Novel phosphoneamides, method for their preparing and their using

FIELD: chemistry of organophosphorus compounds, chemical technology.

SUBSTANCE: invention relates to novel compounds used for extraction of rare-earth metal ions and comprising phosphoneamide compound represented by he formula [1]: wherein R1 means aryl group, aralkyl group under condition that each group can comprise a substitute chosen from alkoxy-groups; R2 means alkyl group, alkenyl group, aryl group, aralkyl group under condition that each group can comprise a substitute chosen from alkyl groups, alkoxy-groups; R3 means hydrogen atom, aryl group, aralkyl group under condition that each group can comprise a substitute chosen from alkyl groups, alkoxy-groups, halogen atoms; and two radical R can be combined to form alkylene group. Also, invention relates to a method for extraction of rare-earth metal ions and to a method for reverse extraction of rare-earth metal ions. Invention provides preparing novel phosphoneamide compounds and method for extraction and reverse extraction of rare-earth metal ions.

EFFECT: improved preparing method, valuable properties of compounds.

3 cl, 4 tbl, 44 ex

 

The technical field

This invention relates to a new phosphamidon connection, which is used as the extraction agent ion rare earth metal or similar, method thereof and method of extraction of the ion of the rare earth metal from the aqueous solution containing the ion of the rare earth metal, using the specified connection.

The level of technology

Rare earth elements (common name of scandium, yttrium and the 15 lanthanide elements) are used in large quantities as elements forming part of important materials, such as a magnet, abrasive hard drive, hydrogen batteries, catalyst for treatment of exhaust gases, drugs for imaging by NMR and the like. These elements are isolated and recovered from the above materials, as well as extracted from monazite, latest or centime, which are mineral ore, and clean.

As conventional methods of separation of rare earth elements are known (1) a method of ion exchange, (2) deposition method, and (3) the extraction solvent. Among them, the most effective method of allocation is the method (3)as the extraction solvent provides a continuous secretion of large quantities of rare earth element.

In the shown above method solvent extraction of rare earth element may be selected as the result of contacting an aqueous solution, containing rare earth element, with the extraction agent or an aqueous solution containing the extraction agent, and the transfer of an element from the aqueous layer in the organic layer. As the extraction agent can be applied widely known acidic compounds such as dialkylphosphorous acid and carboxylic acid, described on page 251 "Rare Metal Jiten" (editor Masao Douyama, publisher Fujitec Corporation, 1991), and neutral compounds such as phosphate esters, described on page 21 "Kidoruigenso No Called" (author N.E. Topp, translation Jiro Shiokawa and Ginya Adachi, publisher Called-Dojin Publishing Co. Inc., 1974).

However, when contacting with an aqueous solution containing rare earth element, the above acidic compounds release hydrogen ions in aqueous solution and significantly alter the characteristics of an aqueous solution, particularly the concentration of hydrogen ions in aqueous solution. This creates a problem, which is a large decrease in the transfer efficiency of rare earth element from the aqueous layer in the organic layer.

On the other hand, it is known that above the neutral compound prior art also create the problem, which lies in the low transfer efficiency of rare earth element from the aqueous layer in the organic layer.

Description of the invention

The purpose of this invention is the method of extraction and the rare-earth metal, in which ion rare earth metal can be effectively extracted by a simple operation and efficient extraction agent for the specified method.

The authors of this invention have conducted intensive studies for solving the above problems. As a result, they found that phosphoramide compound having a specific structure, can very effectively be used as an agent for the extraction of rare earth ion of the metal. Thus was created the invention.

This invention relates to phosphamidon the compound represented by the General formula [1]

(where R1is an alkyl group, cycloalkyl group, alkenylphenol group, cycloalkenyl group, alkenylphenol group, aryl group, aranceles group or heterocyclic group, provided that each group may have a Deputy; R2is a hydrogen atom, alkyl group, cycloalkyl group, alkenylphenol group, cycloalkenyl group, aryl group, aranceles group or heterocyclic group, provided that each group may have a Deputy; and R3is a hydrogen atom, alkyl group, cycloalkyl group, alkenylphenol group, cycloalkenyl group, aryl group and the alkyl group or the heterocyclic group, assuming that each group may have a substituent. Also in the formula two R3can be combined with education alkalinous group, cycloalkanones group or Allenova group).

Also, this invention relates to a method for producing the above phosphoramides connection, in which aminosidine or ammonium salt and phosphoryl compound is introduced into the reaction of the formation of ties phosphorus-nitrogen in the presence of a basic compound.

In addition, this invention relates to a method for producing the above phosphoramide compounds in which the amide of phosphoric acid and an ORGANOMETALLIC compound is introduced into the reaction of the formation of ties phosphorus-carbon.

Further, this invention relates to a method for producing the above phosphoramides connection, in which phosphoramide compound and the organic compound having a leaving group is introduced into the reaction of the formation of ties nitrogen-carbon.

Also, this invention relates to the extraction agent ion rare earth metal containing above phosphoramide connection.

Further, this invention relates to a method of extraction of the ion of the rare earth metal from the aqueous solution containing the ion of the rare earth metal, characterized by using the above phosphoramides connection as Agen is and extraction.

Further, this connection refers to the return path of the ion extraction of rare earth metal, wherein the layer of organic solvent containing the extracted ion rare earth metal, are mixed and injected into contact with water, thereby transferring metal ion in the aqueous layer.

The preferred embodiment of the present invention

In the above General formula [1] the alkyl group, if R1is an alkyl group which may have a Deputy, is, for example, linear or branched alkyl group having from 1 to 40 carbon atoms, preferably from 1 to 30 carbon atoms, more preferably from 1 to 18 carbon atoms, preferably, for example, methyl group, ethyl group, n-sawn group, isopropyl group, n-, ISO-, sec - or tert-bucilina group, n-, ISO-, sec-, tert - or neo-pencilina group, n-exilda group, n-anjilina group, 2-aktiline group, 2-ethylhexyl group, n-nanlina group, n-decile group, n-Godzilla group, catilina group and the like.

Cycloalkyl group, if R1is cycloalkyl group which may have a Deputy, is, for example, monocyclic or polycyclic cycloalkyl group having 5 to 30 carbon atoms, preferred is compulsory from 5 to 20 carbon atoms, more preferably from 5 to 10 carbon atoms, preferably cyclopentene group, tsiklogeksilnogo group, cyclooctyl group and the like.

Alkenylphenol group, if R1is alkenylphenol group which may have a Deputy, for example, is one of the above alkyl groups having 2 or more carbon atoms, having at least one double bond, preferably, for example, vinyl group, allyl group, 1-protanilla group, Isopropenyl group, 2-bucinellina group, 1,3-butadienyl group, 2-penttila group, 2-examilia group and the like.

Cycloalkenyl group, if R1is cycloalkenyl group which may have a Deputy, for example, is one of the above cycloalkyl groups having at least one unsaturated bond such as a double bond, preferably, for example, cyclopentenyl group, cyclohexenyl group and the like.

Alkenylphenol group, if R1is alkenylphenol group which may have a Deputy, for example, is one of the above alkyl groups having 2 or more carbon atoms, having at least one unsaturated bond, such as a triple bond, preferably, for example, those who ilen group, 1-proponila group, 2-proponila group and the like.

Aryl group, if R1is an aryl group which may have a Deputy, is, for example, monocyclic, polycyclic or condensed cyclic aryl group having from 6 to 42 carbon atoms, preferably from 6 to 26 carbon atoms, more preferably from 6 to 22 carbon atoms, preferably phenyl group, naftalina group, biphenylene group and the like.

Aranceles group, if R1is aranceles group which may have a Deputy, is, for example, monocyclic, polycyclic or condensed cyclic kalkilya group having from 7 to 30 carbon atoms, preferably from 7 to 20 carbon atoms, more preferably from 7 to 15 carbon atoms, preferably benzyl group, penicilina group, naphthylmethyl group, naphthylethylene group and the like.

Heterocyclic group, if R1is a heterocyclic group which may have a Deputy, is, for example, saturated or unsaturated monocyclic, polycyclic or condensed cyclic heterocyclic group having at least one nitrogen atom, oxygen atom or sulfur atom in the ring, to who m the one ring is a 5-20-membered ring, preferably 5-10-membered ring, more preferably a 5-7 membered ring, and condensed above cycloalkyl group, cycloalkenyl group or aryl group, preferably Peregrina group, Taanilinna group, phenylthiourea group, thiazolidine group, furilla group, piperideine group, piperacilline group, pyrrolidine group, morpholinopropan, imidazolidine group, indayla group, kinolinna group, piramidalnaya group and the like.

As Deputy alkyl group, cycloalkyl group, alkenylphenol group, cycloalkenyl group, alkenylphenol group, aryl group, aranceles group and heterocyclic group may be any Deputy who is not involved in the production method of the compounds in accordance with this invention and does not have a negative impact when phosphoramide the connection represented by the General formula [1], is used as an agent for the extraction of rare earth ion of the metal. For example, can be used alkoxygroup consisting of the above alkyl groups (such as methoxy group, ethoxypropan, isopropoxide, tert-butoxypropyl, 2-ethylhexyloxy or aktionsgruppe), allylthiourea (such as methylthiourea or ethylthiourea), dialkylamino (such as dimethyl who kinogruppa or diethylaminopropyl), tizamidine silyl group (such as trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group or triphenylsilane group), tizamidine celoxica (such as trimethylsiloxy, triethylsilyl, tert-butyldimethylsiloxy or triphenylsilane), halogen atom such as chlorine, bromine, fluorine or iodine, alkylenedioxy, such as methylendioxy or dimethylethylenediamine, cyano and the like.

Also, if R1General formula [1] for the above alkyl group, cycloalkyl group, alkenylphenol group, cycloalkenyl group, alkenylphenol group, aryl group, aranceles group and heterocyclic group there is a possibility of substitution groups to each other, these groups can be substituted for each other. For example, can be alkyl-substituted cycloalkyl group, alkyl-substituted aryl group, alkyl-substituted cycloalkenyl group, alkyl-substituted kalkilya group, cycloalkyl-substituted alkyl group, cycloalkyl-substituted Alchemilla group, cycloalkyl-substituted Alchemilla group, alkenyl-substituted aryl group, the aryl-substituted Alchemilla group, aryl-substituted Alchemilla group and the like.

In General formula [1] definitions and specific examples of the alkyl group, if R 2is an alkyl group which may have a Deputy, cycloalkyl group, in the case cycloalkyl group which may have a Deputy, alkenylphenol group, in the case alkenylphenol group which may have a Deputy, cycloalkenyl group, in the case cycloalkenyl group which may have a Deputy, aryl group, in the case of the aryl group which may have a Deputy, aranceles group, in the case aranceles group which may have a Deputy, and heterocyclic group, in the case of the heterocyclic group which may have a Deputy, and definitions and examples of substituents are the same as for R1respectively.

In General formula [1] definitions and specific examples of the alkyl group, if R3is an alkyl group which may have a Deputy, cycloalkyl group, in the case cycloalkyl group which may have a Deputy, alkenylphenol group, in the case alkenylphenol group which may have a Deputy, cycloalkenyl group, in the case cycloalkenyl group which may have a Deputy, aryl group, in the case of the aryl group which may have a Deputy, aranceles group, in the case aranceles group which may have a Deputy, and heterocyclic group, in the case of heterocycle eskay group, which may have a Deputy, and definitions and examples of substituents are the same as for R1respectively.

Also Allenova group, cycloalkenes group or Allenova group, when two R3in the formula combined with education alkalinous group, cycloalkanones group or Allenova group is a divalent group that is formed by removing one hydrogen atom of the above alkyl groups, cycloalkyl group and aryl group, respectively. Example alkalinous group is a linear or branched Allenova group having from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferably from 1 to 6 carbon atoms, preferably, for example, methylene group, ethylene group, trimethylene group, metilidinovy group, tetramethylene group, 1,2-dimethylethylene group, pentamethylene group, hexamethylene group and the like.

Example cycloalkanones group is a monocyclic, polycyclic or cycloalkenes group condensed cycles, having 3 to 30 carbon atoms, preferably from 3 to 20 carbon atoms, more preferably from 3 to 10 carbon atoms, preferably cyclopropylamino group, cyclopentyloxy group, the cycle is jaksilikova group, cyclooctylamino group and the like.

Example Allenova group is monocyclic, or polycyclic divalent aromatic hydrocarbon group condensed cycles, having from 6 to 30 carbon atoms, preferably from 6 to 20 carbon atoms, more preferably from 6 to 14 carbon atoms, preferably, for example, fenelonov group, Torrenova group, killenemy group, naftalanovaja group, methylnaphthalene group, biphenylene group and the like.

Phosphoramide connection in accordance with this invention represented by the General formula [1]can be obtained by the interaction of the amino compounds or ammonium salt and phosphoryl connection with the formation of the connection, the phosphorus-nitrogen in the presence of a basic compound.

As phosphoryl compounds in the above method is used, for example, a compound represented by the General formula [2]

(where R1described above; X1is a leaving group).

As the amino compounds in the above production method of use, for example, a compound represented by the General formula [3]

R2R4NH[3]

(where R2described above; R4is a hydrogen atom, alkyl group, cycloalkyl group, alkenylphenol group, cycloalkane Inoi group, aryl group, aranceles group or heterocyclic group, provided that each group may have a Deputy), the compound represented by the General formula [4]

R2NH-R5-Other2[4]

(where R2described above; R5is alkalinous group, cycloalkanones group or Allenova group) and the like.

As the ammonium salt in the above method is used, for example, a compound represented by the General formula [5]

R2R4NH2X2[5]

(where R2and R4defined above; X2is an anionic group), the compound represented by the General formula [6]

X2R2NH2-R5-NH2R2X2[6]

(where R2, R5and X2defined above) and the like.

In the above General formula [2] leaving group represented by X1not limited to, until it can be easily replaced with a new connection, the phosphorus-nitrogen in the method of obtaining, in accordance with this invention, and is, for example, a halogen atom such as chlorine, bromine or iodine, alkoxygroup, such as a methoxy group, ethoxypropan, isopropoxy or tert-butoxypropan, arroceros, such as fenoxaprop or naftussya, alkylthiol, such as methylthiourea or ethylthiourea, Ari is tigraphy, such as phenylthiourea, tolylthiourea or naphthylthiourea, and the like.

The alkyl group represented by R4that may have a Deputy, and other monovalent groups in the above formulas [3] and [5], and Allenova group represented by R5and other divalent group in the General formula [4] and [6] correspond to a monovalent group, and the divalent group represented by R3in the above General formula [1], respectively.

In the above formulas [5] and [6] the anionic group represented by X2for example, in addition to the halide ion such as chloride ion, bromide ion or iodide ion may be represented by various anionic groups, such as hypochlorite ion, perchlorate ion, triftorbyenzola ion, pentafluorobenzenesulfonyl ion, tetrafluoroborate ion, hexaflurophosphate ion, p-toluensulfonate ion, bansilalpet ion, methanesulfonate ion, a hydroxide ion, triptorelin ion, pentafluorobenzoate ion, acetate ion, a benzoate ion and tartrate ion.

In the reaction of the compounds represented by the General formula [2]with the compound represented by the General formula [3], or compounds represented by the General formula [2]with the compound represented by the General formula [5], is equivalent to the amount used of the compound represented by the General formula [3] or General formula [5], is not limited, however, the usual it ranges from 1.5 to 20 equivalents, preferably from 2 to 10 equivalents relative to the compound represented by the General formula [2].

In the reaction of the compounds represented by the General formula [2]with the compound represented by the General formula [4], or compounds represented by the General formula [2]with the compound represented by the General formula [6], an equivalent amount of used compounds represented by the General formula [4] or General formula [6], is not limited, however, it usually ranges from 0.5 to 10 equivalents, preferably 1 to 5 equivalents relative to the compound represented by the General formula [2].

The reaction of the compound represented by the General formula [2]with the compound represented by any of General formulas [3]-[6], can be performed at different temperatures, however, it is usually performed at a temperature of from -100 to 180°C, preferably from -70 to 150°C.

The reaction of compounds represented by the General formula [2]with the compound represented by any of General formulas [3]-[6], it is preferable in any case to apply the solvent.

The solvent can be used in various hydrocarbon solvents, ethers, highly polar aprotic solvents. Specific examples include, for example, hexane, decane, benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, N,N-dimethylformamide, acetonic is l, benzonitrile, hexamethylene phosphoric acid, dimethyl sulfoxide and the like. The amount of solvent is not limited, however, it usually ranges from 0.1 to 100 ml, preferably from 1 to 20 ml, relative to 1 mmol of the compound represented by the General formula [2]. Also, if applicable, the basis has the form of a liquid at the above temperatures, it can be used as a solvent.

In the reaction of the compounds represented by the General formula [2]with the compound represented by any of General formulas [3]-[6], a favorable reaction rate is achieved when applying Foundation.

As the base can be used inorganic or organic bases. Specific examples include, for example, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium acetate, sodium acetate, potassium acetate, magnesium oxide, calcium oxide, barium hydroxide, teletypist, trisodium phosphate, tribalistic, cesium fluoride, cesium carbonate, aluminum oxide, trimethylamine, triethylamine, tributylamine, N,N,N',N'-tetramethylethylenediamine, diisopropylethylamine, N-methylpiperidine, 2,2,6,6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine, atoxic sodium tert-piperonyl potassium and the like.

The base used in the ratio of from 0.01 to 100 equivalents, PR is doctitle from 0.1 to 20 equivalents, with respect to the compound represented by the General formula [2]. Also each of these bases can be used in pure form or in combination with other grounds. Next, compounds represented by the above General formula [3] or [4], can also be used as a basis.

Phosphoramide connection in accordance with this invention represented by the General formula [1]can also be obtained by the reaction of formation of carbon-phosphorus between Amida phosphoric acid and an ORGANOMETALLIC compound.

As the amide of phosphoric acid in the above production method of use, for example, a compound represented by the following General formula [7]

(where R2and R3described above; X3is a leaving group).

As ORGANOMETALLIC compounds in the above production method of use, for example, a compound represented by the General formula [8]

R1-M[8]

(where R1described above; M is metallography).

In the above General formula [7] leaving group represented by X3not limited to, until it can be easily substituted with the formation of new carbon-phosphorus in the method of obtaining, in accordance with this invention, and is, for example, a halogen atom, so the AK chlorine, bromine or iodine, alkoxygroup, such as a methoxy group, ethoxypropan, isopropoxy or tert-butoxypropan, arroceros, such as fenoxaprop or naftussya, alkylthiol, such as methylthiourea or ethylthiourea, arylthioureas, such as phenylthiourea, tolylthiourea or naphthylthiourea, and the like.

In the above General formula [8] as metallography represented by M, apply the metal 1 or group 2 of the Periodic table or its derivative, specific examples of which include, for example, lithium, harmegnies group, romagnieu group, yodmanee group and the like.

In the reaction of the compounds represented by the General formula [7], with the compound represented by the General formula [8], an equivalent amount of used compounds represented by the General formula [8], is not limited, however, it usually ranges from 0.5 to 10 equivalents, preferably 1 to 5 equivalents relative to the compound represented by the General formula [7].

The reaction of the compound represented by the General formula [7], with the compound represented by the General formula [8], can be performed at different temperatures, however, it is usually performed at a temperature of from -100 to 180°C, preferably at a temperature of from -70 to 150°C.

In the reaction of the compounds represented by the General formula [7], Saedinenie, represented by the General formula [8], it is preferable to use a solvent.

The solvent can be used in various hydrocarbon solvents, ethers, highly polar aprotic solvents. Specific examples include, for example, hexane, decane, benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, hexamethylene phosphoric acid and the like. The amount of solvent is not limited, however, it usually ranges from 0.1 to 100 ml, preferably from 1 to 20 ml, relative to 1 mmol of the compound represented by the formula [5].

Phosphoramide connection in accordance with this invention represented by the General formula [1]can also be obtained by the interaction of the acidic phosphoramide compounds and organic compounds having a leaving group, with formation of carbon-nitrogen.

Sour phosphoramide connection in accordance with this invention is phosphoramide connection with one atom of hydrogen or more, attached to the nitrogen atom.

As acidic phosphoramides connection in the above production method of use, for example, a compound represented by the following General formula [9]

(where R1and R3defined above).

As organic compounds having a leaving group, in the above method of obtaining used as a compound represented by the General formula [10]

R2-X4[10]

In the above General formula [10] leaving group represented by X4not limited to, until it can be easily substituted with the formation of new carbon-nitrogen method of obtaining, in accordance with this invention, and, in addition to the halogen atom such as chlorine atom, bromine atom or iodine atom, can be used different leaving groups, including the group iodone, such as acetoacetanilide or phenyl(tripterocalyx)iodone, sulfonyloxy group, such as methanesulfonyl group or trifloromethyl group, and the like.

In the reaction of the compounds represented by the General formula [9], with the compound represented by the General formula [10], a favorable reaction rate is achieved when applying Foundation.

As the base, in addition to the grounds specified for the reaction of compounds represented by the General formula [2]with the compound represented by any of General formulas [3]-[6], can be applied hydride compound of the metal, such as sodium hydride or alumoweld lithium amide compound of the metal, such as diisopropylamide lithium, lithium amide or sodium amide, ORGANOMETALLIC compound represented by the above General formula [8 (where R 1and M such as described above), and the like. The base used in the ratio of from 0.01 to 100 equivalents, preferably from 0.1 to 20 equivalents relative to the compound represented by the General formula [9]. Each of the bases can be used in pure form or in combination with other grounds.

An equivalent amount of used compounds represented by the General formula [10], in the reaction of the compounds represented by the General formula [9], with the compound represented by the General formula [10], is not limited, and it usually ranges from 1.5 to 10 equivalents, preferably 2 to 5 equivalents relative to the compound represented by the General formula [9].

The reaction of the compound represented by the General formula [9], with the compound represented by the General formula [10], can be carried out at different temperatures, but usually it is carried out at a temperature of from -100 to 180°C, preferably from -70 to 150°C.

The reaction of compounds represented by the General formula [9], with the compound represented by the General formula[10], it is preferable to use a solvent.

The solvent can be used in various hydrocarbon solvents, ethers, highly polar aprotic solvents. Specific examples include, for example, hexane, decane, benzene, toluene, xylene, diethyl ether, Tetra drofuran, dioxane, hexamethylene phosphoric acid, acetonitrile and the like. The amount of solvent is not limited, however, it usually ranges from 0.1 to 100 ml, preferably from 1 to 20 ml, relative to 1 mmol of the compound represented by the formula [9].

The obtained compound phosphoramide can be cleaned by known methods, such as distillation, column chromatography and recrystallization.

Phosphoramide connection in accordance with this invention can be used as an agent for the extraction of rare earth metal.

Extraction of rare earth metal with the use of phosphoramide compounds in accordance with this invention as an agent for the extraction is carried out by mixing and introduction to the contact of the aqueous solution containing the ion of the rare earth metal, phosphoramide compounds represented by the General formula [1], and an organic solvent, at a suitable temperature by means such as stirring or shaking, and carrying out separation of layers in the organic layer (the layer of extraction agent and an aqueous layer.

As the organic solvent for extraction is preferably used a solvent which can dissolve phosphoramide connection in accordance with this invention and which is not full of the stew miscible with water, examples include halogenated hydrocarbons, hydrocarbons, ethers, alcohols, nitro compounds, phosphate esters, and the like. Specific examples include chloroform, carbon tetrachloride, methyl isobutyl ketone, nitrobenzene, octanol, hexane, octane, decane, dodecane, benzene, toluene, xylene, ethylbenzene, tributyl phosphate and the like.

Each of these organic solvents can be used in pure form, or more organic solvents may be used in combination. If phosphoramide the connection represented by the General formula [1]is a liquid and not completely miscible with water, phosphoramide connection can serve as an organic solvent (solvent extraction).

It is desirable to maintain the pH value of an aqueous solution containing the ion of the rare earth metal, which is used for the extraction, the pH of 7 or below by means of an appropriate acid. The acid can be used various inorganic and organic acids, specific examples include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, carbonic acid, phosphoric acid, citric acid, tartaric acid, ethylenediaminetetraacetic acid and the like.

Each of these acids may be used in pure form or in the op is Tania's story with others if necessary.

The concentration of ions of rare-earth metal contained in the aqueous solution when carrying out the extraction is not limited, but usually ranges from 1.0·10-9up to 10 mol/l, preferably from 5.0·10-7to 5.0 mol/L.

The number of moles phosphoramide compounds represented by the General formula [1]used for the extraction is not limited, but preferably, it is 0.01-fold or more relative to the total number of ions of rare-earth metal.

The volumetric ratio of the aqueous solution containing the ion of the rare earth metal to an organic solvent containing phosphoramide connection, which is used for the extraction is not limited, but is usually from 0.001:1 to 100:1, preferably from 0.02:1 to 50:1.

The temperature of extraction when performing the extraction is not limited, but usually it ranges from 0 to 100°C, preferably from 10 to 70°C.

Ion rare earth metal extracted and transferred from the aqueous layer into the layer of organic solvent extraction conditions can be back extracted from the layer of organic solvent in the aqueous layer contacting the layer of organic solvent with water, other than water layer.

By mixing and contacting the layer of organic solvent containing rare-earth ion is atalla, extracted the above method of extraction, with water metal ion can be transferred into the aqueous layer, thus ion rare earth metal can be back extracted into the water layer.

In the way back extraction in accordance with this invention as water used for back-extraction ion rare earth metal from the layer of organic solvent containing the extracted ion rare earth metal, it is preferable to use acid or acidic water. Preferably, the pH of the water used for back-extraction was below pH 7, which is achieved by use of a suitable acid. As the acid used to maintain the pH, use of various inorganic and organic acids, specific examples include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, carbonic acid, phosphoric acid, citric acid, tartaric acid, ethylenediaminetetraacetic acid and the like. Each of these acids may be used in pure form or in combination with other acids, if necessary. The pH adjustment can be carried out with the use of salts of acids, various buffer agents (buffer solutions) or the like, instead of acid.

The volumetric ratio of the organic layer to aq is th layer, which is used for the back extraction is not limited, but usually it is from 0.001:1 to 1000:1, preferably from 0.02:1 to 50:1.

The temperature of the back extraction is not limited, but usually it ranges from 0 to 100°C, preferably from 10 to 70°C.

Full description contained in the application JP-A-2002-057419 included in this description.

Examples

Below the invention is explained in more detail using examples, which, however, do not limit the scope of the present invention.

Example 1

In a glass bottle 1.44 g (10 mmol) of N,N'-diisopropylethylamine (General formula [4], R2= ISO-propyl group, R5= ethylene group), 0.24 g (2 mmol) of 4-dimethylaminopyridine and 3 ml of triethylamine dissolved in 50 ml of tetrahydrofuran, and the capacity is kept in a water bath. There gradually add 1,95 g (10 mmol) dichlorophenylphosphine acid (General formula [2], R1= phenyl group and X1= a chlorine atom) and stirred for 5 hours. The reaction mixture is filtered and 1,94 g (7.3 mmol) of 2,5-diaza-2,5-aminobutiramida-1-oxo-1-phenylphosphine (General formula [1], R1= phenyl group, R2= the isopropyl group and two R3combined with the formation of the ethylene group) obtained by distillation of the residue under reduced pressure (180°C/2 mm RT. Art.), which receive koncentrira is of the filtrate under reduced pressure. This connection is a new connection that has not yet been described.

The spectral data and the results of elemental analysis of the compound obtained in example 1, below.

1H-NMR (CDCl3that δ 0,85-0,90 (6N, m), 1,07-1,22 (6H, m), 3,12-3,19 (2H, m), 3,26-to 3.35 (4H, m), 7,32-7,38 (3H, m), 7,71-7,79 (2H, m).

l3C-NMR (CDCl3that δ, ppm): 20,5 (d, J=4.3 Hz), 21,5 (d, J=2.3 Hz), and 39.9 (d, J=9.8 Hz)and 44.6 (d, J=6.2 Hz), USD 128.0 (d, J=30,5 Hz), 128,7 (d, J=156,7 Hz), 131,0 (d, J=2,9 Hz), to 132.8 (d, J=13.3 Hz).

31P-NMR (CDCl3that δ, ppm): 24,3.

MS (EI): m/z 266,77.

Elemental analysis calculated for C14H23ON2P: C, 63,14; H, TO 8.70; N, 10,52%. Found: C, 63,02; H, 8,81; N, 10,45%.

Example 2

In a glass bottle 1.44 g (10 mmol) of N,N'-dipropylenetriamine (General formula [4], R2= sawn group, R3=ethylene group), 0.24 g (2 mmol) of 4-dimethylaminopyridine and 3 ml of triethylamine dissolved in 50 ml of tetrahydrofuran, and the capacity is kept in a water bath. There gradually add 1,95 g (10 mmol) dichlorophenylphosphine acid (General formula [2], R1= phenyl group and X1= a chlorine atom) and stirred for 5 hours. The reaction mixture is filtered and 1.51 g (5.7 mmol) of 2,5-diaza-2,5-dipropyl-1-oxo-1-phenylphosphine (General formula [1], R1= phenyl group, R2= various group and two R3combined with the formation of the ethylene group) receive distilla what their residue under reduced pressure (180° With/2 mm RT. Art.), which is obtained by concentration of the filtrate under reduced pressure. This connection is a new connection that has not yet been described.

The spectral data and the results of elemental analysis of the compound obtained in example 2, below.

1H-NMR (CDCl3that δ 0,76 (6N t, J=7,3 Hz), 1,37-1,49 (4H, m), 2,67 is 2.75 (4H, m), 3,20-and 3.31 (2H, m), 3,37 is 3.40 (2H, m), 7,38-the 7.43 (3H, m), 7.68 per-7,72 (2H, m).

l3C-NMR (CDCl3that δ, ppm): 11,7, 21,7 (d, J=4,1 Hz)45,7 (d, J=9.3 Hz), 46,9 (d, J=5,2 Hz), 128,1 (d, J=13,4 Hz), 131,2 (d, J=3.1 Hz), 132,4 (d, J=156.3 Hz), 132,5 (d, J=9,3 Hz).

31P-NMR (CDCl3that δ, ppm): 28,3.

MS (EI): m/z 266,77.

Elemental analysis calculated for C14H23ON2P: S, 63,14; H, TO 8.70; N, 10,52%. Found: C, 63,08; H, 8,76; N, 10,47%.

Example 3

In a glass bottle, a 2.12 g (10 mmol) of N,N'-diphenylethylenediamine (General formula [4], R2= phenyl group, R5=ethylene group), 0.24 g (2 mmol) of 4-dimethylaminopyridine and 3 ml of triethylamine dissolved in 50 ml of tetrahydrofuran, and the capacity is kept in a water bath. There gradually add 1,95 g (10 mmol) dichlorophenylphosphine acid (General formula [2], R1= phenyl group and X1= a chlorine atom) and stirred for 5 hours. The reaction mixture is filtered and of 2.56 g (of 7.70 mmol) of 2,5-diaza-1-oxo-1,2,5-triphenylphosphorane (General formula [1], R1=R2= phenyl group, and two R3bhavnani with the formation of the ethylene group) obtained by distillation of the residue under reduced pressure (180° With/2 mm RT. Art.), which is obtained by concentration of the filtrate under reduced pressure. This connection is a new connection that has not yet been described.

The spectral data and the results of elemental analysis of the compound obtained in example 3, below.

1H-NMR (CDCl3that δ, ppm): 3,93-a 4.03 (4H, m), 6,92 (2H, t, J=7.2 Hz), 7,15-7,24 (8H, m), 7,37-7,40 (3H, t), 7,81-a 7.85 (2H, t).

l3C-NMR (CDCl3that δ, ppm): 43,8 (d, J=8.6 Hz), 116,5 (d, J=4,8 Hz), the level of 121.8, 128,7 (d, J=14,5 Hz), 129, 2mm, 132,1, 132,2 (d, J=3.1 Hz), 132,5 (d, J=10,7 Hz), 141, 3mm (d, J=7,6 Hz).

31P-NMR (CDCl3that δ, ppm): 18,8.

MS (EI): m/z 334,77.

Elemental analysis calculated for C20H19ON2P: C, 71,85; H, 5,73; N, 8.38%AS. Found: C, 71,83; H, 5,64; N, 8,30%.

Example 4

In glass containers of 4.11 g (20 mmol) of p-octylaniline (General formula [3], R2= p-octylaniline group, and R4= a hydrogen atom) and 3 ml of triethylamine dissolved in 50 ml of acetonitrile, and the capacity is kept in a water bath. There gradually add 1,95 g (10 mmol) dichlorophenylphosphine acid (General formula [2], R1= phenyl group and X1= a chlorine atom), stirred for 1 hour and then stirred for 1 hour at the boil under reflux. The resulting reaction mixture is filtered and 3.19 g (5,98 mmol) of N,N'-bis(p-octylphenyl)phenylphosphonite (General formula [1], R1= phenyl group, R2= p-octyl anilina group, and R 3= a hydrogen atom) is obtained by recrystallization of the resulting solid from ethyl acetate. This connection is a new connection that has not yet been described.

The spectral data and the results of elemental analysis of the compound obtained in example 4, below.

1H-NMR (CDCl3that δ, ppm): of 0.87 (6H, t, J=7.0 Hz), 1,25 (20H, users), 1,50-and 1.54 (4H, m), 2,48 (4H, t, J=7.5 Hz), 5,38 (2H, d, J=9.6 Hz), 6,94 (8H, s), 7,39-of 7.48 (2H, m), 7,49-of 7.55 (1H, m), of 7.90 (2H, DD, J=6,9, and 13.4 Hz).

l3C-NMR (CDCl3that δ, ppm): 14,1, 22,6, 29,2, 29,4, 30,9, 31,5, 31,9, 35,1, 118,5 (d, J=6.2 Hz), 128,7 (d, J=13.5 Hz), 129,1, 130,4 (d, J=173,7 Hz), 131,7 (d, J=10.3 Hz), 132,3, 136,6, 137,5.

31P-NMR (CDCl3that δ, ppm): 10,0.

Elemental analysis calculated for C34H49ON2P: S, 76,65; H, 9,27; N, 5,26%. Found: C, 76.86 Euros; H, 9,27; N,5,15%.

Example 5

In a glass bottle 6,63 g (30 mmol) of p-activationlink (General formula [3], R2= p-octyloxyphenyl group, and R4= a hydrogen atom) and 9 ml of triethylamine are dissolved in 60 ml of acetonitrile, and the capacity is kept in a water bath. There is gradually added with 2.93 g (15 mmol) dichlorophenylphosphine acid (General formula [2], R1= phenyl group and X1= a chlorine atom), stirred for 1 hour and then stirred for 1 hour at the boil under reflux. The reaction mixture is filtered and 4,88 g (7,60 mmol) of N,N'-bis(p-octyloxyphenyl)f is of nilpotence (General formula [1], R1= phenyl group, R2= p-octyloxyphenyl group, and R3= a hydrogen atom) is obtained by recrystallization of the resulting solid from ethyl acetate. This connection is a new connection that has not yet been described.

The spectral data and the results of elemental analysis of the compound obtained in example 5, below.

1H-NMR (CDCl3that δ, ppm): from 0.88 (6H, t, J=6.9 Hz), 1.28 (in 16H, users), 1,36-of 1.41 (4H, m), 1.70 to 1.77 in (4H, cunt, J=7.5 Hz), 5,11 (2H, d, J=9.1 Hz), of 6.71 (4H, d, J=8,4 Hz), 6,98 (4H, d, J=8,4 Hz), 7,41-the 7.43 (2H, m), 7,44-7,46 (1H, m), 7,83-of 7.90 (2H, m).

l3C-NMR (CDCl3that δ, ppm): 14,1, 22,6, 26,0, 29,2, 29,3, 29,7, 31,8, 68,3, 115,2, 120,8 (d, J=6.2 Hz), of 128.6 (d, J=13.5 Hz), 131, 6mm (d, J=157,2 Hz), 131, 6mm (d, J=10.4 Hz), 132,2, 132,7, 154,7.

31P-NMR (CDCl3that δ, ppm): 10,9.

Elemental analysis calculated for C34H49O3N2P: C, 72,31; H, IS 8.75; N, 4,96%. Found: C, 72,64; H, Of 8.92; N, Equal To 4.97%.

Example 6

In a glass bottle 6,69 g (10 mmol) of dihydrobromide N,N'-dietilatsetamida (General formula [6], R2= catilina group, R5= ethylene group and X2= bromide ion), 0.24 g (2 mmol) of 4-dimethylaminopyridine and 3 ml of triethylamine dissolved in 50 ml of tetrahydrofuran, and the capacity is kept in a water bath. There gradually add 1,95 g (10 mmol) dichlorophenylphosphine acid (General formula [2], R1= phenyl group and X1= a chlorine atom) and premesis the ut for 5 hours. The resulting reaction mixture is filtered and 1.58 g (2.5 mmol) of 2,5-diaza-2,5-Dicetyl-1-oxo-1-phenylphosphine (General formula [1], R1= phenyl group, R2= catilina group and two R3combined with the formation of the ethylene group) is obtained by purification of the residue obtained by concentration of the filtrate under reduced pressure, chromatography on a column of silica gel using hexane as eluent. This connection is a new connection that has not yet been described.

The spectral data and the results of elemental analysis of the compound obtained in example 6, below.

1H-NMR (CDCl3that δ, ppm): from 0.84 (6H, t, J=6.9 Hz), 1,13 (4H, users), a 1.25 (48H, users), 1,41 was 1.43 (4H, m), was 2.76 (4H, q, J=7,6 Hz), 3,21-3,30 (2H, m), 3,36 is 3.40 (2H, m), 7,32-7,41 (3H, m), 7.68 per-7,80 (2H, m).

l3C-NMR (CDCl3that δ, ppm): 14,1, 22,7, 26,8, 28,5 (d, J=4.5 Hz), 29,2, 29,4, 29,5, 29,55, 29,63, 29,67, 29,70, 31,9, 45,1 (d, J=5,2 Hz), 45,8 (d, J=9.4 Hz), 128,2 (d, J=13,7 Hz), 131,2, 132,5 (d, J=157,0 Hz), to 132.6 (d, J=9.8 Hz).

31P-NMR (CDCl3that δ, ppm): 28,4.

Elemental analysis calculated for C40H75ON2P: C, 76,14; H, 11,98; N, OF 4.44%. Found: C, 76,10; H, 12,15; N, Or 4.31%.

Example 7

In a glass bottle 2,12 g (45 mmol) of N,N'-dietilatsetamida (General formula [4], R2= catilina group, and R5=ethylene group), 0.24 g (9 mmol) of 4-dimethylaminopyridine and 15 ml of triethylamine are dissolved in 200 ml tetrahydrofuran is a, and the capacity is kept in a water bath. There gradually add 8,78 g (45 mmol) dichlorophenylphosphine acid (General formula [2], R1= phenyl group and X1= a chlorine atom) and stirred for 2 hours. The reaction mixture is filtered and 14.9 g (to 22.5 mmol) of 2,5-diaza-2,5-Dicetyl-1-oxo-1-phenylphosphine (General formula [1], R1= phenyl group, R2= catilina group and two R3combined with the formation of the ethylene group) is obtained by purification of the residue obtained by concentration of the filtrate under reduced pressure, chromatography on a column of silica gel using hexane as eluent.

Example 8

In a glass bottle 0,285 g (1.0 mmol) 1-bromo-4-octyloxybenzoic and 0,030 g (1.25 mmol) of magnesium metal are mixed in tetrahydrofuran (1 ml), heated to a temperature of 50°C and stirred for 30 minutes. The resulting solution of bromide 4-octyloxyphenyl (General formula [8], R1= 4-octyloxyphenyl group and M = bromania group) mixed with 0,210 g (1.0 mmol) of 2,5-diaza-2,5-dimethyl-1-oxo-1-proxyfactory (General formula [7], R2= methyl group, X3= fenoxaprop and two R3combined with the formation of the ethylene group) and stirred for 7 days at a temperature of 67°C. To the obtained mixture is added 0.2 ml of water, and then the solid UD is collected by filtration, the filtrate is concentrated under reduced pressure. The obtained oily substance is purified by chromatography on a column of silica gel, using diethyl ether as eluent, to obtain the 0,196 g (of 0.58 mmol) of 2,5-diaza-2,5-dimethyl-1-(4-octyloxyphenyl)-1-oxaphosphorin (General formula [1], R1=4-octyloxyphenyl group, R2= methyl group, and two R3combined with obtaining ethylene group). This connection is a new connection that has not yet been described.

The spectral data and the results of elemental analysis of the compound obtained in example 8, below.

1H-NMR (CDCl3that δ, ppm): from 0.88 (3H, t, J=6.9 Hz), of 1.26 to 1.31 (10H, users), 1.41 to to 1.45 (2H, m), of 1.78 (2H, cunt, J=6,7 Hz), 2,50 (6H, d, J=10.1 Hz), 3,19-3,24 (2H, m), 3.33 and-to 3.38 (2H, m), 3,98 (2H, t, J=6,7 Hz), 6,92 (2H, DD, J=to 2.6, 8.6 Hz), a 7.62 (2H, DD, J=8,6, 12.3 Hz).

l3C-NMR (CDCl3that δ, ppm): 14,1, 22,7, 26,0, 29,2, 29,3, 31,7 (d, J=5.6 Hz), 48,6, 68,1, to 114.4 (d, J=14,8 Hz), of 120.5, 134,5 (d, J=11.3 Hz), 162,0.

31P-NMR (CDCl3that δ, ppm): 30,2.

MS (EI): m/z 338.

Elemental analysis calculated for C18H31O2N2P: C, 63,88; H, 9,23; N, OF 8.28%. Found: C, 63,57; H, To 9.45; N, 8,19%.

Example 9

In a glass bottle 1.68 g (5.0 mmol) of N,N'-bis(p-were)phenylphosphonite (General formula [9], R1= phenyl group, and R3= p-methylphenylene group), 3 ml of activated (General formula [10], R2= anjilina group and X4= at the m bromine), 0.9 g of sodium hydride and 30 ml of acetonitrile are mixed and the mixture is stirred for 24 hours at room temperature. After removing the solids by filtration of the reaction mixture to 2.41 g (4,56 mmol) N,N'-bis(p-were)-N,N'-dioctylfluorenyl (General formula [1], R1= phenyl group, R2= anjilina group, and R3= p-methylphenylene group) is obtained by purification of the residue obtained by concentration of the filtrate under reduced pressure, chromatography on a column of silica gel using ether as eluent. This connection is a new connection that has not yet been described.

The spectral data and the results of elemental analysis of the compound obtained in example 9, below.

1H-NMR (CDCl3that δ, ppm): or 0.83 (6H, t, J=6.9 Hz), 0,95 was 1.43 (24H, m)to 2.29 (6H, s), 3,17-of 3.23 (2H, m), 3,29-to 3.35 (2H, m), to 6.95 (4H, d, J=8.0 Hz), 7,02 (4H, d, J=8.0 Hz), 7,34-7,41 (3H, m), 7,71 for 7.78 (2H, m).

l3C-NMR (CDCl3that δ, ppm): 14,0, 20,9, 22,6, 26,7, 28,5 (d, J=3.1 Hz), 29,1, 29,2, 31,7, 50,5 (d, J=4,1 Hz), to 127.9 (d, J=13.5 Hz), 128,5 (d, J=3.1 Hz), 129, 2mm, 131,0, 132,2 (d, J=157,3 Hz), to 132.6 (d, J=9.3 Hz), 135,0, 140,0 (d, J=2.0 Hz).

31P-NMR (CDCl3that δ, ppm): 21,3.

Elemental analysis calculated for C36H53ON2P: C, 77,10; H, AT 9.53; N, 5,00%. Found: C, 77,24; H, Of 9.56; N, At 4.99%.

Example 10

According to the method of example 9, except for the application of 1.84 g (5.0 mmol) of N,N'-bis(p-methoxyphenyl)phenylphosphonite (is BSA formula [9], R1= phenyl group, and R3= p-metoksifenilny group) instead of N,N'-bis(p-were)phenylphosphonite, gain of 1.34 g (3,40 mmol) N,N'-bis(p-methoxyphenyl)-N,N'-dioctylfluorenyl (General formula [1], R1= phenyl group, R2= anjilina group, and R3= p-metoksifenilny group). This connection is a new connection that has not yet been described.

The spectral data and the results of elemental analysis of the compound obtained in example 10, below.

1H-NMR (CDCl3that δ, ppm): or 0.83 (6H, J=7.2 Hz), 0,94-1,23 (24H, m), is 3.08-up 3.22 (2H, m), 3,23-3,26 (2H, m), 3,76 (6H, s), 6,74 (4H, d, J=7.9 Hz), 6,94 (4H, d, J=7.9 Hz), 7,31-of 7.48 (3H, m), 7,70-7,76 (2H, m).

l3C-NMR (CDCl3that δ, ppm): 14,0, 22,6, 26,7, 28,5 (d, J=3.1 Hz), 29,1, 29,2, 31,7, 50,7 (d, J=4,1 Hz), 55,3, 113,8, to 127.9 (d, J=12,4 Hz), to 130.1 (d, J=3.1 Hz), 130,9 (d, J=3.1 Hz), 132,1 (d, J=153,1 Hz), 132,7 (d, J=8,3 Hz), 135,3 (d, J=3.1 Hz), 157,4.

31P-NMR (CDCl3that δ, ppm): 21,7.

Elemental analysis calculated for C36H53O3N2P: C, 72,94; H, 9,01; N, 4,73%. Found: C, 72,90; H, 9,01; N, 5,01%.

Example 11

In a glass bottle and 3.72 g (7.0 mmol) of N,N'-bis(p-octylphenyl)phenylphosphonite (General formula [9], R1= phenyl group, and R3= p-octylaniline group), 5 ml of methyliodide (General formula [10], R2= a methyl group and X4= iodine atom), 1.0 g of sodium hydride and 100 ml of acetonitrile are mixed and the mixture is stirred for 24 hours is at room temperature. After removing the solids by filtration of the reaction mixture is 2.88 g (5,15 mmol) of N,N'-bis(p-octylphenyl)-N,N'-dimethylphenylphosphine (General formula [1], R1= phenyl group, R2= methyl group, and R3= p-octylaniline group) is obtained by purification of the residue obtained by concentration of the filtrate under reduced pressure, chromatography on a column of silica gel using ether as eluent. This connection is a new connection that has not yet been described.

The spectral data and the results of elemental analysis of the compound obtained in example 11, below.

1H-NMR (CDCl3that δ, ppm): of 0.87 (6H, t, J=6.9 Hz), 1.26 in (20H, users), 1,53-of 1.57 (4H, m), 2,52 (4H, t, J=7,6 Hz), 3,05 (6N, d, J=9.3 Hz), 6,99 (4H, d, J=8,4 Hz), to 7.09 (4H, d, J=8,4 Hz), 7,26-7,41 (3H, m), 7,70-7,76 (2H, m).

l3C-NMR (CDCl3that δ, ppm): 14,1, 22,7, 29,3, 29,5, 31,5, 31,6 (d, J=3.1 Hz), 31,9, 35,3, 38,2 (d, J=5,2 Hz), 125,2 (d, J=4, 2 Hz), 128,1 (d, J=13.5 Hz), 128,7 (2C), 131,7 (d, J=90,0 Hz), to 132.6 (d, J=9.3 Hz), 139,2, of 142.8 (d, J=3.1 Hz).

31P-NMR (CDCl3that δ, ppm): 22,5.

Elemental analysis calculated for C36H53ON2P: C, 77,10; H, AT 9.53; N, 5,00%. Found: C, 77,00; H, 9,68; N, Of 5.03%.

Example 12

In a glass bottle 1.13 g (2.0 mmol) of N,N'-bis(p-octyloxyphenyl)phenylphosphonite (General formula [9], R1= phenyl group, and R3= p-octyloxyphenyl group), 1 ml of methyliodide (General formula [10], R2 = a methyl group and X4= iodine atom), 0.3 g of sodium hydride and 20 ml of acetonitrile are mixed and the mixture is stirred for 24 hours at room temperature. After removing the solids by filtration of the reaction mixture 0,834 g (1,41 mmol) of N,N'-bis(p-octyloxyphenyl)-N,N'-dimethylphenylphosphine (General formula [1], R1= phenyl group, R2= methyl group, and R3= p-octyloxyphenyl group) is obtained by purification of the residue obtained by concentration of the filtrate by chromatography on a column of silica gel using ether as eluent. This connection is a new connection that has not yet been described.

The spectral data and the results of elemental analysis of the compound obtained in example 12, below.

1H-NMR (CDCl3that δ, ppm): from 0.88 (6H, t, J=6.9 Hz), 1,29 (16H, users), 1,38 was 1.43 (4H, m), 1,74 (4H, cunt, J=6.6 Hz), 2,99 (6H, d, J=10,2 Hz), 3,88 (4H, t, J=6.6 Hz), 6,74 (4H, d, J=9.0 Hz), 7,07 (4H, d, J=9.0 Hz), 7,34-7,39 (3H, m), 7,60 to 7.75 (2H, m).

l3C-NMR (CDCl3that δ, ppm): 14,1, 22,6, 29,19, 29,24, 29,3, 31,8, 38,7 (d, J=5,2 Hz), 68,1, 114,6, of 127.5 (d, J=4,1 Hz), USD 128.0 (d, J=13,4 Hz), 130, 8mm (d, J=157,4 Hz), RB 131.1 (d, J=2.1 Hz), 132,5 (d, J=8,3 Hz), 137,9 (d, J=3.1 Hz), 156,5.

31P-NMR (CDCl3that δ, ppm): 22,6.

Elemental analysis calculated for C36H53O3N2P: C, 72,94; H, 9,01; N, 4,73%. Found: C, 72,85; H, 9,07; N, At 4.99%.

Example 13

In a glass bottle 0.88 g (10 mmol) of N,N'-d is methylethylenediamine (General formula [4], R2= methyl group, and R5= ethylene group) and 3 ml of triethylamine dissolved in 50 ml of tetrahydrofuran, and the capacity is kept in a water bath. There gradually add 1,95 g (10 mmol) dichlorophenylphosphine acid (General formula [2], R1= phenyl group and X1= a chlorine atom) and stirred for 2 hours. The reaction mixture is filtered, the filtrate is concentrated under reduced pressure, and distillation of the residue under reduced pressure (180°C/2 mm RT. Art.) get to 1.79 g (8.5 mmol) of 2,5-diaza-2,5-dimethyl-1-oxo-1-phenylphosphine (General formula [1], R1= phenyl group, R2= methyl group, and two R3combined with the formation of the ethylene group). This connection is a new connection that has not yet been described.

The spectral data of the compounds obtained in example 13, below.

1H-NMR (CDCl3that δ, ppm): 2,44 (6H, d, J=7,6 Hz), 3.15 and is 3.23 (2H, m), 3,32-3,37 (2H, m), 7,38 was 7.45 (3H, m), of 7.64-7,71 (2H, m).

l3C-NMR (CDCl3that δ, ppm): 31,6 (d, J=6.3 Hz), 48,4 (d, J=8,8 Hz), 128,3 (d, J=13,7 Hz), 131,0 (d, J=of 156.6 Hz), 131, 5mm (d, J=2,9 Hz), 132,5 (d, J=9.8 Hz).

31P-NMR (CDCl3that δ, ppm): 29,5.

MS (EI): m/z 210,77.

Comparative example 1

To 4 ml of 1 mol/l aqueous solution of nitric acid containing 1,00·10-4mol/l of ions of trivalent lanthanum and 1.00·10-4mol/l trivalent ions is bropia, add 4 ml of dichloromethane and shaken for 10 minutes at a temperature of 25°C. After separation of the layers by centrifugation concentration remaining in the aqueous solution of ions of trivalent lanthanum ions and trivalent europium measured emission spectrochemical analysis in inductively coupled plasma (ICP), which shows that all ions of trivalent lanthanum ions and trivalent europium remained in aqueous solution.

Examples 14-33

To 4 ml of 1 mol/l aqueous solution of nitric acid containing 1,00·10-4mol/l of ions of trivalent lanthanum and 1.00·10-4mol/l of ions of trivalent europium, add 4 ml of dichloromethane solution containing 1 mmol of different phosphoramidic compounds, and shaken for 10 minutes at a temperature of 25°C. After separation of the layers by centrifugation concentration remaining in the aqueous solution of ions of trivalent lanthanum ions and trivalent europium measured emission spectrochemical analysis in inductively coupled plasma (ICP) and calculate the coefficient of extraction of ions of trivalent lanthanum and trivalent europium. The results are shown in table 1.

In all cases below, the extraction ratio shows the ratio of the number of moles of ions transferred from the aqueous layer in the organic layer, what about the relation to the number of moles of ions, contained in the original water layer for each ion.

Example 34

To 4 ml of 1 mol/l aqueous solution of nitric acid containing 1,00·10-4mol/l of ions of trivalent lanthanum and 1.00·10-4mol/l of ions of trivalent europium add 4 ml of dichloromethane solution containing 200 Ámol phosphoramide compound obtained in example 8 (General formula [1], R1=4-octyloxyphenyl group, R2= methyl group, and two R3combined with obtaining ethylene group), and shaken for 10 minutes at a temperature of 25°and carry out the separation of the layers. The concentration remaining in the aqueous solution of ions of trivalent lanthanum ions and trivalent europium measured emission spectrochemical analysis in inductively coupled plasma (ICP) and calculate the coefficient of extraction of ions of trivalent lanthanum and trivalent europium. The result found that 94.2 percent (0,376 mmol) of ions of trivalent lanthanum and 97.0% (0,388 mmol) of ions of trivalent europium extracted from the aqueous layer in the organic layer.

Comparative example 2

According to the method of comparative example 1, except for using dodecane instead of dichloromethane, concentration remaining in the aqueous solution of ions travalent the th lanthanum ions and trivalent europium measured emission spectrochemical analysis in inductively coupled plasma (ICP). As a result, all ions of trivalent lanthanum ions and trivalent europium were found in aqueous solution.

Examples 35-38

To 4 ml of 1 mol/l aqueous solution of nitric acid containing 1,00·10-4mol/l of ions of trivalent lanthanum and 1.00·10-4mol/l of ions of trivalent europium, add 4 ml of dodecane containing different concentrations phosphoramide compound obtained in example 8 (General formula [1], R1= 4-octyloxyphenyl group, R2= methyl group, and two R3combined with obtaining ethylene group), and shaken for 10 minutes at a temperature of 25°C. After separation of the layers by centrifugation concentration remaining in the aqueous solution of ions of trivalent lanthanum ions and trivalent europium measured emission spectrochemical analysis in inductively coupled plasma (ICP) and calculate the coefficient of extraction of ions of trivalent lanthanum and trivalent europium. The results are shown in table 2, where a means the number of mmol phosphoramides connection.

Table 2
AndThe recovery factor (%)
Lanthanum Europium
Comparative example 2000
Example 350,2a 94.297,0
Example 360,1of 40.959,1
Example 370,0522,835,0
Example 380,026,710,2

Example 39

To 4 ml of 1 mol/l aqueous solution of nitric acid containing 1,00·10-4mol/l trivalent ions of lanthanum, 1,00·10-4mol/l of ions of trivalent cerium, 1,00·10-4mol/l of ions of trivalent praseodymium, 1,00·10-4mol/l trivalent ions of neodymium, 1,00·10-4mol/l of ions of trivalent samarium, 1,00·10-4mol/l of ions of trivalent europium, 1,00·10-4mol/l trivalent ions of gadolinium, 1,00·10-4mol/l of ions of trivalent terbium, 1,00·10-4mol/l of ions of trivalent dysprosium, 1,00·10-4mol/l of ions of trivalent holmium, 1,00·10-4mol/l trivalent ions of erbium, 1,00·10-4mol/l trivalent ions of ytterbium and 1.00·10-4mol/l trivalent ions lutetium, add 4 ml of dichloromethane solution containing 1 mmol phosphoramide compound obtained in example 13(General formula [1], R1= phenyl group, R2= methyl group, and two R3combined with obtaining ethylene group), and shaken for 10 minutes at a temperature of 25°C. After separation of the layers of the ion concentration of each rare earth metal remaining in the aqueous solution, measured emission spectrochemical analysis in inductively coupled plasma (ICP) and calculate the coefficient of extraction of ions of each compound. The results are shown in table 3.

Example 40

According to the method of example 39, except dodecane instead of dichloromethane, and using phosphoramide compound obtained in example 8 (General formula [1], R1=4-octyloxyphenyl group, R2= methyl group, and two R3combined with obtaining ethylene group), instead of phosphoramide compound obtained in example 13, calculate the coefficient of extraction of ions of each compound. The results are shown in table 3 together with the results of example 39.

As follows from table 3, in both examples, can be selectively extracted ions of trivalent ytterbium and lutetium ions of trivalent.

Examples 41-44

To 12 ml of 1 mol/l aqueous solution of nitric acid containing 1,00·10-4mol/l of ions of trivalent lanthanum and 1.00·10-4mol/l of ions t is hvalenogo europium, add 12 ml of dichloromethane solution containing 3 mmol phosphoramide compound obtained in example 13 (General formula [1], R1= phenyl group, R2= methyl group, and two R3combined with obtaining ethylene group), and shaken for 10 minutes at a temperature of 25°and carry out the separation of the layers. At this time of 94.8% (1,14 mmol) of ions of trivalent lanthanum and 95.3 per cent (to 1.14 mmol) of ions of trivalent europium is transferred from the aqueous layer in the layer dichloromethane. Then the organic layer is separated into aliquots of 2 ml each and separately add 2 ml of aqueous solutions (aqueous solutions of nitric acid and aqueous solutions of acetic acid/sodium acetate at various concentrations), shaken for 10 minutes at a temperature of 25°and carry out the separation of the layers. The concentration of ions of trivalent lanthanum ions and trivalent europium, in aqueous solution, measured emission spectrochemical analysis in inductively coupled plasma (ICP) and calculate the coefficient of the inverse extraction. The coefficient of the inverse extraction shows, if ion rare earth metal contained in the layer dichloromethane, extracted aqueous layer, the ratio of the number of moles of ions transferred from the dichloromethane layer into the aqueous layer, relative to the original amount of the Olga ions, contained in dichloromethane layer, for each ion. The coefficients of the inverse of the ion extraction of trivalent lanthanum and ion trivalent europium are given in table 4.

Table 4
View an aqueous solutionThe recovery factor(%)
LanthanumEuropium
Example 413 mol/l aqueous solution of nitric acid98,6>to 99.9
Example 421 mol/l aqueous solution of nitric acid>to 99.9>to 99.9
Example 430.1 mol/l aqueous solution of nitric acid99,2>to 99.9
Example 44An aqueous solution of 0.5 mol/l acetic acid and 0.5 mol/l sodium acetate>to 99.9>to 99.9

Industrial applicability

This invention provides a new phosphoramide connection, which is used as an agent for the extraction of ions of rare-earth metal or the like, the method of its production and extraction ion rare earth metal from an aqueous solution containing rare earth ion is about metal, using the connection. When applying phosphoramide compounds in accordance with this invention as an agent for extraction, ion rare earth metal can be extremely effectively extracted by a simple method from an aqueous solution containing the ion of the rare earth metal.

Also ion rare earth metal extracted and transferred from the aqueous layer into the layer of organic solvent the extraction method can be effectively back extracted from the layer of organic solvent in the aqueous layer by mixing and contacting the layer of organic solvent with slightly acid water than that of the original aqueous layer.

1. Agent extraction ion rare earth metal containing phosphoramide the connection represented by the General formula (1)

where R1is an aryl group, aranceles group, provided that each group may have a Deputy selected from alkoxygroup; R2is an alkyl group, alkenylphenol group, aryl group, aranceles group, provided that each group may have a Deputy selected from alkyl groups, alkoxygroup; R3is a hydrogen atom, aryl group, aranceles group, provided that each group may have a Deputy selected from alkyl groups, alkoxygroup, halogen atoms; two of R3can be combined with education alkalinous group.

2. Extraction ion rare earth metal from the aqueous solution containing the ion of the rare earth metal, characterized in that the applied agent extraction ion rare earth metal containing phosphoramide the connection represented by the General formula (1)

where R1is an aryl group, aranceles group, provided that each group may have a Deputy selected from alkoxygroup; R2is an alkyl group, alkenylphenol group, aryl group, aranceles group, provided that each group may have a Deputy selected from alkyl groups, alkoxygroup; R3is a hydrogen atom, aryl group, aranceles group, provided that each group may have a Deputy selected from alkyl groups, alkoxygroup, halogen atoms; two of R3can be combined with education alkalinous group,

in which an aqueous solution containing the ion of the rare earth metal, phosphoramide the connection represented by the General formula (1), and an organic solvent which is not completely miscible with water, mixed and injected into the contact, resulting metal ion TRANS is worn in the layer of organic solvent.

3. Way back extraction ion rare earth metal, wherein the layer of organic solvent containing the extracted ion rare earth metal extracted by the extraction method according to claim 2, mix and put in contact with water, thereby transferring the metal ion in the aqueous layer, in which water for mixing and contacting is a weak acid or acidic water.



 

Same patents:

FIELD: rare-earth element technology.

SUBSTANCE: invention relates to technology of recovering rare-earth elements from phosphogypsum obtained from processing of apatite concentrate into mineral fertilizers. Phosphogypsum is treated with 22-30% sulfuric acid solution at liquids-to-solids ratio 1.8-2.2 to recover rare-earth elements and sodium into solution. Insoluble precipitate is separated and degree of oversaturation of solution regarding rare-earth elements is increased by means of providing sodium concentration 0.4-1.2 g/L, after which crystallization of rare-earth element concentrate is allowed to proceed and concentrate is then separated from mother liquor. Treatment duration is 20-30 min to prevent spontaneous crystallization of rare-earth element concentrate in solution before insoluble precipitate is separated. Content of sodium in solution is controlled by adding a sodium salt thereto, preferably sodium sulfate or sodium carbonate. Degree of recovery of rare-earth elements from phosphogypsum into concentrate achieves 71.4%.

EFFECT: increased degree of rare-earth element recovery and simplified procedure due to eliminated operation of dilution of recycle sulfuric acid solutions and shortened sulfuric acid treatment duration by a factor of 2-3.

2 cl, 1 tbl, 3 ex

FIELD: hydraulic metallurgy, namely processes for extracting rare and rare-earth metals from natural organic raw materials such as coals and their burning products such as ash-slag waste materials.

SUBSTANCE: method is realized by using nitric acid for leaching. Selective extraction of rare-earth metal nitrates is realized due to extraction with use of organic solutions of tributyl phosphate and due to using part of heat of coal burning for regeneration of nitric acid by thermal decomposition of refined products and contained in them nitrates of potassium, aluminum, iron and other metals.

EFFECT: lowered consumption of reagents (acids) for leaching rare-earth elements from coals or ash-slag waste materials, simplified process for extracting and purifying rare-earth metals after processing leaching solutions.

4 ex

FIELD: mining industry.

SUBSTANCE: invention relates to rare-earth element recovery technology in integrated processing of mineral stock, especially to hydrogen chloride technology of eudialyte concentrate. Method according to invention comprises introduction of nitrate ion into initial chloride solution containing rare-earth and impurity elements. Chloride-nitrate solution thus obtained is treated with tributyl phosphate extractant to transfer nitrates of rare-earth elements and a part of impurity elements into first organic phase, which is then separated from chloride-nitrate solution to form first extract and first raffinate containing major part of impurity elements. First extract is washed with nitrate solution and wash solution is then returned into initial chloride solution. Rare-earth element nitrates are reextracted with water and first reextract is separated. Concentrated 35-37% hydrochloric acid is added to the first raffinate to provide 5-10% excess of the acid relative to nitrate ion content. Raffinate is treated with tributyl phosphate to transfer nitric acid into second organic phase and to form chloride solution of the major part of impurity elements. Second organic phase is separated to form extract and second raffinate, after which nitric acid is reextracted from the second extract with alkali solution to form second reextract in the form of nitrate solution, which is used to wash the first extract.

EFFECT: increased rare-earth element recovery efficiency under better environmental conditions.

5 cl, 1 dwg, 3 ex

FIELD: hydrometallurgy; ore concentrates processing.

SUBSTANCE: the invention is pertaining to the field of hydrometallurgy, in particular, to processing of the loparite concentrate. The method includes a decomposing of the loparite concentrate at the temperatures of 103-105°C and the concentration of hydrofluoric acid of 38-42 mass % with production of the pulp containing fluorides of titanium, rare earth elements (REE), niobium, tantalum and sodium. The pulp is filtered at the temperature of 90-95°C with extraction into the fluorotitanium solution of fluorides of niobium and tantalum and no less than 58 % of sodium in terms ofNa2O and separation of the sediment containing fluorides of rare earth elements (REE) and a residual sodium. The produced solution is cooled down to 18-24°C with separation of the second sediment of sodium fluorotitanate. After that they extract niobium and a tantalum from the solution by octanol-1 extraction at a ratio of the organic and water phases as 1.1 : 1. The sediment of REE fluorides is washed from fluorotitanate by sodium water in a single phase at the temperature of 90-95°C and at the solid :liquid ratio = 1:2-2.5. The cleansing solution is separated and evaporated with extraction of the additional sediment of sodium fluorotitanate. After extraction of niobium and tantalum the fluorotitanium solution is evaporated and filtered with separation of the first sediment of sodium fluorotitanate from the concentrated solution of fluorotitanium acid, which is directed to extraction of titanium. The gained first, second and additional sediments of sodium fluorotitanate are combined and subjected to conversion with production of sodium fluorosilicate and the conversional fluorotitanium acid added to fluorotitanium solution before its evaporation. The technical result of the invention is a decrease in 2.0-2.5 times of the volume of the cleansing solutions at provision of a high degree of extraction of compounds of titanium and other target products. The produced sodium fluorotitanate contains the decreased amount of the impurity ingredients of calcium and strontium.

EFFECT: the invention ensures a decrease in two-two and a half times of the volume of the used cleansing solutions at provision of a high degree of extraction of compounds of titanium and other target products and a decreased amount of impurities of calcium and strontium in the sodium fluorotitanate.

7 cl, 1 dwg, 1 tbl, 3 ex

FIELD: non-ferrous metallurgy; methods of production of scandium-containing ligatures.

SUBSTANCE: the invention is pertaining to the field of non-ferrous metallurgy. The method of production of scandium-containing addition alloys includes a metallothermic restoration in halogenide melts. According to the invention the halogenide melt containing 1.0-1.4 mass % of scandium oxide is added with 1.4-1.7 mass % of zirconium oxide and conduct restoration by an alloy of aluminum with magnesium at the ratio of the halogenide melt to the aluminum-magnesium alloy from 1.2 up to 1.6. The technical result of the invention is production of a synthesized addition alloy containing scandium and zirconium with the maximal strengthening effect, decreased value of the produced addition alloy (by 30-40 %) due to decrease of consumption of the cost intensive scandium oxide by 50 %.

EFFECT: the invention ensures production of a synthesized scandium and zirconium ligature with maximal strength, allows to decrease significantly its production cost and consumption of expensive scandium oxide.

1 tbl, 1 ex

FIELD: metallurgy; hydrochemical methods of a complex processing of a multicomponent, polymetallic scrap.

SUBSTANCE: the invention is pertaining to the field of metallurgy, in particular, to the hydrochemical methods of a complex processing of a multicomponent, polymetallic scrap used in nonferrous metallurgy with extraction of valuable components and production of various commercial products. The technical result at reprocessing and neutralization of wastes of production of titanium tetrachloride consists in concentration of radioactive metals in the "head" of the process, transfer of the secondary wastes of production in an ecologically secure form suitable for a long-term entombment and-or storing, as well as in production of an additional commercial products - deficient and expensive black thermo- resistant inorganic pigments based on iron oxides, manganese and copper oxides. The method provides for a discharge of the spent melt of titanium chlorates into water; concentrating of a pulp by circulation; the pulp thickening; settling of metals oxyhydrates from the clarified solutions in succession in three stages: on the first stage - conduct a settling at pH = 3.-5.0 with separation of the formed settling of hydroxides of chrome, aluminum and scandium from the solution; on the second stage - conduct settling at presence of an oxidizing agent at pH = 2.5-3.5 within 20-50 hours with separation of the settling; on the third stage - conduct settling at pH = 9.5-11.0. The pulp at its circulation and concentration is added with sodium sulfite in amount of 5 - 15 g/dm3, then after circulation the pulp is treated with a solution of barium chloride in amount of 10-20 g/dm3 for cosettling of ions of thorium and radium, in the formed pulp of the first stage of settling introduce a high-molecular flocculant, and before settling process on the third stage of the process the solution is previously mixed with copper(II)-containing solution formed after lixiviation of a fusion cake of the process of cleanout of the industrial titanium tetrachloride from vanadium oxychloride by copper powder, then the produced settling of iron, manganese and copper oxyhydrates is filtered off, cleansed, dried and calcined at the temperature of 400-700°C.

EFFECT: the invention allows to concentrate radioactive metals in the "head" of the process, to transfer the process secondary wastes in the ecologically secure deficient and expensive black thermo-resistant inorganic pigments.

5 cl, 1 ex

FIELD: non-iron metallurgy, in particular scandium oxide recovery from industrial waste.

SUBSTANCE: method for preparation of scandium oxide from red mud being waste of alumina production includes: multiple subsequent leaching of red mud with mixture of sodium carbonate and hydrocarbonate solutions; washing and precipitate separation; addition into obtained solution zinc oxide, dissolved in sodium hydroxide; solution holding at elevated temperature under agitation; precipitate separation and treatment with sodium hydroxide solution at boiling temperature; separation, washing, and drying of obtained product followed by scandium oxide recovery using known methods. Leaching is carried out by passing through mixture of sodium carbonate and hydrocarbonate solutions gas-air mixture containing 10-17 vol.% of carbon dioxide, and repeated up to scandium oxide concentration not less than 50 g/m3; solid sodium hydroxide is introduced into solution to adjust concentration up to 2-3.5 g/m3 as calculated to Na2O (caustic); and mixture is hold at >=800C followed by flocculating agent addition, holding, and separation of precipitate being a titanium concentrate. Obtained mixture is electrolyzed with solid electrode, cathode current density of 2-4 A/dm3, at 50-750C for 1-2 h to purify from impurities. Zinc oxide solution in sodium hydroxide is added into purified after electrolysis solution up to ratio ZnO/Sc2O3 = (10-25):1, and flocculating agent is introduced. Solution is hold at 100-1020C for 4-8 h. Separated precipitate is treated with 5-12 % sodium hydroxide solution, flocculating agent is introduced again in amount of 2-3 g/m3, mixture is hold, and precipitate is separated. Method of present invention is useful in bauxite reprocessing to obtain alumina.

EFFECT: improved recovery ratio of finished product into concentrate; decreased impurity concentration in concentrate, reduced sodium hydrocarbonate consumption, as well as reduced process time due to decreased time of fine-dispersed precipitate.

2 cl, 2 ex

FIELD: chemical technology; deactivation and decontamination of radioactive industrial products and/or wastes.

SUBSTANCE: proposed method designed for deactivation and decontamination of radioactive industrial products and/or production wastes incorporating Th-232 and its daughter decay products (Ra-228, Ra-224), as well as rare-earth elements, Fe, Cr, Mn, Al, Ti, Zr, Nb, Ta, Ca, Mg, Na, K, and the like and that ensures high degree of coprecipitation of natural radionuclides of filtrates, confining of radioactive metals, and their conversion to environmentally safe form (non-dusting water-insoluble solid state) includes dissolution of wastes, their treatment with barium chloride, sulfuric acid, and lime milk, and separation of sediment from solution. Lime milk treatment is conducted to pH = 9-10 in the amount of 120-150% of that stoichiometrically required for precipitation of total content of metal oxyhydrate; then pulp is filtered and barium chloride is injected in filtrate in the amount of 0.4 - 1.8 kg of BaCl2 per 1 kg of CaCl2 contained in source solution or in pulp and pre-dissolved in sulfuric acid of chlorine compressors spent 5-20 times in the amount of 0.5 - 2.5 kg of H2SO4 per 1 kg of BaCl2. Then lime milk is added up to pH = 11 - 12 and acid chloride wash effluents of equipment and production floors are alternately introduced in sulfate pulp formed in the process at pulp-to-effluents ratio of 1 : (2-3) to pH = 6.5 - 8.5. Filtrate pulp produced in this way is filtered, decontaminated solution is discharged to sewerage system, sediment of barium and calcium sulfates and iron oxysulfate are mixed up with oxyhydrate sediment formed in source pulp neutralization, inert filler and 0.5 - 2 parts by weight of calcium sulfate are introduced in pasty mixture while continuously stirring them. Compound obtained in the process is placed in molds, held therein at temperature of 20 - 50 oC for 12 - 36 h, and compacted in blocks whose surfaces are treated with water-repelling material.

EFFECT: reduced radioactivity of filtrates upon separation of radioactive cakes.

8 cl, 1 dwg, 1 ex

FIELD: metallurgy; reworking wastes of alumina production process.

SUBSTANCE: proposed method includes preparation of batch of charge containing red mud and carbon reductant, heating the charge in melting unit to solid-phase iron reduction temperature, three-phase reduction of ferric oxides in charge by carbon reductant and saturation of iron with carbon in charge thus prepared, melting the reduced charge for obtaining metal phase in form of cast iron and slag phase in form of primary slag, separation of cast iron from primary slag in melt heated to temperature of 40 C, reduction of silicon and titanium from oxides contained in primary slag by aluminum and removal of cast iron and primary slag from melting unit; during preparation of charge, concentrate of titanomagnetite ore containing titanium oxide in the amount from 1 to 15% is added to red mud; besides that, additional amount of carbon reductant and additives are introduced; after separation of primary slag from cast iron in melting unit, cast iron is heated to 1500-1550 C and product containing ferric oxide is added to it; iron is reduced by carbon of cast iron for converting the cast iron into steel at obtaining secondary slag; main portion of steel is removed from melting unit, secondary slag is added to primary slag and silicon and titanium are converted into steel residue in melting unit by reduction with aluminum, thus obtaining final slag-saturated slag and master alloy containing iron, titanium and silicon; main portion of master alloy is removed from melting unit; after removal of final slag for converting the master alloy residue to steel in melting unit, titanium and silicon are converted into slag phase by oxidation and next portion of charge is fed to slag phase formed after converting the master alloy residue to steel. Proposed method ensures high efficiency due to obtaining iron-titanium silicon master alloy in form of independent product and production of alumina from high-alumina final slag or high-alumina cement and concentrate of rare-earth metals.

EFFECT: enhanced efficiency due to avoidance of intermediate remelting of steel.

10 cl, 2 dwg

The invention relates to a technology developing concentrates of rare earth elements from natural phosphate concentrates

FIELD: non-ferrous metallurgy, in particular, production of spongy titanium by metal reduction of titanium tetrachloride.

SUBSTANCE: method involves heating reduction unit; melting condensate and draining condensate of magnesium chloride; feeding argon into unit and creating excessive pressure therein; discharging argon from said unit into vacuum-type crucible; pouring magnesium into unit from vacuum crucible under hermetically sealed mode while maintaining equal excessive pressure in unit and vacuum crucible; feeding titanium tetrachloride and providing reduction process while periodically pouring out magnesium chloride; after pouring out condensate of magnesium chloride, positioning magnesium level measuring device into branch pipe for feeding of titanium tetrachloride; pouring magnesium into device until magnesium comes into electric contact with electrode of level sensor; stopping feeding of magnesium when signal is generated by level indicator; removing level sensor from branch pipe and feeding titanium tetrachloride. Apparatus has reduction unit comprising retort with drain device, hermetical cover, titanium tetrachloride and argon feeding branch pipes positioned on cover, magnesium pouring branch pipe wherein drain pipe of vacuum crucible is located, compensating device, detachable magnesium level measuring device formed as signaling device and level sensor made in the form of electrode located within protective enclosure, said level sensor being positioned within titanium tetrachloride feeding branch pipe. Lower end of electrode is deepened into retort up to the level of magnesium so as to come into electric contact with it, and upper end of level sensor is connected to signaling device. Electrode is formed as rod made from stainless steel, its lower end is deepened by distance determined on the basis of ratio of distance from cover to magnesium level to diameter of apparatus of 1:(3.5-4.5). Protective enclosure for electrode is made from electrically isolating material such as asbestos on liquid glass. Retort is earthed relative to ground. Also, signaling device is provided with serviceability control button connected to power source. Signaling device has two signal lamps.

EFFECT: increased speed and hour capacity of apparatus, provision for producing of spongy titanium blocks having standard weight to simplify further processing thereof.

8 cl, 2 dwg

FIELD: metallurgy, namely processes for producing master alloys, possibly production of zirconium alloys used in nuclear power engineering and chemical machine engineering.

SUBSTANCE: according to method main component such as zirconium- containing material is placed onto bottom of crystallizer of electron-beam installation and alloy component is charged onto it such as niobium. At first niobium is melted due to action of electron beam and then zirconium containing material is melted in combination with electromagnetic agitation of melts.

EFFECT: possibility for producing master alloy of uniform chemical content without significant expenses.

7 cl, 1 tbl, 1 dwg

FIELD: extraction of valuable metals from super-alloys by electrochemical decomposition.

SUBSTANCE: super-alloy is used as both electrodes, anode and cathode. Electrochemical decomposition is realized at changing polarity of electric current with frequency 0.005 - 5 Hz while using non-organic acid as electrolyte.

EFFECT: possibility for extracting valuable metals in industrial scale, lowered cost of simplified extraction process, effective solution of part of metals, separation of metal groups.

6 cl, 2 dwg, 1 ex

FIELD: complex processing of non-traditional kinds of raw materials - serpentinites and serpentinite waste of gaugue into chrysotile-asbestos and chromite deposits; production of chromite concentrate from lean chromium-containing ores.

SUBSTANCE: proposed method includes grinding of ore, heat treatment, leaching-out by mineral acid solutions followed by filtration of suspension, washing and drying of end product. Heat treatment is performed at temperature of 500-550°C ; leaching-out and filtration processes are performed in two stages including additional treatment of solid residue by caustic soda solution followed by filtration. First leaching-out stage consists in treatment of roasted ore by acid circulating filtrate at concentration of 230-250 g/l or sulfuric acid of hydrochloric acid at concentration of 90-110 g/l followed by filtration of suspension and transfer of solid residue to the second stage. Second stage includes treatment of solid residue by solution of sulfuric or hydrochloric acid at concentration of 300-550 g/l and 110-220 g/l, respectively followed by filtration of suspension and transfer of filtrate to the first leaching-out stage.

EFFECT: extended field of application of use of lean ore mixtures at simultaneous complex extraction of valuable components from raw material.

5 tbl, 6 ex

FIELD: hydrometallurgical processing of sludges, for example electrolysis sludges of copper-nickel process.

SUBSTANCE: proposed method includes treatment of sludges by oxidant in acid medium for converting silver into solution. Prior to treatment of sludges, they are reduced for converting silver and platinoids into metal powders; treatment is carried out in sulfamic acid medium. Used as oxidant is hydrogen peroxide of potassium or ammonium persulfate; treatment is accompanied by heating. Proposed method makes it possible to separate and clean silver from non-noble metals and accompanying metal of platinum group and gold due to obtaining selective solutions concentrated in silver.

EFFECT: chemically and ecologically safe technology; low cost of reagents.

2 cl, 2 tbl, 2 ex

FIELD: hydrometallurgy of platinum; extraction of platinum from hydrochloric acid solutions of complex composition, for example from mother liquor of platinum refining process by sorption.

SUBSTANCE: proposed method includes sorption of platinum on complexion of ionite which is selective to platinum; complexion of ionite contains thiourea functional groups; then, ionite is washed with acidulous water and platinum is desorbed by thiourea solution acidified by hydrochloric acid. Prior to sorption, oxidation-reduction potential of initial solution is brought to magnitude equal to or lesser than magnitude determined by the following equation: E=0.62-0.591 g CCl, where E is oxidation-reduction potential of solution relative to hydrogen electrode, V; CCl is total concentration of chloride ion in solution, mole/l. Sorption is performed by treatment with reductant.

EFFECT: high degree of extraction of platinum; increased productivity of process; increased yield of platinum; increased concentration of platinum.

2 tbl, 5 ex

FIELD: hydrometallurgy and mining industry; ecological methods of extraction of metals.

SUBSTANCE: proposed method of extraction of metals from solid metal-containing materials or ores includes treatment or underground leaching-out with solution of reagent obtained by electrolysis treatment of solution containing halogenide-anion and separation of metal from this solution. Electrolysis treatment is carried out under condition of positive mass transfer on revolving electrode or on electrode moving at acceleration of no less than 0.1 m/s. After electrolysis treatment, water-soluble polymer used as surfactant is introduced into reagent solution in the amount of no less than 0.01%.

EFFECT: enhanced efficiency and ecological safety due to reduced power requirements, intensification of process, avoidance of toxic emissions and use of safe chemicals.

7 cl, 2 dwg, 6 ex

FIELD: hydrometallurgy of extraction of non-ferrous, rare-earth and noble metals from rebellious raw materials containing natural carbon or other rebellious compounds.

SUBSTANCE: proposed method includes treatment of rebellious carbon-containing mineral raw material by oxygen-containing oxidant followed by extraction of noble metal compounds from liquid phase. Treatment of carbon-containing mineral raw material by oxygen-containing oxidant is carried out in presence of reductants possessing donor-acceptor properties which are expressed in the fact that at first stage of chemical reactions, reductants give off their electrons to oxygen-containing oxidant, forming stronger oxidant as compared with first one in form of short-lived radicals and intermediate products of oxidation of donor-acceptor reductants which are also used as oxidants.

EFFECT: increased extraction of non-ferrous, rare-earth and noble metals; low cost of process.

3 ex

FIELD: non-ferrous metallurgy; methods of refining gallium.

SUBSTANCE: proposed method includes treatment of gallium with acid at mixing in drum-type reactor. Treatment is carried out at temperature of 40-60°C and rotational speed of reactor of 1-20 rpm.

EFFECT: high degree of cleaning; increased good-to-bad yield; reduced losses of gallium.

1 dwg, 1 tbl, 1 ex

FIELD: metallurgy.

SUBSTANCE: proposed method is used in processing the ilmenite concentrate into ferro-titanium, highly titanous slag suitable for production or titanium sponge or pigment and into carbon-free iron suitable for fusion with metallic chromium into alloy used for production of tube or sheet stainless steel billets. Proposed method includes forming liquid metal substrate in melting unit, setting the substrate in rotation by means of electromagnetic field for forming of parabolic dimple to which titanium-containing burden is fed; this burden is molten for slag by energy of electromagnetic field and metals are reduced from slag oxides with the aid of reductant; reduced metals are fused together with substrate and slag is added with reductant oxide and metal and slag phases drained from melting unit. Portion of titanium-containing burden is delivered in two parts: first part is delivered to dimple for metal substrate formed from ferro-aluminum; during delivery of this part of portion, portion of fluor spar is molten in dimple for reduction of metals from oxides of first part of burden portion by substrate aluminum and fusing them with metal substrate which is lean in aluminum; aluminum oxide thus formed is dissolved in fluor spar to tolerable dissolving limit at temperature of molten fluor spar of 1600-1700°C. Fluor spar and dissolved aluminum oxide from melting unit are drained into ladle and are cooled to 1450°C for conversion of aluminum oxide into solid phase which is separated from molten fluor spar together with part of aluminum oxide remaining in it. After drainage of fluor spar and dissolved aluminum oxide on metal substrate whose chemical composition is changed, second part of burden portion is delivered and is molten; metal oxides in second part of burden portion are reduced by titanium of substrate; oxide forming free energy of these oxides is lesser than that of titanium oxide; thus, highly titanous slag is formed; 70-80% of metal phase lean in titanium is drained from melting unit. Titanium is reduced from oxide of slag remaining in melting unit and is fused together with remaining metal phase; aluminum oxide formed at reducing of titanium is fused together with fluor spar which is delivered to melting unit together with reductant. Then, fluor spar is fully drained from melting unit together with dissolved aluminum oxide, after which metal phase added with titanium is fully drained and substrate is immediately formed from ferro-aluminum in melting unit and procedure is repeated.

EFFECT: reduction of power requirements; waste-free technology.

7 cl, 2 dwg

FIELD: chemistry of organophosphorus compounds, biochemistry, medicine, pharmacy.

SUBSTANCE: invention relates to new bisamidate phosphonate compounds that are inhibitors of fructose 1,6-bis-phosphatase. Invention describes a compound of the formula (IA): wherein compound of the formula (IA) is converted in vivo or in vitro to compound of the formula M-PO3H2 that is inhibitor of fructose 1,6-bis-phosphatase and wherein M represents R5-X- wherein R5 is chosen from a group consisting of compounds of the formula or wherein each G is chosen from the group consisting of atoms C, N, O, S and Se and wherein only one G can mean atom O, S or Se and at most one G represents atom N; each G' is chosen independently from the group consisting of atoms C and N and wherein two G' groups, not above, represent atom N; A is chosen from the group consisting of -H, -NR42, -CONR42, -CO2R3, halide, -S(O)R3, -SO2R3, alkyl, alkenyl, alkynyl, perhaloidalkyl, haloidalkyl, aryl, -CH2OH, -CH2NR42, -CH2CN, -CN, -C(S)NH2, -OR2, -SR2, -N3, -NHC(S)NR42, -NHAc, or absent; each B and D is chosen independently from the group consisting of -H, alkyl, alkenyl, alkynyl, aryl, alicyclyl, aralkyl, alkoxyalkyl, -C(O)R11, -C(O)SR11, -SO2R11, -S(O)R3, -CN, -NR92, -OR3, -SR3, perhaloidalkyl, halide, -NO2, or absent and all groups except for -H, -CN, perhaloidalkyl, -NO2 and halide are substituted optionally; E is chosen from the group consisting of -H, alkyl, alkenyl, alkynyl, aryl, alicyclyl, alkoxyalkyl, -C(O)OR3, -CONR42, -CN, -NR92, -NO2, -OR3, -SR3, perhaloidalkyl, halide, or absent; all groups except for -H, -CN, perhaloidalkyl and halide are substituted optionally; J is chosen from the group consisting of -H, or absent; X represents optionally substituted binding group that binds R5 with phosphorus atom through 2-4 atoms comprising 0-1 heteroatom chosen from atoms N, O and S with exception that if X represents urea or carbamate then there are 2 heteroatoms that determine the shortest distance between R5 and phosphorus atom and wherein atom bound with phosphorus means carbon atom and wherein X is chosen from the group consisting of -alkyl(hydroxy)-, -alkynyl-, - heteroaryl-, -carbonylalkyl-, -1,1-dihaloidalkyl-, -alkoxyalkyl-, -alkyloxy-, -alkylthioalkyl-, -alkylthio-, -alkylaminocarbonyl-, -alkylcarbonylamino-, -alkoxycarbonyl-, -carbonyloxyalkyl-, -alkoxycarbonylamino- and -alkylaminocarbonylamino- and all groups are substituted optionally; under condition that X is not substituted with -COOR2, -SO3H or -PO3R22; n means a whole number from 1 to 3; R2 is taken among the group -R3 and -H; R3 is chosen from the group consisting of alkyl, aryl, alicyclyc and aralkyl; each R4 is chosen independently from the group consisting of -H and alkyl, or R4 and R4 form cycloalkyl group; each R9 is chosen independently from the group consisting of -H, alkyl, aryl, aralkyl and alicyclyl, or R9 and R9 form in common cycloalkyl group; R11 is chosen from the group consisting of alkyl, aryl, -NR22 and -OR2; each R12 and R13 is chosen independently from the group consisting of hydrogen atom (H), lower alkyl, lower aryl, lower aralkyl wherein all groups are substituted optionally, or R12 and R13 in common are bound through 2-5 atoms comprising optionally 1-2 heteroatoms chosen from the group consisting of atoms O, N and S to form cyclic group; each R14 is chosen independently from the group consisting of -OR17, -N(R17)2, -NHR17, -NR2OR19 and -SR17; R15 is chosen from the group consisting of -H, lower alkyl, lower aryl, lower aralkyl, or in common with R16 is bound through 2-6 atoms comprising optionally 1 heteroatom chosen from the group consisting of atoms O, N and S; R16 is chosen from the group consisting of -(CR12R13)n-C(O)-R14, -H, lower alkyl, lower aryl, lower aralkyl, or in common with R15 is bound through 2-6 atoms comprising optionally 1 heteroatom chosen from the group consisting of atoms O, N and S; each R17 is chosen independently from the group consisting of lower alkyl, lower aryl and lower aralkyl and all groups are substituted optionally, or R17 and R17 at atom N are bound in common through 2-6 atoms comprising optionally 1 heteroatom chosen from the group consisting of atoms O, N and S; R18 is chosen independently among the group consisting of hydrogen atom (H), lower alkyl, aryl, aralkyl, or in common with R12 is bound through 1-4 carbon atoms forming cyclic group; each R19 is chosen independently from the group consisting of -H, lower alkyl, lower aryl, lower alicyclyl, lower aralkyl and -COR3; and under condition that when G' represents nitrogen atom (N) then the corresponding A, B, D or E are absent; at least one from A and B, or A, B, D and E is chosen from the group consisting of -H, or absent; when G represents nitrogen atom (N) then the corresponding A or B is not halide or group bound directly with G through a heteroatom; and its pharmaceutically acceptable salts. Also, invention describes a method for treatment or prophylaxis of diabetes mellitus, a method for inhibition of activity 0f fructose 1,6-bis-phosphatase, a method for decreasing blood glucose in animals, a method for treatment of diseases associated with glycogen deposition, a method for inhibition of gluconeogenesis in animal and a pharmaceutical composition based on compounds of the formula (IA).

EFFECT: valuable medicinal and biochemical properties of compounds.

69 cl, 7 tbl, 64 ex

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