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IPC classes for russian patent Novel water hydrogen peroxide solutions (RU 2336225):
Method of molecular ethylene oxidation / 2335498
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.
 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 molecular ethylene oxidation / 2335498
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.
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.
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FIELD: chemistry. SUBSTANCE: claimed is water solution of hydrogen peroxide, suitable for olefine epoxidation, which includes: I) in total less than 50 wt fraction/mln of alkaline metals, alkaline-earth metals or their combinations irrespective of whether said alkaline or alkaline-earth metals are in catione-active or complex form; II) in total at least 50 wt fraction/mln of amines, which have pkb value less than 4.5, or respective protonated compounds; and III) in total at least 100 wt fraction/mln anions or compounds, which are able to dissociate with anion formation, according to which values in wt fraction/mln are given in terms of hydrogen peroxide weight. Claimed is method of obtaining hydrogen peroxide solution. Claimed is application of water solution of hydrogen peroxide. EFFECT: economically efficient production of water solution of hydrogen peroxide and improved long-term activity and selectivity of catalyst. 18 cl, 5 ex, 2 tbl
The present invention relates to a special aqueous solution of hydrogen peroxide, which is characterized by a maximum content of alkali metals, alkaline earth metals and amines having a pk valueBless than 4.5, which is particularly suitable for use in processes for the epoxidation of olefins, and to a method for producing such an aqueous solution of hydrogen peroxide. Background of invention Currently, the vast quantity of hydrogen peroxide get on well known antrahinonovye method. Review antrahinonovye method and its numerous modifications described in G.Goor, J.Glenneberg, S.Jacobi: "Hydrogen Peroxide" Ullmann''s Encyclopedia of Industrial Chemistry, Electronic Release, 6thed. Wiley-VCH, Weinheim June 2000, p.14. Usually antrahinonovye technological circuit includes the following stages: (a) hydrogenation of a working solution comprising an organic solvent or mixture of organic solvents and one or more active antrahinonovye connections (b) oxidation of the hydrogenated working solution with obtaining hydrogen peroxide, (C) extraction of the hydrogen peroxide water, (g) stabilizing the extracted aqueous solution of hydrogen peroxide, (d) drying the working solution after extraction and (e) regenerative and clean working solution. For each of the above is shown separate process steps in the link to work in Ullmann describes the many different possibilities. Crude solutions of hydrogen peroxide or concentrated solutions of hydrogen peroxide obtained by antrahinonovye method, in addition to hydrogen peroxide, contain low concentrations of many compounds. These compounds are either impurities or additives such as stabilizers. Impurities are compounds that are extracted from the working solution aqueous phase. They are mainly ionic or polar materials such as carboxylic acids, alcohols, carbonyl compounds, and amines. Therefore, these impurities are also contained in the technical solutions of hydrogen peroxide. As examples of solvents hydroquinone, which is usually used in the above process, it should be mentioned nitrogen-containing compounds, such as amides and urea derivatives (see the above-mentioned work Ullmann, p.6). Especially preferred tetraalkylammonium, such as tetrabutyltin. The result of applying these solvents are contained in the final solutions of hydrogen peroxide amine impurities such as monoalkyl - and dialkyl, mainly monobutyl and dibutylamine. For example, the technical solution of hydrogen peroxide HYPROX®available on the company Degussa AG, contains up to 200 wt. part./million mono and dibutylamino in terms of mass perox is Yes hydrogen. Depending on the final application of solutions of hydrogen peroxide, in order to meet the technical requirements for the respective purpose of application of hydrogen peroxide solution, it is also known implementation of additional stages of refinement. For example, in DE-A 10026363 described method of purification of aqueous solutions of hydrogen peroxide, in accordance with which these solutions are treated with anion exchange resin, non-ionic absorbent resin, which has a special structure, and neutral absorbent resin, which also has a special macroporous structure. Solutions of hydrogen peroxide produced in this way, practically free from cationic, anionic and organic contaminants. Therefore, such solutions are particularly effective for use in microelectronics. Similarly in the US 4999179 described method of cleaning solutions of hydrogen peroxide, which contain after cleaning each metal cation in an amount of less than 5 hours/bn, each anion in the amount of less than 10 h/bn and organic impurities in an amount of not more than 5 hours/million in terms of total organic carbon atoms. The drawback of such methods is that cleaning is very expensive, and for economic reasons in the case of obtaining the mass of chemical products, such as propylene oxide,it may not hold. Moreover, such high-purity solutions of hydrogen peroxide essentially free of anionic components such as phosphates and nitrates, which are necessary for the stabilization of water, mostly highly concentrated solutions of hydrogen peroxide for security reasons. From EP-A 100119 known that using hydrogen peroxide propene can be converted into the oxide, propene, if the catalyst is to apply a titanium containing zeolite. Since published the results of many studies on the effects or add basic, acidic and ionic compounds during cooking titanosilicate catalyst, or their presence in the reaction mixture on the activity and selectivity of catalysts. From EP-A 230949 known neutralization of strong bases titanosilicate catalyst before its use in the epoxidation reaction or in situ with the introduction thus in the reaction mixture of large quantities of ions of alkali or alkaline-earth metals. The result of the neutralization is increased activity and selectivity for target olefin oxide in a periodic process. However, as described in EP-A 757043 experiments show that if in a continuous process, the catalyst is neutralized before or during the reaction, its concentration activity of the ΓΌ is much lower. Therefore, the catalyst serves to process before or during the epoxidation reaction is neutral or acidic salt. Experimental data on the EP AND 757043 confirm that the addition of neutral or acidic salts increase the selectivity, but the activity is lower in comparison with that achieved by adding grounds. But in EP-A 757043 are only examples, in which the catalyst is treated with salt before the reaction and the catalyst used in the form of suspension. In addition, the experiments were conducted only for 8 hours, but nevertheless they show a sharp drop in catalyst activity after 4 h, which is in any way unacceptable for industrial process. Similarly, in EP-A 712852 the idea is that during the process of epoxidation catalyzed by silicalite titanium, in the presence of a minor salt selectivity increases. The experiments are all examples of conduct in the form of a periodic process with a stirring suspension of catalyst in one hour. Despite the opportunity to confirm that the presence of minority salts can have a positive effect on the selectivity of the catalyst for a short-term experiment, it was found that even if the reaction mixture continuous epoxidation reaction are present with minor and, the activity and selectivity over time is significantly reduced. Thus, the information contained in EP-A 712852, does not create a reaction system that can be cost-effectively applied in a continuous process of epoxidation using hydrogen peroxide in the presence of a heterogeneous catalyst. In WO 00/76989 discusses the influence of ionic components in the commercially available aqueous solutions of hydrogen peroxide, which is used in epoxidation reactions as described in the above-mentioned dedicated to the art documents. To reduce the risk of decomposition of hydrogen peroxide in the commercially available aqueous solutions of hydrogen peroxide as stabilizers add ionic components, mainly phosphates and nitrates. In contrast to the abovementioned dedicated to the art documents WO 00/76989 the idea is that the presence of ionic components in the reaction mixture, even those that are added as stabilizers in technical hydrogen peroxide, has a negative impact on long-term selectivity during the continuous catalyzed silicalite titanium epoxidation reaction, and therefore, their content must be reduced to a minimum. In across the lagoon to the falsity described in the above-mentioned dedicated to the art documents continuous reaction, which lasted for up to 300 h, showed that if the ionic components are contained in amounts greater than 100 ppm million, long-term selectivity is reduced. To resolve this problem prior to use in epoxidation reactions proposed removal of ionic components from solutions of hydrogen peroxide with the aid of ion exchangers. Moreover, in WO 00/76989 we are talking about the fact that ammonium compounds and ammonia should be avoided under any circumstances, because the presence of these compounds can lead to the formation of undesirable by-products due to reactions tripping oxiranes rings formed by the olefin oxide. Although the information contained in WO 00/76989, allows us to come to some improvement in long-term selectivity in comparison with the specified in the above documents, dedicated to the art, this improvement is still insufficient for carrying out the process on an industrial scale. Moreover, this improvement can only be achieved by the implementation of complicated and related costs for research and technology economically undesirable additional process stage of ion exchange. And finally, but not less importantly, the removal from solution of hydrogen peroxide stabilizing ions, such as FOS is atnie and nitrate, makes the process more dangerous, and to guarantee security during the process as a whole should be taken additional measures. In contrast described in WO 00/76989 in WO 01/57012 says that the use of crude solutions of hydrogen peroxide directly obtained by antrahinonovye method, including, for example, large amounts of sodium, nitrate, phosphate and organic impurities, has an advantage in terms of selectivity with respect to the product, in comparison with the use of high-purity solutions of hydrogen peroxide, containing very small amounts of sodium, nitrate and phosphate. However, the experiments carried out within just several hours, resulting in a long-term activity and selectivity of the catalyst according to this link it is impossible to judge. In addition, as another technical acceptance selected the one described in the application WO 01/92242, according to which the proposed method catalyzed by silicalite titanium epoxidation of olefins using crude solutions of hydrogen peroxide in the presence of compounds with aminocarbonyl functional group in which the nitrogen atom carries at least one hydrogen atom. In the examples shown, a process of periodic type, which spend up to 85%conversion of hydrogen peroxide. Last the two hours the reaction is stopped even if you do not achieve 85%conversion. Although experimental data demonstrate improvement in terms of speed of response, in comparison with the cases of using compounds with aminocarbonyl functional group containing a hydrogen atom bound to the nitrogen atom, according to information contained in WO 01/92242, long-term activity and selectivity of the catalyst in a continuous process it is impossible to judge. In DE-A 19936547 describes how continuous catalyzed silicalite titanium epoxidation of olefins by hydrogen peroxide, in the exercise of which a constant degree of conversion is supported by the increase of the reaction temperature and the regulation of the pH of the reaction mixture. During the long term experiment (1000 h) could be sure that the regulation of pH temperature rise and rate of rise could be reduced in comparison with the data of the experiment without pH regulation. But the conversion and selectivity remained the same regardless of regulating the pH or not. Thus, an object of the present invention is to provide an aqueous solution of hydrogen peroxide, which can be obtained in an economically efficient way, which can be safe in handling, storage and transportation and which is acceptable to epoxidase the Oia olefin in the presence of a heterogeneous catalyst, and ensures improved long-term activity and selectivity of the catalyst. The invention This goal is achieved by creating an aqueous solution of hydrogen peroxide, including: I) a total of less than 50 parts by weight per million of alkali metals, alkaline earth metals or combinations thereof, regardless of whether these are alkaline or alkaline-earth metals in cationic or complex form; II) a total of less than 50 parts by weight per million amines having a pk valueBless than 4.5, or the corresponding protonated compounds; and III) a total of at least 100 parts by weight per million anions or compounds that are capable of dissociate with the formation of anions, in accordance with the values in parts by weight per million specified in terms of the weight of hydrogen peroxide. Proposed by the present invention an aqueous solution of hydrogen peroxide can be obtained according to the method of producing hydrogen peroxide solution in accordance with the technology with antrahinonovye circuit, comprising the following stages: (a) hydrogenation of a working solution comprising an organic solvent or mixture of organic solvents and one or more active antrahinonovye connections (b) oxidation of the hydrogenated working solution with obtaining hydrogen peroxide, (C) extra is tion of hydrogen peroxide water, (g) stabilizing the extracted aqueous solution of hydrogen peroxide, (d) concentration of an aqueous solution of hydrogen peroxide to a concentration of hydrogen peroxide of at least 50 wt.% in recalculation on weight of a solution of hydrogen peroxide, (e) drying the working solution after extraction and (g) regenerative and clean working solution, thanks to that during the whole process either alkaline or alkaline-earth metals or amines having a pk valueBless than 4.5, or compounds forming such amines during the process, do not enter in quantities which determine the concentration I) a total of 50 parts by weight per million or more of alkali metals, alkaline earth metals or combinations thereof, regardless of whether these are alkaline or alkaline-earth metals in cationic or complex form; or II) a total of 50 parts by weight per million or more amines having a pk valueBless than 4.5, or the corresponding protonated compounds; in the resulting aqueous solution of hydrogen peroxide, in accordance with the values in parts by weight per million specified in terms of the weight of hydrogen peroxide. The hydrogen peroxide solution of the present invention is particularly suitable for use in the process of epoxidation of olefins in the presence of a heterogeneous catalyst. Not idanim the execution result of the present invention, the hydrogen peroxide solution, which meets the above requirements and can be safe in handling, storage and during transportation, can be easily obtained by carrying out a cost-effective process. Moreover, the unexpected was that this aqueous solution of hydrogen peroxide leads to improved long-term activity and selectivity of heterogeneous catalyst in the epoxidation process. Therefore, using the proposed aqueous solution of hydrogen peroxide could be significantly improved overall economic performance of the epoxidation process, because this solution can be obtained cost-effectively and results in reduced deactivation of the catalyst so that it can be increased the duration between cycles regenerating in the epoxidation process. Detailed description of the invention When creating the present invention dignity was the recognition of the fact that, contrary to the information contained in the documents related to this technical field, the presence of alkaline and alkaline-earth metals in amounts exceeding a certain limit, in the epoxidation reactions of olefins has a negative impact on the activity and selectivity of the used catalyst. Over the CSOs, when creating the present invention, it was found that, in addition to alkali and alkaline-earth metals, amines having a pk valueBless than 4.5, have a more negative impact on the activity and selectivity of the catalyst, and therefore, their content in solutions of hydrogen peroxide, which is used in the epoxidation reactions of olefins, should be carefully adjusted so that it was below the specified limits. On the other hand, anions such as phosphate and nitrate, which are often used to stabilize aqueous solutions of hydrogen peroxide, do not have or have only a very weak influence on the activity and selectivity of the epoxidation catalyst. Because these anions are needed to stabilize to ensure safety in handling, storage and transportation of an aqueous solution of hydrogen peroxide, they must be contained in stabilizing quantities of at least 100 parts per million, calculated on the weight of the hydrogen peroxide in solution. Contrary to the information contained in the documents on the art for a cost-effective process for the epoxidation of olefins is unacceptable neither the use of a crude solution of hydrogen peroxide obtained by antrahinonovye method, without careful regulation of the amount of alkali is of yellow and amines, with the value of the pkBbelow 4.5, nor the use of treated solutions of hydrogen peroxide, which, in addition to the metal cations, deleted stabilizing anions. Although the number of alkaline or alkaline-earth metals is less than 50 parts by weight per million, calculated on the weight of the hydrogen peroxide in the solution is acceptable, in the preferred embodiment, to further improve the long-term activity and selectivity of the catalyst, the amount of these components must be lowered to less than 40 parts by weight per million, more preferably less than 35 parts by weight of/million Still the negative impact of amines having a pk valueBless than 4.5 on the long-term selectivity and activity of the epoxidation catalyst in the literature is not recognized. The influence of the presence of such amines is even more pronounced than the influence of alkali or alkaline-earth metals. Therefore, in a particularly preferred embodiment, the number of amines having a pk valueBless than 4.5, in an aqueous solution of hydrogen peroxide in total is reduced to less than 40 parts by weight per million, preferably less than 30 parts by weight per million, more preferably less than 20 parts by weight per million, and most preferably less than 10 parts by weight per million, calculated on the weight of hydrogen peroxide in the solution. Especially negatively on AK is Yunosti and selectivity epoxidation catalyst due to the presence of alkylamines followed, mainly secondary and tertiary alkylamines followed. Another unexpected result of research in creating the present invention is that although amines having a pk valueBbelow 4.5, at a content exceeding some number, sharply reduce long-term activity and selectivity of the epoxidation catalyst, the addition of at least 100 parts by weight per million bases having a value pkBat least 4,5, even improves long-term activity and selectivity of the epoxidation catalyst. Thus, in accordance with the preferred implementation of the present invention an aqueous solution of hydrogen peroxide contains, in addition, a total of at least 100 parts by weight per million bases having a value pkBat least 4.5, or the corresponding protonated compounds in terms of the weight of hydrogen peroxide. These grounds can either be entered during the process of obtaining hydrogen peroxide, or can be added to the hydrogen peroxide solution at any stage between getting a solution and end use in the epoxidation reaction. Such grounds in the preferred embodiment, is contained in the hydrogen peroxide solution in an amount of at most 3000 parts by weight per million, more preferably from 150 to 2000 parts by weight per million), especially p is edocfile from 200 to 1500 parts by weight per million, and most preferably from 300 to 1200 parts by weight per million, calculated on the weight of hydrogen peroxide. In a preferred embodiment, such grounds are selected from organic amines and amides having a value pkBat least 4,5, organic hydroxylamines having a value pkBat least 4,5, ammonia and hydroxylamine. Particularly preferred ammonia. A special advantage of the proposed solution of hydrogen peroxide is that the anions may be contained in the usual stabilizing amounts. In the preferred embodiment, these stabilizing anions are anions of any type of oxaphosphorin anions, such as orthophosphates, acid phosphate, monopotassium phosphate, pyrophosphate, nitrate. These stabilizing anions or compounds in which the hydrogen peroxide solution can dissociate with the formation of these stabilizing anions, in the preferred embodiment is contained in a quantity of at most 1000 parts by weight per million, preferably from 100 to 1000 parts by weight per million, more preferably from 200 to 800 parts by weight per million, most preferably from 200 to 600 parts by weight per million, calculated on the weight of hydrogen peroxide. Thus, the hydrogen peroxide solution according to the present invention ensures high selectivity and activity of the catalyst in the epoxidation reaction without at the Erba for safety in handling, storage and during transportation of the hydrogen peroxide solution. Another advantage of hydrogen peroxide solution of the present invention is that it can be easily and economically efficient way to cook using well-known antrahinonovye method, allowing additional purification stages are optional, and if the implementation of the method according to the present invention in a preferred variant, they do not exercise. The only requirement for implementing the method of the present invention in comparison with known modifications antrahinonovye method is that the process must be carefully controlled in order to avoid the introduction of alkali metals, alkaline earth metals, amines having a pk valueBless than 4.5, or compounds that during the implementation antrahinonovye method capable of forming such amines upon receipt of a solution of hydrogen peroxide, in amounts that would have caused concentrations higher than specified in accordance with the present invention limits. Although compliance with this requirement may be many ways antrahinonovye method, with the purpose of drying the working solution of the above stage (e) without the use of compounds of alkali or alkaline-earth metals, which are usually the use of Aut for drying in the implementation known in the art antrahinonovye method and for regenerating a working solution in stage (g) the processing of active aluminum oxide is particularly preferred to use the working solution, which is almost free from organic nitrogen compounds. In a preferred embodiment, the drying is carried out by evaporation of water under vacuum. Thus, the implementation of the method according to the present invention provides for obtaining the proposed solution of hydrogen peroxide, which is particularly effective in the epoxidation reactions, without implementation-related costs and the consumption of a large number of work stages of purification. Thus, the crude hydrogen peroxide solution obtained by carrying out the method according to the present invention, can be used directly, without any additional stages of refinement. In a preferred embodiment, the hydrogen peroxide solution to concentrate the content of hydrogen peroxide is more than 50 wt.%, preferably more than 60 wt.%, most preferably 60 to 70 wt.% in terms of the total weight of hydrogen peroxide solution. When creating the present invention it was found that such concentrated solutions of hydrogen peroxide is particularly effective in the epoxidation reaction, because they additionally improve long-term activity and selectivity of the catalyst. Estabelecida hydrogen according to the present invention can be used in any reaction of epoxidation using hydrogen peroxide, known in the art. In a particularly preferred variant of the proposed hydrogen peroxide solution used in the continuous epoxidation process conducted in the presence of mixing with the water solvent and a heterogeneous catalyst. In a preferred embodiment, the solvent is methanol, the olefin is propene and the heterogeneous catalyst is titanosilicate catalyst. The essence of the present invention are described in more detail with reference to the following examples. Examples Example 1 Obtaining an aqueous solution of hydrogen peroxide in accordance with the present invention In the experimental setup for the process circuit in accordance with antrahinonovye method of obtaining hydrogen peroxide, comprising a stage of hydrogenation, oxidation, extraction, drying and regenerating, used working solution, consisting of 0.11 mol/l 2-ethylanthraquinone, 0.29 mol/l 2-ethyltetrafluoroethylene, 0.13 mol/l 2-isohexadecane and 0.12 mol/l 2-isohexadecane in a mixture of solvents, including 75% vol. With9/S10alkyl substituted aryl compounds and 25 vol.% Tris(2-ethylhexyl)phosphate. On stage hydrogenation reactor with circulation worked under hydrogen pressure of 0.35 MPa and at a temperature of 58°C. as kata is Isadora hydrogenation used palladium black (0,5:1 g/l). Equivalent of hydrogen peroxide in the process of hydrogenation was 13,0 g/l After the hydrogenation portion of the hydrogenated working solution was regenerated using active alumina. After that, the combined working solution was oxidized using the method of oxidation Laporte so, as stated in the above mentioned work in Ullmann, p.14. Then hydrogen peroxide was extracted using deionized water. In the extraction water was added 50 PM/million N3PO4and 20 hours/million HNO3both the number specified in terms of the weight of hydrogen peroxide. The concentration of the extracted aqueous solution of hydrogen peroxide was 41%. The working solution was dried by evaporation of water under vacuum and then returned to the process at stage hydrogenation. The crude hydrogen peroxide solution stabilized with the use of 200 hours/million pyrophosphate of sodium, calculated on the weight of hydrogen peroxide and concentrated under vacuum by evaporation of water. The hydrogen peroxide concentration in the solution obtained in this way was 43 wt.% in terms of the total weight of the solution; it contained 250 mg/kg N2About2phosphate, 20 mg/kg of nitrate and 30 mg/kg of sodium. Examples 2 through 5 and comparative examples 1 to 3 The hydrogen peroxide solution obtained in example 1 was concentrated until the end of the ation of hydrogen peroxide, which are listed in table 1. Moreover, as indicated in table 1, was added ions of alkali metals and/or amines having a pk valueBless than 4.5. In addition, it was added ammonia in the amount of 500 parts by weight per million (1000 parts by weight per million ammonia in example 5) in terms of the weight of hydrogen peroxide. All of the examples used titanosilicate catalyst. Using a colloidal solution of silicic acid as a binder in accordance with example 5 of EP-A 1138387 of titanosilicates powder was molded 2 mm extrudates. Epoxidation was carried out by conducting a continuous process in the reaction tube with a volume of 300 ml, with a diameter of 10 mm and a length of 4 m moreover, the equipment consisted of three containers for liquids and associated pumps, as well as the vessel for separating liquid. Three containers for liquids contained methanol, a solution of peroxide of hydrogen and propene. The reaction temperature regulated water coolant, which is circulated in the cooling jacket, so with a thermostat regulating the temperature of the coolant. Absolute pressure during the reaction was 27 bar. The mass flow rate of the supply pump was controlled so that the concentration of propene was 38 wt.%, the initial concentration of methanol was 48.7 wt.%, as the concentration of the situation of the original hydrogen peroxide was equal to 8 wt.%. The reactor worked in peritoneum mode. The temperature in the cooling jacket brought up to 35°and the total mass flow rate was equal to 0.35 kg/h Productivity and product concentration probenecid was determined by gas chromatography, and the degree of conversion of hydrogen peroxide was determined by titration. The selectivity for hydrogen peroxide was calculated, taking into consideration the number. The results are presented in table 1.
Table 2 shows the values of the PKinfor the nitrogenous bases.
Evaluation of the experimental results, summarized in table 1, it is obvious that a high degree of conversion of hydrogen peroxide and values of selectivity can be maintained for a long period of time of the experiment, if the concentration of alkali metal is equal to less than 50 parts by weight per million, calculated on the weight of hydrogen peroxide. If you evaluate the comparative examples, it is obvious that in case of exceeding the specified limits for the ions of alkali metals and amines having a pk valueBbelow 4.5, the degree of conversion and selectivity of the catalyst over time is dramatically reduced. 1. An aqueous solution of hydrogen peroxide are suitable for the epoxidation of olefins, including: I) a total of less than 50 parts by weight per million of Molochny the metals, alkaline-earth metals or combinations thereof, regardless of whether these are alkaline or alkaline-earth metals in cationic or complex form; And in total, less than 50 parts by weight per million amines having a pk valueBless than 4.5, or the corresponding protonated compounds; and III) a total of at least 100 parts by weight per million anions or compounds that are capable of dissociate with the formation of anions, in accordance with the values in parts by weight per million specified in terms of the weight of hydrogen peroxide. 2. An aqueous solution of hydrogen peroxide according to claim 1, in which the number of components of group (I) in total amounts to less than 40 parts by weight per million, preferably less than 35 parts by weight per million, calculated on the weight of hydrogen peroxide. 3. An aqueous solution of hydrogen peroxide according to claim 1, in which the number of components group II) in total is less than 40 parts by weight per million, preferably less than 30 parts by weight per million, more preferably less than 20 parts by weight per million, and most preferably less than 10 parts by weight per million, calculated on the weight of hydrogen peroxide. 4. An aqueous solution of hydrogen peroxide according to claim 1, in which the amines are selected from primary, secondary and tertiary alkylamines followed. 5. An aqueous solution of hydrogen peroxide according to claim 1, further including: IV) a total of at least 100 parts by weight/ml of the grounds, with the value of the pkBat least 4.5, or the corresponding protonated compounds in terms of the weight of hydrogen peroxide. 6. An aqueous solution of hydrogen peroxide according to claim 5, in which the number of components group IV) a total of at most 3000 parts by weight per million, preferably from 150 to 2000 parts by weight per million, more preferably from 200 to 1500 parts by weight per million, and most preferably from 300 to 1200 parts by weight per million, calculated on the total weight of hydrogen peroxide. 7. An aqueous solution of hydrogen peroxide according to claim 5, in which the base of the group (IV) is chosen from organic amines and amides having a value pkBat least 4,5, organic hydroxylamines having a value pkBat least 4,5, ammonia and hydroxylamine, preferably ammonia. 8. An aqueous solution of hydrogen peroxide according to claim 1, in which the hydrogen peroxide concentration exceeds 50 wt.%, preferably more than 60 wt.%, most preferably ranges from 60 to 70 wt.% in terms of the total weight of hydrogen peroxide solution. 9. A method of producing hydrogen peroxide solution according to one of claims 1 to 8 is suitable for the epoxidation of olefins, in accordance with antrahinonovye technological circuit, comprising the following stages: (a) hydrogenation of a working solution comprising an organic solvent or mixture the organic solvents and one or more active antrahinonovye connections (b) oxidation of the hydrogenated working solution with obtaining hydrogen peroxide, (C) extraction of the hydrogen peroxide water, (g) stabilizing the extracted aqueous solution of peroxide of hydrogen (d) concentration of an aqueous solution of hydrogen peroxide to a concentration of hydrogen peroxide of at least 50 wt.% in recalculation on weight of a solution of hydrogen peroxide, (e) drying the working solution after extraction and (g) regenerative and clean working solution, thanks to that during the whole process either alkaline or alkaline-earth metals or amines having a pk valueBless than 4.5, or compounds forming such amines during the process, do not enter in quantities which cause concentration I) a total of 50 parts by weight per million or more of alkali metals, alkaline earth metals or combinations thereof, regardless of whether these are alkaline or alkaline-earth metals in cationic or complex form; or II) a total of 50 parts by weight per million or more amines having a pk valueBless than 4.5, or the corresponding protonated compounds; in the resulting aqueous solution of hydrogen peroxide, in accordance with the values in wt. hours/million specified in terms of the weight of the peroxide odor is Yes. 10. The method according to claim 9, in which the working solution free from organic nitrogen-containing compounds, drying of the working solution of stage e) is carried out without the use of compounds of alkali or alkaline-earth metals, and regenerative working solution at the stage f) carry out the processing of active aluminum oxide. 11. The method according to claim 10, in which the drying is carried out by evaporation of water under vacuum. 12. The method according to claim 9, in which no additional purification extracted aqueous solution of hydrogen peroxide is omitted. 13. The method according to claim 9, in which at least one base having a value pkBat least a 4.5, not including alkaline or alkaline-earth metals, add in the number of contributing content in total of at least 100 parts per million of such bases or the corresponding protonated compounds in terms of the weight of hydrogen peroxide in the final aqueous solution of hydrogen peroxide. 14. The method according to item 13, wherein the base is chosen from organic amines and amides having a value pkBat least 4,5, organic hydroxylamines having a value pkBat least 4,5, ammonia and hydroxylamine, preferably ammonia. 15. The method according to item 13, in which the base is added either at the time of receipt of the RA the creators of hydrogen peroxide, or at any stage between getting and end use of hydrogen peroxide solution. 16. The use of an aqueous solution of hydrogen peroxide according to one of claims 1 to 8, for the epoxidation of olefins. 17. The application of article 16, where the epoxidation is carried out in mixing with the water solvent and in the presence of a heterogeneous catalyst, preferably in the form of a fixed layer, in a flow reactor with continuous action. 18. The application 17 in which the solvent is methanol, the olefin is propene and the heterogeneous catalyst is titanosilicate catalyst.
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