DE2119750C3 - Production of deuterated methanol - Google Patents

Description

Temperature is preheated. When passing through the heated catalyst, the gases react with the formation of deuterated methanol, which is collected in the product reservoir 7, which is externally cooled by the cooling jacket 8 and which is arranged in such a way that unconverted gas mixtures can be recirculated by convection through the lower part of the line 11 in d ^: f. catalyst column is facilitated. In this way, the mixture of D ₂ , CO and methanol-d ₄ continuously leaving the catalyst column is stripped from the latter through the product reservoir, and an essentially pure mixture of D _s and CO continuously enters the catalyst column in order to be partly used there Formation of "methanol-d _4" to react. After filling the product reservoir 7 by closing valve V ₂ , removing the cooling jacket 18, heating the reservoir to ambient temperature and, with the valve K ₁ open, evacuating the deuterated methanol through a liquid Nitrogen-cooled glass template 2 emptied by means of a conventional laboratory pump 1.

The method according to the invention represents a marked improvement over the known methods, since it requires little labor and only modest apparatus and can be carried out under conditions which provide methanol-d _{4 of} high isotopic purity (99 to 99.4 atomic percent D), where Furthermore, the utilization of the deuterium gas is high and the only loss is that caused by by-product formation.

The following examples serve to further illustrate the process according to the invention. Naturally, within the scope of the invention, modifications within those described above can also be made Pressure and temperature ranges as well as other modifications as with respect to the specific catalyst and the scope of the experiment.

example 1

Working at 9.6 at initial pressure and 275 ° C

In the case of a methanol device of the type shown in the drawing

tion explained and described above

with closed valves V ₂ and V ₃ and open

Netem valve V ₁ , the gas reservoir 9 was labeled ,,,,. charged, and carbon monoxide Deutum to 6 ^ 3 at dam . ^

^W ü "i ^de H ^ Heizelf ment 6 which included the zinc oxide HeizeienT"? · _{3§ / chromium oxide)}

i ₅ evacuated, where ^ og ^ 'γ _o ".

Example 2

Working at 14 at and 250 ° C, o The procedure of Example 1 was followed with au

Deuterium gas to a total pressure of 14 at e »n- ³⁵ iZVJi V. and pumping out"«^" ^ g '

^ Ä, S "i ⁸⁸ v-äur» i ^,. ^D s 5.9 at.

1 sheet of drawings

Claims (5)

Patent claims: 1. A process for the preparation of methanol-d ₄ , characterized in that 1 part of carbon monoxide and 2 parts of deuterium gas in the presence of a methanol catalyst and at a pressure in the range of about 7 to 28 atmospheres at a temperature in the range of about Heated between 200 and 400 ° C. 2. The method according to claim 1, characterized in that the methanol catalyst is used a mixture of zinc oxide and chromium oxide is used. It has been found that by deuterating carbon monoxide at a pressure in the range from about 7 to 28, preferably Hat and a temperature in the range from about 200 to 400 ⁰ C, one S preferably from 275 ° C, in the presence of any commercial, for The methanol synthesis used catalyst, preferably a mixture of zinc oxide and chromium oxide, preferably 74% zinc oxide and 23% chromium oxide, can receive daily yields of purified, fully deuterated methanol of on average around 50 g According to a preferred embodiment of the invention, a pretreated catalyst is used. When using a fresh batch, 3. The method according to claim I or 2, characterized in that the reaction at nol-d ₄ can be carried out at a temperature of about 275 ° C. in the first 3 or 4 batches of product. a low isotopic purity (<99 atoia percent D) 4. Process according to one or more of the present, since the catalyst is exchangeable » Claims 1 to 3, characterized in that it can contain hydrogen. This is easy to do to avoid the reaction at a pressure of about 20 in the following way: Give the ge-14 at performs. desired amount of catalyst and then suffice ^ 5. The method according to one or more of the deuterium oxide in a flask to cover the catalyst claims 2 to 4, characterized in that, and closes the flask. After one with a catalyst having a content of 24 hours, the heavy water is / o of zinc oxide and 23 ^and / or of chromium oxide 25 animals removed, a second post deuterium oxide operates by Dekanvon 74 °. added and the flask closed again and 'left to yourself for 24 hours. The catalyst will dried by heating under the steam hood and the heavy water in one to one 30 vacuum pump connected, cooled template The invention relates to a technically feasible collected. The first batch of methanol, CD., OD, a compound which contains methanol-d ₄ > 99 atomic percent D.
is known as a proton CMR solvent Since the method according to the invention is suitable because, while methanol itself signals through relatively low pressure is carried out, proton CMR delivers and these are on the compressors or circulating pumps, how to analyze the compound due to interfering- they avoid this problem when working at the higher pressures of the th, deuterated methanol- state of the art required, not necessary. The fact that deuterium does not respond to proton CMR method according to the invention is easily understood by those skilled in the art. The use of deuterated methanol for a work opportunity on a larger scale thus ensures that only the rod in solution is determined by enlarging the material used here and not the solvent.
Fully deuterated methanol is also suitable for
microbiological oxidation studies, for infrared spectral work and for the investigation of reac- 45
mechanisms. Methanol-d ₄ can be used at any pressure of i Ü System components or adaptable by combining several such units, and such modifications are within the scope of the invention. A device suitable for carrying out the method according to the invention is shown in the drawing tion explains in which V _x , V., and V _3, respectively k i Negative pressure up to overpressure of several hundred mean a valve, P is a pressure gauge "and SR synthesize atmospheres. High pressures amplify a safety output. A gas supply creates methanol, but the use of 50 container 9 is via lines 10 and II to the Specialized materials, pumps and compressors connected to the catalyst column 5, which are necessary at the top. By means of the present invention with a thermometer 4 and also a heating dung, such costly factors are unnecessary, element 6. The column is fed by the reaction at pressures is carried out, with the methanol synthesis catalyst, which can easily occupy the interior space up to the inlet of the line 10, however and conventional metal valves are not manageable by means of conventional metal piping 55, and does not require pumps or compressors to mix the gases external, such as pressures of 7 b is 28, but preferably 14 at. not shown storage tank in the gas, the reaction may proceed at temperatures of about reservoir 9, where valve F is open _1200-400 ^'1 C are carried out to give 60 and the valves V ₂ and F _{3 are} closed. Vorzugswcisc, however, works at 275 ° C. Higher, preferably, "the gases in the ratio of temperatures shift the reaction equilibrium - 2 parts of deuterium to 1 part of carbon monoxide weighted in the direction of the reagents (CO + D ₂ ). After charging with the correct gas, however, intensify the formation of the methanol-d Mixing and achieving the desired pressure The reaction should therefore be carried out at the lowest _{possible temperature. Valve F 1 is closed} and valve F is opened so that the possible temperature can be achieved which, with the merged gases through the line, increases the methanol formation per unit of time 10 and Π flow into the catalyst column