![]() Method of obtaining magnesium hydride
专利摘要:
1. A method of producing hydrated magnesium by hydrogenation with magnesium water in an organic solvent medium in the presence of a catalyst, characterized in that, in order to improve the quality of the target product, the hydrogenation is carried out at a temperature from 0 to and from 1 to 300 bar the catalyst uses a system consisting of a transition metal compound of 4-8 side groups of the periodic system and a metal hydride or an organometallic compound of a metal of 1-3 groups as such, and obtained in situ by reacting the corresponding metal and anthracene, with a ratio of magnesium and transition metal 10 - and a transition metal and organometallic compound or metal hydride 0.1 - 10: 1. 2. The method according to paragraphs. 1 and 2, which is based on the fact that the process is carried out in the presence of an activator, in F as which is used a polyC cyclic aromatic compound or a tertiary amine of the formula M (h, where C is alkyl or cycloalkyl, or aryl, or pyridyl, or a mixture of each Of these compounds with a magnesium halide of the formula MqV2 where X is Ct, iBtT,, when the ratio of magnesium and magnesium halide is 1: 1. about 4 公开号:SU1109047A3 申请号:SU792719151 申请日:1979-02-02 公开日:1984-08-15 发明作者:Богданович Борислав 申请人:Штудиенгезельшафт Коле Мбх (Фирма); IPC主号:
专利说明:
This invention relates to methods for producing magnesium hydride by a catalytic method. Dp of obtaining magnesium hydride using known methods requires high temperatures and high pressures. It is known to obtain magnesium hydride at 140-170 ° C and a pressure of 135 bar in the presence of aluminum triethyl; at a temperature of 15Cf С and a pressure of 200 to a temperature of 380-450 С and a pressure of 100-200 bar GZ. The closest to the invention to the technical essence and the achieved result is the method of obtaining magnesium hydride, which consists in hydrogenating magnesium in hydrogen in tetrahydrofuran medium in the presence of vanadium tetrachloride as a catalyst at a pressure of 1 bar C4. The disadvantage of these methods is the rapid decrease in the catalytic activity of the system. In addition, under these conditions, the supernatant absorbs hydrogen in not sufficient quantities. The purpose of the invention is to show the quality of the target product. The goal is achieved by the fact that, according to a known method, hydrogenation is carried out at a temperature of from 0 to 200 ° C and a pressure of from 1 to 300 bar, using a system consisting of a transition metal compound 4-8 side groups of a periodic system and a metal hydride as a catalyst or an organometallic compound of a metal of 1-3 groups as such, and obtained in situ by reacting the corresponding metal and anthracene, with a ratio of magnesium and transition metal IO - 10: 1 and a transition metal and organometallic Compound or Metal Hydride O The process of hydrogenation can be carried out in the presence of an activator. As a polycyclic aromatic compound or a tertiary dmin of the formula NRi, where R is alkyl or cycloalkyl, or aryl, or pyridyl, or a mixture of each of these compounds with magnesium halide of the formula MqYJ where AG, Br, H, with a ratio of magnesium and magnesium halide 1: 1. According to the invention, in order to obtain magnesium hydride, magnesium metal is reacted with hydrogen in the presence of a catalyst; if necessary, an activator can be added. Anhydrous magnesium halides are additionally introduced into the reaction medium to obtain soluble magnesium hydride halides. The process is carried out in the medium of a solvent, which can simultaneously serve as an activator. Tetrahydrofuran is preferably used as a solvent. Halides, alkoxides, enolts, carboxylic acid derivatives, allylic acids are predominantly used as transition metal compounds of the 4–8 side groups of the catalytic system. and cyclodentadienyl compounds of these metals. . The transition metal compounds preferred for use are the chromium, iron and titanium halides. . Magnesium anthracene or magnesium and butadiene compounds are preferably used as organometallic compounds. Polycyclic aromatic hydrocarbons such as naphthalene, tetracene, pentacene, phenaltrene, perylene, anthracene, and tertiary amines, for example triztilamine, tributylamine, are used as activators. The invention makes it possible to directly produce magnesium hydride catalytically under mild conditions. Magnesium hydride, obtained according to the proposed method, is superior in its function to the hydrogen accumulator of magnesium hydrides obtained by known methods. It can be quantitatively dehydrogenated and then the resulting magnesium can be subjected to hydrogenation again, with no change in the rate or ability of hydrogen accumulation observed. Magnesium hydride prepared according to the invention can be used as a reducing agent instead of LiAtw ..,; Example. A suspension of 97.2 g (4 mol) of magnesium powder (50 mesh) in 400 ml of absolute tetrahydrofuran (T GF is mixed with I ml of methyl bromide ethyl, and after stirring for half an hour, with 8 g (45 mmol of anthracene. After 3 hours stirring the mixture (this gives magnesium anthracene), 7 g (44 mol) CvCl4 is added, and then stirred for another 25-30 minutes. The resulting olive The green suspension is hydrogenated with hydrogen in a 2-liter autoclave with a stirrer at an initial pressure of 135 bar. After 5 hours, the hydrogen pressure is 92 bar, after 8 hours - 82 bar, and after 20 hours of the process the pressure remains constant. em approximately 72 bar. The pressure drop corresponds to the absorption of 100 liters of hydrogen or the quantitative conversion of Mo in. Magnesium hydride from the catalyst solution can be separated by filtering the resulting suspension, followed by washing with tetrahydrofuran or pentane and vacuum drying. The result is magnesium hydride in a solid pyrophoric form. The product yield is quantitative. Example 2, .97.2 gS4 mol of magnesium powder in 250 ml of absolute THF was placed in a 2-liter autoclave with a stirrer and 0.4 g of iodine was activated by adding it. A suspension of 3.8 g (19 mmol) of magnesium anthracene and 0.5 g (20 mmol t of magnesium bean and 180 ml of THF is mixed with a solution consisting of 3 g (17.5 mmol of PeCC-i, and 20 ml of THF, mixture After 20 minutes, the mixture is hydrated with hydrogen at 52 ° C and an initial pressure of 120 bar. After 24 hours of the process, the hydrogen pressure is VOBAR and after 48 hours the hydrogen pressure remains constant, about 62 bar. . The pressure drop corresponds to a total absorption of 3.4 mol of hydrogen or a complete conversion of Mcj to Mc Hj. PRI me R 3-AND. A suspension of 4.86 g (0.2 mol of magnesium powder (50 meth) in 50 ml of absolute THF is mixed with 0.05 ml of ethyl bromide and, after stirring for half an hour, with 0.36 g (2 mmol of Anthramine). After 3 stirring the initial mixture frequently (at this time, magnesium anthracene is formed, which can be detected by precipitating an orange precipitate. 2 mmol of the corresponding compounds are added to the suspension. transition metals (see tab. 1) and still mix 15-20 -min. The reaction vessel at normal pressure is filled with hydrogen, and the absorption of hydrogen at 20 ° C with stirring is measured using a gas burette. The absorption of hydrogen takes place over several days at almost constant speed. Data on the amount of hydrogen absorbed after 48 hours, or the percentage of conversion of Ma into are given in Table. I. Examples 12-15. The process is carried out analogously to Example 4, with the molar ratio (20: magnesium anthracene ranging from I: 0, 5 to 1:10. The values of Fl2 absorbed after 48 hours or the percentage of Mq conversion are given in Table 2. EXAMPLE 16-18. The process is carried out analogously to Example 4, and the initial mixtures are mixed with 10 mmol of amine, see Table 1, before passing on hydrogen. 2). The values of hydrogen absorbed after 48 hours and the percentage of conversion of MS to MoHj are given in table. 3 Examples 19. The process is carried out in a manner analogous to Example 4, a mixture of 40 ml of toluene and 10 ml of THF being used as the solvent. Hydrogen uptake after 48 hours is 500 ml. EXAMPLE 20 The process is carried out analogously to Example 4, with 1,2-dimethoxyethane (50 ml) being used as a solvent instead of THF. Hydrogen uptake after 48 hours is 220 ml. Examples 21-27. The process is carried out analogously to Example 4, in which the organometallic compounds Mmol are used as the component of the catalyst instead of magnesium anthracetic. Data on the absorption of hydrogen after 48 h are given in Table. four. Example 28. A suspension of 0.6 mmol of magnesium powder in 10 ml of absolute THF is mixed with 0.02 ml of ethyl bromide and, after stirring for half an hour, with 0.6 g of 0.37 mmol of anthracene. After three hours of stirring, 0.06 g (0.37 mmol) of C Cdj was added to the suspension, and after another 13 minutes a solution of 4.9 g {27 mol) M (j Vg Oez5P aqueous in 120 ml of THF) was added. hydrogen in a 500 ml autoclave with a stirrer equipped with a glass nozzle for 12 hours at a pressure of 100 bar. Suspensions are allowed to stand for 20 hours; 25 total 130 ml of clear supernatant solution give 140 ml of NO, solution during deuterolysis. / also contains 1.15 g (47 mmol Mq and 4.29 g (53.6 mgat of BG. This composition corresponds to the yield of soluble fiHiBt- mixed with MaBj), equal to about 60%. PRI me R 29. 97 g (4 mol of magnesium powder in 370 ml of absolute THF is placed in a two-liter autoclave with a meihalka and with an aid of a ml of ethyl bromide, it is activated. 2 liters (83 mmol) of gaseous butadiene and contents Indicators 3 | 4 I 5 1 6 CrCd, RECESE, Compound re0, 32. 0.32 0.71 0.38 of the starting metal (g / 2 mmol, Absorption N 2000 1500 300 1300 after 48 h, ml Conversion to MoI in 42 31 6 27 48 h,% acac - acetylacetonate Indicators 12 Fe CC J, g / mmol 0.32 (2) 0.32 Anthracene, g (mmol) Absorption 11 after 48 h WI Turning into MAN after 48 h,% table 2 Examples R L .. 13 - 15 0.36 (2.) 1500 7. Autoclave E is heated for 1.5 hours to 80 ° C (an organo-magnesium compound is formed. After cooling to room temperature, 3.2 g (9 9 mmol Ce in 30 ml of THF) are added to the contents of the autoclave. The loaded mixture is hydrogenated with hydrogen at 20–22 ° C and an initial pressure of 120 bar. After 20 hours, the pressure I u uai. Uu jni; I bar ii h pressure of hydrogen drops to 97 bar and after 4 hours the pressure remains constant, about 92 bar. The pressure drop corresponds to a total absorption of 2 mol of hydrogen or the conversion of MQ to Mq "g - equal to about 50%. EXAMPLE 30 The ess was carried out analogously to example 3, and instead of using CfCOj as a component of the catalyst, (3 d g – 2 mmol) was used. The hydrogen uptake in 48 hours was 850 T.bl and c 1 Examples 7 I 8 I 9 I 10 I P UOKts MoCtg MnCI CoC, NiC 0.39 0.56 0.25 0.26 0.26 500 700 950 250, 200, 10 15 20 5 0.32 0.71 (4) 850
权利要求:
Claims (2) [1] 1. METHOD FOR PRODUCING MAGNESIUM HYDRIDE by hydrogenating magnesium with hydrogen in an organic solvent in the presence of a catalyst, characterized in that, in order to improve the quality of the target product, hydrogenation is carried out at a temperature of from 0 to 200 ° C and a pressure of from 1 to 300 bar and as The catalyst used is a system consisting of a compound of a transition metal of 4-8 side groups of the periodic system and a metal hydride or an organometallic compound of a metal of 1-3 groups, either as such or obtained in situ by reacting with Resp metal and anthracene at a ratio of magnesium to transition metal of 10 - 1 D * 1: 1 and a transition metal and an organometallic compound or metal hydride 0.1 - 10: 1. [2] 2. The method according to PP. 1 and 2, characterized in that the process is carried out in the presence of an activator, which is used as a polycyclic aromatic compound or a tertiary amine of the formula, where 2 is alkyl or cycloalkyl, or aryl, or pyridyls, or a mixture of each of these compounds with halogen -_ the house of magnesium of the formula , Bt, D, with a ratio of magnesium to magnesium halide 1: 1. > I I 10904 7
类似技术:
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同族专利:
公开号 | 公开日 AU4388079A|1979-08-09| IE790199L|1979-08-02| MX151049A|1984-09-18| EP0003564B1|1982-04-07| DE2804445A1|1979-08-09| JPS54112799A|1979-09-03| DD141297A5|1980-04-23| DK151374B|1987-11-30| ATA73879A|1985-09-15| US4554153A|1985-11-19| AT380223B|1986-04-25| IL56562A|1982-04-30| ES477378A1|1979-07-01| AU526947B2|1983-02-10| DK44479A|1979-08-03| JPS6346001B2|1988-09-13| DK151374C|1988-06-13| CA1135480A|1982-11-16| US4957727A|1990-09-18| DE2962411D1|1982-05-19| BR7900628A|1979-08-28| IE48062B1|1984-09-19| EP0003564A1|1979-08-22|
引用文献:
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申请号 | 申请日 | 专利标题 DE19782804445|DE2804445A1|1978-02-02|1978-02-02|METHOD FOR MANUFACTURING MAGNESIUM HYDRIDS| 相关专利
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