Method of molecular ethylene oxidation |
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IPC classes for russian patent Method of molecular ethylene oxidation (RU 2335498):
 Method of perfecting process of producing ethylene oxide / 2329259
Invention pertains to ethylene oxide and to the method of obtaining 1,2-ethanediol or a simple ether of 1,2-ethanediol, from ethylene oxide, obtained using the proposed method. The process of producing ethylene oxide involves an epoxidation reactor system, containing a volume of a high octane epoxidation catalyst. The method involves replacing part of the volume of the high octane epoxidation catalyst with a volume of highly selective catalyst and modification of the process system so as to provide for initial raw materials of the reactor of the epoxidation system, with low concentration of carbon dioxide.
 Method of reduction of (-halogenketones to secondary (-halogenspirits / 2326860
Method involves a stage of interaction of one or more α-halogenketones with general formula I
 Method of production of limonene diepoxides / 2324690
Invention covers production of mixture of stereoisomers of limonene diepoxides (1.2-8.9-diepoxide-p-terpanes) used as resin components or composites for technical purposes, in fine organic synthesis and in perfumes. The method includes epoxidation of double bonds in limonene with diluted hydrogen peroxide in water solution of acetonitrile, N,N-dimethylformamide or methanol at ambient temperature under catalytic action of manganese sulphate mixed with sodium bicarbonate and salicylic acid. Further reaction products are extracted from the reaction mixture with organic solvent, extractant is distilled. Crude epoxide thus obtained undergoes purification by established methods (vacuum distillation or absorption). The method allows to obtain diepoxides mixture with 93-97% purity and yield up to 85%.
 Method for epoxidation of olefins / 2320650
Invention relates to a method for continuous epoxidation of olefins with hydrogen peroxide in the presence of a heterogeneous catalyst accelerating the epoxidation reaction. Aqueous reaction mixture comprises the following components: (1) olefin; (2) hydrogen peroxide; (3) less 100 ppm of alkaline metals, alkaline-earth metals in ionogenic, complex or covalently bound form, as bases or base cations possessing pH value pkB less 4.5, or their combination, and at least 100 ppm of bases or base cations possessing pH value pkB at least 4.5, or their combination. Values in ppm are given as measure for the total mass of hydrogen peroxide in the reaction mixture.
Method for preparing styrene / 2315760
Invention relates to a method for synthesis of styrene. At the first step the method involves interaction of ethylbenzene hydroperoxide with propene in the presence of catalyst to yield propylene oxide and 1-phenylethanol followed by separate treatment of reaction flow and removing propylene oxide. At the second step the method involves interaction of 1-phenylethanol-containing distillate with a heterogenous dehydration catalyst at temperature 150-320°C to obtain styrene. Distillate contains 0.30 wt.-%, not above, compounds of molecular mass at least 195 Da. Invention provides decreasing the content of by-side compounds in styrene and to enhance it's the conversion degree.
Propylene epoxidation process / 2314300
Invention relates to technology of epoxidation of unsaturated compounds with hydrogen peroxide, in particular to production of propylene oxide and propylene glycol. Epoxidation is conducted in presence of organic solvent and catalytically active compound including zeolite catalyst. Product mixture contains propylene oxide, unreacted propylene, and α-hydroperoxypropanols, which are reduced with hydrogen into corresponding propylene glycols. As organic solvent, alcohols, preferably methanol, or their mixtures with water are used. Propylene oxide as well as unreacted propylene and solvent are separated by distillation at column vat temperature below 80°C and residence time less than 4 h. Hydrogenation catalyst is selected from group comprising heterogeneous catalysts containing as active metal Ru, Ni, Co, Pd, and Pt, individually or as two- or more-component mixture on suitable carrier.
 Method for preparing 2,10-epoxypinane / 2303034
Invention relates to a method for synthesis of 2,10-epoxypinane (β-pinene epoxide). Method involves epoxidation of β-pinene double bond with diluted hydrogen peroxide in an aqueous solution of polar solvents (methanol, N,N-dimethylformamide or acetonitrile) under condition of catalytic effect of manganese sulfate in the presence of sodium hydrocarbonate and salicylic acid. Then epoxide and β-pinene are extracted with aliphatic solvent from the reaction mixture. Polar and aliphatic solvents can be used repeatedly. At final step 2,10-epoxypinane is isolated from crude epoxide by distillation under vacuum with purity degree 95% and the yield 60-70%. Invention provides the development of technological method for synthesis of intermediate compound used in preparing some medicinal, technical and perfume preparations.
Organic hydroperoxide production process / 2300520
Invention relates to production of alkylaryl hydroperoxides useful as starting material in production of propylene oxide and alkenylaryl. Process of invention comprises following stages: oxidation of alkylaryl compound to form reaction product containing alkylaryl hydroperoxide; contacting at least part of reaction product with basic aqueous solution; separation of hydrocarbon phase containing alkylaryl hydroperoxide from aqueous phase; containing at least part of above hydrocarbon phase with aqueous solution containing waste water, said aqueous solution containing less than 0.2% alkali metal and/or salt (determined as ratio of metal component to total amount of solution); and separation of hydrocarbon phase from aqueous phase. By bringing at least part of above hydrocarbon phase containing alkylaryl hydroperoxide into interaction with propylene and catalyst, alkylaryl hydroxide and propylene oxide are obtained. At least part of propylene oxide is then separated from alkylaryl hydroxide. Dehydration of at least part of alkylaryl hydroxide results in formation of alkenylaryl.
Method and systems for epoxidation of olefin / 2294327
Invention relates to a method for the epoxidation reaction of olefin. Method involves interaction of the parent olefin-containing raw, oxygen and an agent modifying reaction in the presence of a silver-base catalyst. Agent modifying the reaction presents in the relative amount Q that represents the ratio of effective molar amount of active parts of reaction modifying agent presenting in the parent raw to the effective molar amount of hydrocarbons presenting in the parent raw. Proposed method involves the following steps: interaction in the first stage of process wherein Q values are equal to Q1 and the following interaction in the second step of process wherein the composition of the parent raw differs from composition of the parent raw used in the first step of process and Q value is equal to Q2 wherein value Q2/Q1 = 0.5-1.5. Also, invention relates to a method for synthesis of 1,2-diol or 1,2-diol ether, system for realization of method, the end product and a computer system suitable for using with proposed method.
 Method of production of oxirane, installation for its realization and a combined method of production of hydrogen peroxide and oxirane / 2247118
The invention is dealt with a method of production of hydrogen peroxides and oxiranes. The invention provides for conductance of reaction of olefin with hydrogen peroxide at the presence of a catalyst and organic thinner. At that hydrogen peroxide is present as a water solution of hydrogen peroxide extracted mainly with the help of purified water out of a mixture produced as a result of oxidation at least of one alkylanthrahydroquinone without aftertreatment with a cleansing water and-or purification. The technical result is an increase of an output and selectivity of oxirane.
Oxidation catalyst of ethylene / 2331474
Oxidation catalyst of ethylene in ethylene oxide is described, free from rhenium and transition metal, which is solid silver and containing the combination of promoters consisting of (1) alkaline metals in quantity 400-1500 ppm by weight of the catalyst, (2) barium in the quantity 5-500 ppm by the weight of the catalyst and (3) sulfur in the quantity 5-300 ppm by the weight of the catalyst. Also described is the method of obtaining ethylene oxide, including the interaction of ethylene and molecular oxygen in the presence of the above described catalyst.
Method of perfecting process of producing ethylene oxide / 2329259
Invention pertains to ethylene oxide and to the method of obtaining 1,2-ethanediol or a simple ether of 1,2-ethanediol, from ethylene oxide, obtained using the proposed method. The process of producing ethylene oxide involves an epoxidation reactor system, containing a volume of a high octane epoxidation catalyst. The method involves replacing part of the volume of the high octane epoxidation catalyst with a volume of highly selective catalyst and modification of the process system so as to provide for initial raw materials of the reactor of the epoxidation system, with low concentration of carbon dioxide.
Method for olefines epoxidation and applied catalyst / 2328491
Method for olefine epoxidation is invented which includes the reaction of the raw material containing olefine, oxygen and organic halogenide, in presence of the catalyst containing silver and rhenium precipitated on the carrier where the catalyst contains rhenium at 1.5 mol/kg of the catalyst mass, at maximum, and 0.0015 mmol/m3 of the carrier surface, at maximum, and where the reaction temperature is increased so as to partially reduce the effect of catalyst loss, and the halogenide is presented in relative Q amount which is maintained constant and where the relative amount of Q is the ratio of the effective molar amount of the active halogen compound in the raw material, to the effective molar amount of hydrocarbon, in the raw material. The invention also implies the method for producing the 1,2-diol, the simple ether of the 1,2-diol and/or alkanolamine and the catalyst to be applied in the said method.
 Method of producing olefin oxide, method of application of olefie oxide and catalytic composition / 2325948
Principle refers to the method of producing olefin oxide, method of application of the produced olefin oxide and the production of 1,2-diol or simple ether 1-,2-diol and catalytic composition. The mentioned catalytic composition for the production of olefin oxide contains silver and activating agent, that consists of an alkaline metal on a bearer where the activating alkaline metal contains potassium whose quantity is not less than 5 mcmol/g of metal relative to the mass of the catalytic composition and not less than 1 mcmol/g alkaline metal from the group that contains lithium, sodium and there mixtures in which the mentioned bearer contains calcium carbonate joined with silver. The relative mass of silver: calcium carbonate is 1:5 to 1:100, and the unit surface area of the bearer is from 1 m/g to 20 m/g, and the apparent porosity of the bearer is 0.05 ml/g to 2 ml/g. The explained method of producing olefin oxide, include interaction of olefin, that has 3 or more carbon atoms, with oxygen in the presence of the above mentioned catalytic system, and the method of producing 1,2-diol or simple ether 1,2-diol, in which the olefin oxide is produced from the explained method.
Method of improving selectivity of catalyst and a olefin epoxidation process / 2314156
Method of improving selectivity of highly selective epoxidation catalyst on support containing silver in amount at most 0.19 g per 1 m2 of the support surface area comprises bringing catalyst or catalyst precursor containing silver in cationic form into contact with oxygen-containing raw material at catalyst temperature above 250°C over a period of time more than 150 h, after which catalyst temperature is lowered to at most 250°C. Olefin epoxidation process comprises bringing above-described supported catalyst or catalyst precursor into contact with oxygen-containing raw material at catalyst temperature above 250°C over a period of time more than 150 h, after which catalyst temperature is lowered to at most 250°C and catalyst is brought into contact with raw material containing olefin and oxygen.
Method of initiating epoxidation process, catalyst and epoxidation process / 2311229
Invention relates to olefin epoxidation method and methods for preparing 1,2-diol or 1,2-diol ether, or alkylamine including conversion of olefin oxide into 1,2-diol or 1,2-diol ether, or alkylamine. Olefin epoxidation method comprises: (a) preliminarily impregnating high-selectivity silver-based epoxidation catalyst with organohalogen compound; (b) passing, over preliminarily impregnated catalyst, a material free of organohalogen compound or containing it in concentration not higher than 2·10-4 mol % (calculated for halogen) over a period of time from 15 h to 200 h; and (c) contacting resulting catalyst with material containing olefin, oxygen, and organohalogen compound wherein concentration of organohalogen compound is by at least 0.2·10-4 mol % higher than that of compound in step (b). Preparation of 1,2-diol, 1,2-diol ether, or alkylamine is also described.
Method and system for olefin epoxydation / 2296126
Claimed method includes interaction of raw materials containing olefin, oxygen and reaction modifying agent in presence high selective silver-based catalyst at reaction temperature of T. Relative amount of reaction modifying agent is Q, wherein Q is ratio of effective molar amount of active sites of reaction modifying agent representing in raw materials to effective molar amount of hydrocarbon representing in raw materials. Epoxydation process is carried out in the first process phase wherein T=T1 and Q=Q1. Further process is carried out in the second process phase at T=T2 and Q=Q2, wherein T2 and Q2 are differ from T1 and Q1. Q2 is calculated according to equation Q2 = Q1 + B(T2 - T1) wherein B represents constant more than 0. Also disclosed are method for production of 1,2-diol or 1,2-diol ether; reaction system used in investigation; computer program product for calculations and computer system including said program product and information processing system.
Method and systems for epoxidation of olefin / 2294327
Invention relates to a method for the epoxidation reaction of olefin. Method involves interaction of the parent olefin-containing raw, oxygen and an agent modifying reaction in the presence of a silver-base catalyst. Agent modifying the reaction presents in the relative amount Q that represents the ratio of effective molar amount of active parts of reaction modifying agent presenting in the parent raw to the effective molar amount of hydrocarbons presenting in the parent raw. Proposed method involves the following steps: interaction in the first stage of process wherein Q values are equal to Q1 and the following interaction in the second step of process wherein the composition of the parent raw differs from composition of the parent raw used in the first step of process and Q value is equal to Q2 wherein value Q2/Q1 = 0.5-1.5. Also, invention relates to a method for synthesis of 1,2-diol or 1,2-diol ether, system for realization of method, the end product and a computer system suitable for using with proposed method.
Olefin epoxidation catalyst carrier and a method for preparation thereof / 2282497
Invention relates to creating carriers for catalysts used in epoxidation of olefins and provides catalyst containing at least 95% α-alumina with surface area 1.0 to 2.6 m2/g and water absorption 35 to 55%, and which has pores distributed such that at least 70% pore volume is constituted by pores 0.2 to 10 μm in diameter, wherein pores with diameters 0.2 to 10 μm form volume constituting at least 0.27 ml/g of carrier. Also described is a method for preparing catalyst carrier, which envisages formation of mixture containing 50-90% of first α-alumina powder with average particle size (d50) between 10 and 90 μm; 10-50% (of the total weight of α-alumina) of second α-alumina powder with average particle size (d50) between 2 and 6 μm; 2-5% aluminum hydroxide; 0.2-0.8% amorphous silica compound; and 0.05-0.3% alkali metal compound measured as alkali metal oxide, all percentages being based on total content of α-alumina in the mixture. Mixture of particles is then calcined at 1250 to 1470°C to give target carrier.
Ethylene oxidation catalyst and a method for preparing the same / 2278730
Invention provides catalyst for oxidation of ethylene into ethylene oxide, which catalyst contains no rhenium and no transition metals and comprises up to 30% silver on solid support and promoter combination mainly consisted of (i) component containing alkali metal on amount from 700 to 3000 ppm of the mass of catalyst and (ii) component containing sulfur in amount from 40 to 100% by weight of amount required to form alkali metal sulfate and, optionally, a fluorine-containing component in amount from 10 to 300 ppm of the mass of catalyst. Ethylene oxide is produced via reaction of ethylene with molecular oxygen in presence of above-defined catalyst.
 Method for ethylene epoxydation / 2263670
Invention relates to a method for vapor-phase oxidation of ethylene to ethylene oxide. Method involves interaction of ethylene and oxygen in the presence of silver-base highly selective catalyst. On the onset stage of process fresh catalyst is used and on the additional stage of process when cumulative productivity enhances 0.01 kT of ethylene oxide per m3 of catalyst by ethylene oxide the concentration of ethylene is increased in the reaction mixture. Also, invention relates to a method for using ethylene oxide for preparing 1,2-ethanediol or corresponding 1,2-ethanediol ether involving conversion of ethylene oxide to 1,2-ethanediol or 1,2-ethanediol ether wherein ethylene oxide has been prepared by this method for producing ethylene oxide.
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FIELD: chemistry. SUBSTANCE: according to the present invention, ethylene is oxidised in contact with mix of heterogeneous catalyst in particles and solid inert substance in particles, treated with alkali metal, in oxidation conditions. EFFECT: improved efficiency. 3 cl, 1 tbl, 8 ex
The technical field The present invention relates to a method for oxidation of ethylene to ethylene oxide, in which the oxidation is conducted on a solid catalyst in a fixed bed composed of a mixture of heterogeneous active oxidation catalyst, for example, applied silver catalyst, and an inert solid diluent-treated base. The level of technology In the field of oxidation of ethylene to ethylene oxide is commonly used layers with step catalytic activity (British patent 721412) and apply the system in which the waste stream is rapidly cooled by contact with an inert solid substances, see U.S. patent 4061659, 4376209, 5292904 and 4642360. In such systems, where the oxidation catalyst diluted with an inert substance, there is a problem, which consists in that the inert diluent really promotiom decomposition of the target product. In other words, the inert diluent is not completely inert, but rather contains the active centers on the surface, which lead to loss of product. The invention According to the present invention it has been found that undesirable loss product of ethylene oxide caused by the dilution of the catalyst inertly, can be substantially avoided by treating the inert diluent base before mixing with Akti is the principal catalyst. Detailed description of the invention When loading in an industrial reactor of the applied catalyst, for example Ag/alumina, for oxylene of ethylene to ethylene oxide, it is important to introduce an inert substance inside catalyst layer to separate layers or dilution. Or inert substance can be placed on the exit layer. In any case, it is desirable that the particles of inert substances have the same size and configuration as the catalyst particles or tablets. The most appropriate is an inert substance from the same media that was used for the preparation of the catalyst. The authors found that the treatment media of any alkali metal retains its inertness makes it suitable for the dilution of the catalyst layer or delamination, which helps to avoid product loss. For traditional oxidation of ethylene on the catalyst on the basis of silver is chosen as a carrier of aluminum oxide. Usually the carrier of aluminum oxide has an active surface, which can cause decomposition product of ethylene oxide. The authors found that applying a small amount of any salt of an alkali metal on the surface of the carrier will neutralize its activity, leaving him inert, allowing you to avoid decomposition of the product. In the prior art for the preparation of the of talization with increased activity used salt "higher alkali metals". The most commonly used additive is cesium, although it was claimed that a mixture of Cs and other alkali metals also increase the catalytic activity. It was reported that "lower alkali metals" - Li and Na - slightly increase the activity. When this method of preparation, however, the carrier is treated with an alkaline metal, also contains silver and other promoters. The most affordable industrial carriers for catalysts contain one or more alkali metal salts, in particular sodium salt. Part of the alkali metal present on the surface plays the role of catalyst for decomposition on the surface of the carrier. The authors found that the removal of salts of alkali metals from the surface leads to an increase in the activity of the surface and also the destructive capacity of the media. However, usually the amount of alkali metal on the surface of the carrier is insufficient to neutralize all of the centers that cause decomposition. Therefore, according to the present invention, the application of an additional amount of alkali metal is essential to obtain a fully active surface. To determine the minimum number of salts of alkali metals, is required to neutralize all of the centers decomposition on the surface of the medium, difficult. The number of active sites depends on many factors, e.g. the measures of the magnitude of the carrier surface, various additives in its composition, the process of roasting the media, and the chemistry of its surface. However, there is nothing dangerous to add a large number of salts of alkali metals, which exceeds the amount needed to neutralize all of the active centers. In General, the amount of salt of the alkali metal on the surface should be greater than 5 mg-atom/kg of carrier and up to about 2 wt.% from inert carrier. As the alkali metal salts of the invention use salts of sodium, potassium, rubidium and cesium. The concentration of the alkaline metals on the surface of the carrier is determined with the aid acid test villacian. In this test, the sample carrier is placed in a solution of nitric acid. The concentration of alkali metals in the resulting solution is determined by atomic-absorption spectrophotometry instrument Varian AA-I 10" in acetylene-air flame. Or quantitative analysis is performed by placing the solution in a spectrophotometer with an induction-coupled plasma Spectro-analytical EOP ICP". When implementing the present invention with an inert solid substance in the form of particles, the pre-treated base, mixed with conventional oxidation catalyst in such proportions as to obtain the desired dilution. To obtain ethylene oxide-treated inert substance is mixed with t adicionam silver catalyst, for example, such as described in U.S. patents 5504052, 5646087, 57736483, 5703001, 4356312, 4761394. When processing a basis inert carrier is soaked in an aqueous solution of compounds of alkali metals, such as hydroxides, carbonates, acetates and the other in a period of time sufficient for applying Foundation on the surface of the carrier, for example, from 1 minute to 10 hours or longer. The media is removed from a solution of the base and dried, after which it is suitable for mixing with heterogeneous oxidation catalyst. In General, the inert substance is treated with base, mix in amounts in the range of from about 5 to 80 wt.% the total mass of the inert substance and the catalyst, although, as shown above, the inert substance is treated with base, can be 100% solids in the pre-heating zone of the reaction tube. EXAMPLES Example 1 (comparative) The catalyst receipt of ethylene oxide was prepared by impregnation of the carrier of alpha-alumina with an aqueous solution of complex oxalate Ag with Ethylenediamine; the media was represented by a cylinder with an external diameter of 8 mm, height 8 mm and diameter 5 mm Solution also contained a promoter - Sol Cs. The catalyst was progulivali at a temperature sufficient to decompose the complex of silver to metal. The resulting catalyst contained 12% Ag and 500 ppm Cs. This catalyst and is used in all examples, below. The catalyst was tested by loading 9 g in a tubular reactor made of stainless steel, which was heated in a bath of molten salt. After the catalyst was passed a gaseous mixture containing 15% ethylene, 7% oxygen and 78% inert gas, mainly nitrogen and carbon dioxide, at a pressure of 300 pounds per square inch. The reaction temperature was set so as to obtain the performance for ethylene oxide 160 kg/h at 1 m3of the catalyst. The activity of the catalyst remained stable and after a week of work, and calculated the selectivity of the formation of ethylene oxide was 83.3%. Example 2 (comparative) The purpose of this example is the determination of the destructive impact of the active surface of the carrier on receipt of ethylene oxide. The same sample of catalyst 9 g was loaded in the reaction tube of stainless steel. This example was added 2 g of the same carrier of aluminum oxide, which is used in the preparation of the catalyst was mixed with the catalyst. The media were placed in the upper third of the reaction tube. The catalyst was stable and after a week of work, and calculated the selectivity of the formation of ethylene oxide was 81.9%. Example 3 100 g of the same media used for preparation of the catalyst and in which the concentration of Na on the surface was 90 ppm, the industry is Ali 500 ml of 0.3 N aqueous solution of ammonium hydroxide. The solution was separated and the washing was repeated four times. Then the media was twice washed with deionized water and dried at 150°C. analysis of the solutions showed that the total amount of sodium removed from the surface of the media was 55 ppm to Asescu 9 g of catalyst were placed in a reaction tube made of stainless steel. In this example, we also added 2 g of the washed media. The media were placed in the upper third of the layer. After a week of work activity of the catalyst remained stable, and calculated the selectivity of the formation of ethylene oxide was 80.3%. This shows that the removal of the sodium from the surface by washing with a solution of ammonium hydroxide increased the destructive ability of the carrier. Example 4 100 g of the carrier used for the preparation of the catalyst, impregnated 300 ml of 0.05 N aqueous solution of cesium hydroxide. The carrier was dried and analyzed for the content of Cs using acid leaching test. The medium contained 300 ppm Cs. 9 g of catalyst were placed in a reaction tube made of stainless steel. In this example, we also added 2 g of the treated Cs media. The carrier was placed in the upper third layer, as in example 3. After a week of work activity of the catalyst remained stable, and calculated the selectivity of the formation of ethylene oxide was 83.3%. This shows that clicks the processing cesium led to neutralize destructive active centers on the surface of the carrier and a substantial increase in the yield of ethylene oxide. Example 5 The sample carrier was treated with 300 ml of 0.05 N aqueous solution of cesium carbonate. After this treatment the analysis showed that the medium contained 570 ppm cesium. 2 g of this treated media was added to the catalyst layer, as in the previous examples. After a week of work activity of the catalyst remained stable, and calculated the selectivity of the formation of ethylene oxide was 83.2%. This shows that the processing of Cs led to neutralize destructive active centers on the surface of the media. Examples 6-8 Samples of media were treated with aqueous solutions of hydroxides of Li, Na and K, as shown in example 3. Treated media was then analyzed for the content of leachable metals. 2 g sample of each of the processed media was added in a separate reactor containing 9 g of a silver catalyst. After a week of work activity of the three catalysts remained stable, and calculated the selectivity of the formation of ethylene oxide were:
This shows that in all three cases, treatment with an alkaline metal led to neutralize destructive active centers on the surface of the media. 1. The method of molecular oxidation of ethylene in the presence of a heterogeneous oxidation catalyst in the form of particles with the formation of ethylene oxide, consisting in the oxidation of ethylene in contact with a mixture of heterogeneous oxidation catalyst and inert solid substances in the form of particles, treated with a salt of an alkali metal. 2. The method according to claim 1, in which an inert substance in the form of particles is alumina. 3. The method according to claim 1, wherein the oxidation catalyst is a silver supported on alumina.
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