octahedral molecular sieve catalyst is used for catalyzing formaldehyde to be completely oxidized at room temperature to generate carbon dioxide and water; according to the catalyst, a cryptomelane type manganese oxide octahedral molecular sieve is used as a basic framework, and cerium is used for replacing part of manganese on the framework; the preparation method of the catalyst comprises the following steps: mixing a manganese source and a cerium source in a solid phase, uniformly grinding, transferring into a reaction kettle, sealing, crystallizing for 1-3 hours at the temperature of 90-120 DEG C under self-generated pressure, and washing, filtering and drying the solid obtained after crystallization to obtain the catalyst, the molar ratio of cerium in the cerium source to manganese in the manganese source is (0.01-0.2): 1. The noble metal-free catalyst prepared by a specific preparation method can catalyze formaldehyde to be completely oxidized at room temperature to generate carbon dioxide and water, the formaldehyde conversion rate can reach 100%, the carbon dioxide selectivity is always 100%, no intermediate product is generated, and secondary pollution is avoided.

The invention relates to a cryptomelane type mixed manganese oxide catalyst for removing soot of a diesel vehicle through oxidation. The chemical structural formula of the catalyst is KMnOx. The catalyst is prepared by taking potassium permanganate, manganese acetate and acetic acid as raw materials through precipitation reaction and calcination. The used raw materials are cheap and easily available, the conditions are mild, the preparation process method is simple, and important scientific significance and good application prospect are achieved. The prepared KMnOx catalyst has large specificsurface area and pore volume, and has hierarchical pore structure characteristics and good oxidation-reduction capability. The catalyst can be used for efficiently catalyzing and oxidizing soot particles of the diesel vehicle.

The invention discloses a preparation method of a three-dimensional prismatic manganese oxide molecular sieve catalytic material, which comprises the following steps: uniformly mixing a potassium permanganate aqueous solution with an aqueous solution containing a divalent manganese salt, nitric acid and a doping reagent, and stirring and reacting at 25-100 DEG C for 5-24 hours; and filtering, washing and drying the reaction product to obtain the three-dimensional prismatic manganese oxide molecular sieve catalytic material. The manganese oxide molecular sieve catalytic material is a cryptomelane crystal phase, has a three-dimensional prism-shaped morphological structure and a large specific surface area, and can effectively catalyze, oxidize and degrade various organic pollutants in water in cooperation with oxidizing agents such as air, oxygen, hydrogen peroxide and persulfate. In addition, the manganese oxide molecular sieve material with the lamellar structure is prepared through one-pot reflux, the operation method is simple, the yield is high, and the repeatability is good.

The invention provides a metal-doped cryptomelane molecular-sieve catalyst and a preparation method and application thereof. The preparation method comprises the following steps: S1, dissolving manganese sulfate and potassium nitrate in deionized water, conducting mixing to obtain a solution A, dissolving potassium hydrogen persulfate and metal salt in deionized water, and carrying out mixing to obtain a solution B; and S2, mixing the solution A and the solution B, putting the mixture into a high-pressure reaction kettle for a hydrothermal reaction, and filtering, washing, drying and grinding a solid product to obtain the metal-doped cryptomelane molecular-sieve catalyst. The metal-doped cryptomelane molecular-sieve catalyst with uniform particle size and a core-shell structure is prepared by utilizing a hydrothermal synthesis method, and compared with a conventional cryptomelane type molecular sieve, the catalyst has higher surface oxygen hole density, larger specific surface area and more excellent sulfur resistance and water resistance, and can effectively improve the removal rate of NO in flue gas.