A method of obtaining a perfluorinated epoxides
(57) Abstract:The invention relates to a method for producing oxides of perfluorinated olefins, which are of practical use as starting compounds to obtain some valuable organofluorine products. Perfluorinated epoxides obtained by oxidation of the corresponding olefins with oxygen at 15 - 120oC in the presence of initiators is chlorine, fluorine, bromine, triftormetilfullerenov, tetrafluoroethylene in an environment halon or perchloromethane fluid. Gaseous olefin is served in the flow of oxidant under a layer of inert solvent. Exit oxide hexaferrite 77% at a conversion of 78%, the yield of tetrafluoroethylene oxide 87% at a conversion of 93%. The developed method allows to increase the yield of fluorinated epoxides and increase the degree of conversion of the initial olefin, and create reliable industrial technology to obtain oxides of perfluoroolefins. 4 C.p. f-crystals, 1 table. The invention relates to the field of production of oxides of perfluorinated olefins, in particular, oxides of tetrafluoroethylene (OTFE) and oxide hexaferrite (EGFP), which are of practical use as starting products for the synthesis of perfluoroalkyl vinyl ether is TBE caustic soda and chlorine, surfactants, thermo-frost-resistant rubbers, oils, hydraulic fluids and other organofluorine products (Tarrant P. and others, Oxides of perfluoroolefins, IVHO them. Mendeleev, 1970, I. 15, No. 1, page 84).Known methods of oxidation farolatino hydrogen peroxide (Japan's Bid N 63-27487, 05.02.88), hypochlorites of alkali and alkaline earth metals (Japan's Bid N 59-110687, 26.06.84), nagkakamali (Ed. Mon. RF N 317651, 19.11.71), phenoxyimino acid (Patent Germany N 2557655, 30.06.77), anodic oxidation (Patent Germany N 2658328, 29.06.78). However, to date there is no convenient, safe industrial method of producing oxides of perfluorinated olefins, although work is in progress in several directions.Of all known methods, the most preferred is the oxidation of farolatino the most affordable and cheap oxidant is oxygen.A method of obtaining EGFP by liquid-phase oxidation of hexaferrite (HFP) with oxygen at a temperature of 70-120oC at pressures up to 5.0 MPa (50 ATM.) in solvent (Ed. Mon. RF N 608801, 30.05.78) in a steel reactor lined with Teflon, in the presence of a catalyst - Teflon chips, processed products of oxidation of the GUF. For Prigat is up to 140oC. Then begin to barbthroat air at a pressure of 5.0 MPa for 3 hours. After that, the reactor with the oxidation products of the GUF put Teflon shavings, then siphon off the solvent and boiling products. Thus prepared chips are placed in a reactor, fill up the freon and pre-cooled to minus 70oC GUF, heat the reactor up to 70-120oand at a pressure of 50 ATM. bubbled air. Reaction time from 15 to 30 minutes Selectivity reaches 84% at a conversion of 23%.The disadvantages of this method is the frequency, the complexity of the preparation of the catalyst, low conversion, high pressure and explosion hazards in the process.A method of obtaining fluorinated oxides by heating galeolaria CF2=CFX, where X is H, F, Cl, CF3, CF2H and others, with oxygen at an elevated pressure at a temperature of 50-250oC in the presence of inert diluent - N2, CO2, Ar, CF4C2F6, cyclo-C4H8ISO-C6F14, CCl4, CF2Cl2, CF2HCl, C2F3Cl3,
CF3CFBrCF2Br and others (U.S. Patent N 3536733, 27.10.70). Under this method in the autoclave load diluent (F-113) and olefin (TPV or d EGFP - 71%, with a conversion of 70%.The disadvantages of this method is the periodicity of the process and high pressure, which leads to the explosion process.The closest technical solution is the method of producing a tetrafluoroethylene oxidation of tetrafluoroethylene (TPV) by molecular oxygen in the presence of ozone at a temperature of 0-40oC in the environment of PERFLUORO - or perchlorobenzene liquid - 1,1,2-trichloro-1,2,2-triptoreline, tortiglioni, performatilicious (EXT. Mon. N 95620 to French patent N 1526663, 26.03.71). The molar ratio of C2F4:O3is 10:500. For carrying out the synthesis in a reactor filled PERFLUORO - or chlorpheniramine liquid, then with constant stirring in a reaction medium bubbled TPV and ozonized oxygen through two pipelines located at the base of the reactor. Output OTPA is 46-62% conversion TPV 45-58%.The disadvantages of this method include low output OTPA and low conversion TPV.The present invention is to increase the yield of fluorinated epoxides, increase the degree of conversion of the initial olefin, as well as the creation of a universal reliable industrial method of obtaining ainow oxygen in the presence of initiators, when the gaseous perfluoroolefin in the flow of oxidant under a layer of inert liquid at a temperature of 15-120oC.The process is carried out in a flow reactor, which is a cylindrical vessel with external heating and sockets for input of reactants and reaction products. The reagents are injected into the reactor through two tubes placed one inside the other (pipe in pipe), and the inner tube are doing is shorter than the outer, the output end of which is placed in the reactor under a layer of inert liquid. The reaction gases passing through the layer of liquid are discharged through a bottom outlet. To stabilize the process may further mixing of the reacting gases in an inert solvent.In the reactor inert fill fluid, the inner tube serves gaseous perfluoroolefin, and on the external oxygen from the initiator. In the case of oxidation of tetrafluoroethylene with oxygen may be filed with an inert diluent, such as nitrogen. When this mixture components and the oxidation of the olefin occurs at the entrance of gaseous olefin in the gaseous stream of oxidizing mixture under a layer of inert solvent.As the inert solvent used is ausina molecular weight and boiling temperature (150-300oC), and halocarbons, for example, 51-12 (1,6-dichlorphenoxy), 318 (perftorsilanami).As the initiator uses the halogen is chlorine, fluorine, bromine, tetrafluoroethylene, triftoratsetofenona. For the preparation of oxidation of a mixture of halogen and triftoratsetofenona add to oxygen in an amount of 0.1-15 vol. % and tetrafluoroethylene add to HEXAFLUOROPROPYLENE in an amount of 1-15%. The increase in the content of the initiator of the above limits is impractical because in all cases there is a growing number of by-products (carbonitride, triftoratsetofenona). When the content of the initiator is less than the specified limits sharply reduced conversion of a perfluoroolefin.The process is carried out continuously at a temperature of 15-70oC for the oxidation of tetrafluoroethylene and at 60-120oC for hexaferrite. At temperatures below the lower limit of the oxidation rate decreases along with the degree of conversion. The temperature increase leads to the increase of by-products at the expense of deeper oxidation.The reaction products containing perfluorinated epoxide, foramerica and unreacted olefin, condense when cooled to minus 120oC analyze method gazozhidkostnoi the ü hexaferrite with the release of 77.2% of the conversion to 78.3% and tetrafluoroethylene oxide with the release of 87% conversion 93,8%. Found the reception feeding and mixing of components allows to conduct the process in a continuous mode in milder conditions, to exclude his explosiveness and thus makes the process perspective for industrial development.Distinctive features of the proposed method are used as the initiator of halogen, triftormetilfullerenov and tetrafluoroethylene, and the gaseous olefin in the flow of oxidant under a layer of inert solvent. These features distinguishing the claimed method from the prototype, have been identified in other technical solutions.The following examples illustrate the invention.Example 1
In a cylindrical reactor jacketed and heated with a capacity of 310 cm3pour perchlorovinyl liquid 12FEET in the amount of 200 ml In Teflon, axially located tube lowered into the reactor serves gaseous components: internal - HFP with a speed of 3.0 l/h, on the outer - oxidizing mixture of oxygen with triftormetilfullerenov) with a speed of 6.0 liters/hour.The content of triftormetilfullerenov (CF3OF) to oxygen is equal to 5.5%. The volumetric ratio of HFP and oxidative dare composition, about. %: 51,2 EGFP; 18,4 HFP; 30.4 triftoratsetata and carbonitride. The reaction gases are passed through a 5% solution of sodium hydroxide to remove acidic impurities, and then dried in a column of calcium chloride and condense in the trap at a temperature of minus 120oC.The obtained raw rectificatum under pressure and produce 67,14 g EGFP 99.5% purity. Selectivity is 77.2% of the conversion of hexaferrite to 78.3%.Subsequent syntheses (examples 2-12) is carried out analogously to example 1. The conditions of oxidation farolatino and the results are shown in the table.Literature
1. Tarrant P., E. stump, Oxides of perfluoroolefins, IVHO them. Mendeleev, 15, 1, 84 (1970).2. Japan's bid N 63-27487, C 07 D 303/48, publ. 5.02.88, RICH 89, N.3. Japan's bid N 59-110687, C 07 D 301/03, publ. 26.06.84, RICH 85, N.4. Auth.mon. RF N 317651, C 07 D 301/12, publ. 126.96.36.199. Patent Germany N 2557655, C 07 D 301/16, publ. 30.06.77. Fig. for RUB, 1977, V. 24, N 13, S. 163.6. Patent Germany N 2658328, C 25 B 3/02, publ. 29.06.78. Fig. for RUB, 1978, V. 66, No. 11 C. 13.7. Auth.mon. RF N 608801, C 07 D 303/08, publ. 30.05.78.8. U.S. patent N 3536733, 260-348.5, publ. 188.8.131.52. EXT. mon. N 95620 to French patent N 1526663, C 07 D, publ. 26.03.71 (prototype). 2. The method according to p. 1, characterized in that the halogen-free and triftoratsetofenona adds to the oxygen in an amount of 0.1 to 15.0% vol.3. The method according to p. 1, characterized in that the olefin use HEXAFLUOROPROPYLENE, to which is added the tetrafluoroethylene in an amount of 1.0 to 15.0% vol.4. The method according to p. 1, wherein the process is conducted at 15 - 120oC.5. The method according to p. 1, characterized in that as the inert solvent used halocarbons and perchloroethane fluid.
FIELD: updated methods of recuperation of heat in CO2 discharge systems in production of ethylene oxide.
SUBSTANCE: proposed method includes absorption of ethylene oxide from circulating gas flow by washing the gas in scrubber. Washed flow of circulating gas is brought in contact with hot absorbing carbonate solution for absorption of CO2 and flow of circulating gas after absorption of CO2 returning it to ethylene oxide production cycle; proposed method includes also bringing the said washed circulating gas flow in contact with heated liquid after removal of ethylene oxide at first contact stage, transferring the preheated circulating gas to stage of absorption by hot carbonate for removal of CO2, cooling the said circulating gas from stage of absorption by carbonate and removal of carbonate from it by bringing it in contact with said liquid from first contact stage at second contact stage after cooling this liquid, transferring the liquid from second contact stage to first contact stage and transferring the cooled circulating gas from second contact stage to reaction system for obtaining the ethylene oxide.
EFFECT: enhanced operational and economical efficiency of heat recuperation.
1 dwg, 1 ex
SUBSTANCE: invention relates to catalyst supports used for epoxidation. Described is an olefin epoxidation catalyst support, wherein said support has pore volume from pores with diameter smaller than 1 mcm of less than 0.20 ml/g and pore volume from pores with diameter greater than 5 mcm of less than 0.2 ml/l, wherein at least 40% of the pore volume consists of pores having diameter from 1 mcm to 5 mcm. Described is an olefin epoxidation catalyst support, having a support and a catalytically effective amount of silver on it, wherein said support has pore volume from pores with diameter smaller than 1 mcm of less than 0.20 ml/g and pore volume from pores with diameter greater than 5 mcm of less than 0.2 ml/l, wherein at least 40% of the pore volume consists of pores having diameter from 1 mcm to 5 mcm. Described is an olefin epoxidation catalyst which has a support and a catalytically effective amount of silver on it, wherein said support has total pore volume of 0.2-0.6 ml/g, surface area from about 0.3 m2/g to about 3 m2/g, at least 40% of the pore volume from pores with diameter ranging from 1 mcm to 5 mcm and average pore diameter from 1 mcm to 5 mcm, an in which pore volume from pores with diameter greater than 5 mcm is less than 0.20 ml/g, and pore volume from pores with diameter smaller than 1 mcm is less than 0.20 ml/g. Described is a method of oxidising ethylene to ethylene oxide, which involves vapour-phase oxidation of ethylene with molecular oxygen in a fixed bet, in a tubular reactor in the presence of the catalyst described above.
EFFECT: high activity, selectivity and stability of the epoxidation catalyst.
19 cl, 4 tbl, 3 ex
SUBSTANCE: present invention relates to a method of producing alkylene glycol, which can be used as a raw material in production of polyester fibres, polyethylene terephthalate plastic and resins, as well as in antifreeze liquids. The method involves the following steps: (a) reaction of alkene with oxygen in the presence of a catalyst in a reactor to obtain a gaseous composition which contains alkylene oxide, alkene, oxygen, carbon dioxide and water vapour, and removing contaminants from the gaseous composition; (b) feeding the gaseous composition from step (a) into an alkylene oxide absorber, having a column of vertically stacked plates or having a packed column, feeding the impoverished absorbent into the alkylene oxide absorber, bringing the gaseous composition into contact with the impoverished absorbent in the alkylene oxide absorber in the presence of one or more catalysts which facilitate carboxylation and hydrolysis, and removing the saturated absorbent from the alkylene oxide absorber, where the impoverished absorbent contains at least 20 wt % and less than 80 wt % water, wherein at least 50 wt % alkylene oxide coming into the alkylene oxide absorber is converted in the alkylene oxide absorber and where temperature in the alkylene oxide absorber ranges from 50 to 160°C; (c) optionally feeding a portion or all of the saturated absorbent from step (b) into one or more final treatment reactors and removing the product stream from the one or more final treatment reactors, where at least 90% of alkylene oxide and alkylene carbonate coming into one or more final treatment reactors are converted to alkylene glycol in one or more final treatment reactors; (d) optionally feeding the saturated absorbent from step (b) or the product stream from at least one or more final treatment reactors at step (c) into a flash vessel or into an apparatus for evaporating light fractions, and removing the light fractions; (e) feeding the saturated absorbent from step (b) or (d) or the product stream from step (c) or (d) into a dehydrator, removing water and obtaining a stream of dehydrated product; and (f) purifying the stream of dehydrated product from step (e) and obtaining a product stream of purified alkylene glycol.
EFFECT: method enables to reduce the cost and complexity of the apparatus while ensuring high selectivity.
12 cl, 1 ex, 6 dwg
FIELD: process engineering.
SUBSTANCE: invention relates to olefin epoxidation. method of epoxidising of olefin to olefin oxide comprises the following operations: bringing the load including, at least, oxygen and olefin, in reactor with catalyst including carrier with bimodal pore distribution in sizes, first types of pores with mean diameter of 0.01-5 mcm and second type of pores with mean diameter of pores of 5-50 mcm, catalytically active amount of silver or silver-bearing compound, promoting amount of rhenium or rhenium-bearing compound, and promoting amount of one or more alkaline metals or alkaline metal-bearing compound. Note here that said reactor has, at least, its outlet, while said olefin oxide resulted from aforesaid contact features concentration at reactor outlet of 2.2 vol. % of cesium, lithium and tungsten. It may comprise bringing the load including, at least, oxygen and olefin, in reactor with catalyst including carrier with total volume of pores of 0.41 cm3/g and bimodal pore distribution in sizes, first types of pores making 25% of total volume of pores with mean diameter of 0.7 mcm and second type of pores making 75% of total amount of pores with mean diameter of pores of 15.8 mcm, catalytically active amount of silver or silver-bearing compound, promoting amount of rhenium or rhenium-bearing compound, and promoting amount of one or more alkaline metals or alkaline metal-bearing compound. Note here that said reactor has, at least, its outlet, while said olefin oxide resulted from aforesaid contact features concentration at reactor outlet over about of 2.2 vol. % at 236°C.
EFFECT: higher selectivity and efficiency.
34 cl, 2 tbl, 1 dwg, 2 ex
SUBSTANCE: invention relates to a method of producing plasticiser for polymer materials from renewable material, such as esters of fatty acids. In accordance with invention, plasticiser is obtained by oxidation of alkyl esters of fatty acids of vegetable origin with oxygen-containing gas in presence of homogeneous catalysts - molybdic acid esters, and aliphatic dihydric alcohols. Process of oxidising is preferably carried out at 100-120 °C and atmospheric pressure.
EFFECT: simplified process.
2 cl, 2 tbl, 12 ex
FIELD: technological processes.
SUBSTANCE: present invention relates to a method of producing ethylene glycol, involving following steps: (i) supplying ethylene and oxygen and an organic chloride moderator to an ethylene oxide reactor wherein ethylene and oxygen react in presence of a catalyst to produce ethylene oxide, thereby producing a reactor product stream; (ii) supplying reactor product stream to an ethylene oxide absorber wherein ethylene oxide is recovered from reactor product stream by absorption in water in absorber section, thereby producing a rich absorbent stream; (iii) supplying rich absorbent stream to an ethylene oxide stripper wherein rich absorbent stream is steam stripped, thereby producing a concentrated ethylene oxide stream and a lean absorbent stream; (iv) recirculating lean absorbent stream through ethylene oxide absorber; (v) optionally supplying concentrated ethylene oxide stream to one or more carboxylation reactors wherein ethylene oxide reacts with carbon dioxide to form an ethylene carbonate stream; and (vi) supplying concentrated ethylene oxide stream and/or ethylene carbonate stream to one or more hydrolysis reactors wherein ethylene oxide and/or ethylene carbonate reacts with water in presence of a hydrolysis catalyst selected from one or more basic alkali metal salts to form an ethylene glycol stream. Method includes additional steps: (vii) removing a glycol bleed stream from ethylene oxide stripper and (viii) adding a base to ethylene oxide stripper such that pH in bottom section of stripper is maintained in range of from at least 9.5 to at most 12.0.
EFFECT: proposed method reduces amount of chloroethanol present in reaction, and reduces or completely prevents decomposition of hydrolysis catalyst.
10 cl, 2 dwg
SUBSTANCE: invention relates to a method of producing epoxide of dicyclopentene (epoxide of tricyclo-[5,2,1,02.6]decene-3, 9-oxatetracyclo-[5,3,1,02.6,08.10]-undecane). The disclosed method involves hydrogenation of dicyclopentadiene in toluene solution with hydrogen at atmospheric pressure and moderate temperature (30-80°C) using finely dispersed platinum group catalysts and subsequent hydroperoxide oxidation of the obtained high-purity dicyclopentene in the presence of molybdenum-containing catalysts, at temperature of 80-110°C. Hydrogenation is carried out in the presence of an additive of functionally substituted aromatic compounds selected from a group comprising p-oxydiphenylamine, hydroquinone, β-naphthylamine, p-phenylenediamine and 2,6-ditert-butyl-4-methylphenyl, in amount of 1-5 wt % with respect to the catalyst used, and the dicyclopentene solution undergoes hydroperoxide oxidation directly in toluene without further separation of the dicyclopentene from hydrogenation products.
EFFECT: simple technique of producing the end compound and high output.
SUBSTANCE: method involves reaction of a terminal olefin with an oxidising agent in the presence of a catalyst in a two-phase system which contains an organic phase and aqueous reaction medium, the catalyst containing a water-soluble manganese complex, the terminal olefin having solubility at 20°C of at least 0.01-100 g per litre of water, and molar ratio of the terminal olefin to the oxidising agent ranging from 1:0.1 to about 1:1.
EFFECT: method enables to obtain an end product with large number of revolutions and high selectivity.
20 cl, 6 ex, 5 tbl