DD209433A1 - UNIVERSALLY APPLICABLE ARRANGEMENT FOR THE PRODUCTION OF C ISOTOPHYLED CARBON HYDROCARBONS - Google Patents

Abstract

The object of the invention to further develop known processes or arrangements for the preparation of labeled hydrocarbons based on the microcatalytic pulse regime with gas chromatographic product separation so that it is also developed for multi-stage reactions and multicomponent feedstock was achieved by arranging a mixing vessel to the metering device, another reactor for the Main reaction and a reactor for a post-reaction.

Description

Universally applicable assembly for the production of C-isotopically labeled hydrocarbons

Field of application of the invention

The invention relates to a universally applicable arrangement for the production of C-isotopically labeled hydrocarbons, which are used for research work in the field of hydrocarbon-converting processes.

Characteristic of the known technical solutions

The preparation of C-isotope-labeled hydrocarbons requires attention to a few special features compared to conventional preparative chemistry:

1. The low available number of suitable isotope-labeled starting compounds allows only a few possibilities for the preparation of the desired compounds. More complex and less effective synthetic routes are required for more complicated hydrocarbons.

2. The high price of the isotopically labeled starting compounds and the required high isotope content of the preparations to be prepared require a lossless as possible, equipped with the possibility of recycling Arbeitst_echnil <in Milli- or Mi.kromolmaßs t_ab_.

1 & SESS 1982 * 035374

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3. The potential danger of invasion when working with the radioactive carbon isotoo C forces to a safe working technique, which avoids uncontrolled losses and to work in a closed system.

Hitherto, isoto-labeled hydrocarbons have generally been prepared on the basis of classical synthetic routes, taking into account the abovementioned special features in a closed vacuum system made of glass components. Although heterogeneous catalytic routes for C-isoto-labeled hydrocarbons have been known for a long time, they have not been used for the time being because of their low conversions and selectivities and the difficulties in working with the required small amounts of substance in heterogeneous catalytic processes. Also, the commercial offer of the requisite labeled starting compounds included only a few available hydrocarbon bases such as benzene, naphthenes and n-alkanes.

Only with the development of new high-performance catalysts, which are widely used in the chemical industry for analogous hydrocarbon-converting processes z. For example, DE-OS 2,622,318 and with the construction of new arrangements or new apparatuses for the conversion and separation of labeled hydrocarbons, it has been possible to reduce these disadvantages.

So z. B. eliminates a number of the aforementioned difficulties according to DD-PS 149 758 by a combined application of the micro-catalytic pulse regime and the preparative-gas chromatographic separation of the reaction products with product recycling. For this purpose, an arrangement was created, which consists of the following Hauotfunktionsgruppen:

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1. Metering device

2nd reactor for the main reaction

3. Gas chromatograph with cooling system

Although this offers great benefits to the classical working technique such as

high activity yield

- quasi-continuous operation

- high labor productivity

- Work under pressure and thus under thermodynamically more favorable conditions

but it has the disadvantage that only one-step reactions with a use component are possible.

Object of the invention

It is to the advantages that result from the application of the known arrangement and the possible production of C-isotoomarkierten hydrocarbons based on the microcatalytic pulse regime with gas chromatographic product separation, by a further development of this arrangement for multi-stage reactions and / or hehrkorr.oonenteneinsatzprodukte thereby further increasing activity yield and labor productivity, as well as enabling quasi-continuous and stable operation.

Explanation of the essence of the invention

The technical problem to be solved by the invention is to provide a universal arrangement which can produce one-step reactions with a use como

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te and multistage reactions with a feed component or Mehrkorr.Donen teneinsa tzproduk th and further conversion of a separated Reaktionsoroduktes allows.

Features of the invention

This object is achieved in that the metering device forming part of the arrangement equipped both with a microsyringe for product dosing and with an input device for feed products from ampoules and a gas metering valve of this dosing a cool and heatable mixing vessel for the reactants is arranged and the Reactor for the main reaction is preferably downstream of another reactor or that this reactor is designed for the main reaction so that it receives at least 2 different catalysts arranged in layers one above the other.

To one of the cold traps, which belongs to the main functional group "gas chromatograph with cooling system", a reactor for secondary reactions is connected. In the connecting line between this cold trap and the reactor, a hydrogen supply line is integrated. The reactor outlet line has a connection for cold traps and is incorporated in the connecting line (capillary), which is arranged for the purpose of product recycling between the cooling system and the input device for feed products heated.

With the universal arrangement according to the invention, C-isotopically labeled hydrocarbons can be removed after the

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Known heterogeneous catalytic processes under atmospheric pressure and one-step reactions with a Komoonente under a pressure above 0.1 MPa readily produce.

If it is necessary to use comonomer components and heel stage reactions for the preparation of certain marked hydrocarbons and if, in addition, an after-reaction is optionally provided, then the following procedure is followed:

The reactor or reactors for the main reaction and the reactor for the post-reaction are filled with suitable catalysts.

After checking the operation of the device ampoules, each receiving a component of the feedstock in the previously calculated amount, connected sequentially to an input device and transferred by heating the ampoule and applying a vacuum to the input device, the individual components of the feed mixture in a cooled mixing vessel. The closed hischgefäß is heated. The feedstock evaporate and mix. After opening the mixing vessel (sample), the feed products are flushed into or into the reactors for the main reaction with the aid of an H ₂ gas stream.

The reaction product then collects in a cooled loop of a metering cock and, after the entire reaction product is in this loop, is transferred by heating to a gas chromatograph for separation. The individual separate components of the reaction product are passed in a respective cooled collecting trap, optionally optionally selectable, one of the components to a further reaction, for. 8. Hydrogenation, on line in the

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Reactor is transferred for the after-reaction and only then condensed in a collection trap. Unreacted labeled starting material and any reusable by-products are not condensed into cold traps , but returned directly via a heated capillary line for re-use (recycling) in the mixing vessel.

After entering the unlabelled reactants in the desired ratio in the mixing vessel, the process can be continued by trial and error.

This recycling can be repeated until another use is no longer worthwhile.

embodiments

The invention will be explained in more detail below with reference to exemplary embodiments and with reference to a sketch - FIG.

example 1

Preparation of C-nucleated toluene, xylene, methylcyclohexane (MCH) and dimethylcyclohexane (DMCH) with the arrangement according to the invention when using a binary product mixture, with a transalkylation as a single-stage main reaction and a hydrogenation as a post-reaction.

This preparation is based on the transalkylation of benzene-C with trimethylbenzene (TFiB) on a NapO / ho ^ O ^ -modified mordenite catalyst with subsequent partial

14 Hydrogenation of the separated toluene and xylene C on a Ni-Ka taIysator.

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The first reactor for the main reaction 1 serves in this case only as a preheater and is filled with Al-semolina.

The second reactor 2 is charged with the aforementioned mordenite catalyst grain size 0.4 - 0.7 mm. In the reactor for post-reaction, a Ni catalyst is introduced.

Activation and Formation of the Catalyst in the Main Reactor:

- drying under He at 150 ⁰ C.

- Activation with H at 500 ⁰ C.

Forming with 3 to 5 dosages of 150 / ml feed mixture

Reaction and separation conditions:

Amount of catalyst: reaction temperature reaction pressure: separation column:

Separating tempera door: H-passage: input product quantity of feed product:

Hp carrier gas: Detector:

1.0 g 450 ^° C

0.4 MPa

3000 χ 6 mm, 15% dinonyl phthalate on porolite 120 ° C 4 1 per h 150 ^ 1

40 Ma. -% benzene- ¹⁴ C

60 Ma. -% TMB 4 1 Dro h VVelmeleit cell

To check the operation of the catalyst in the reactor 2 is an ampoule with 150, ^ 1 inactive feedstock

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(40 % benzene and 60 % TMS) used in the input device 10, heated and transferred by applying fine vacuum on the three-way cock 11 in the mixing vessel 9; Valve 4.2 is closed. By heating the closed mixing vessel 9, the feedstock is evaporated. The components mix. Now you set the gas metering valve 8 on trial and flushes the gas mixture with H_, which is supplied via an input 5, the valve 4.1 and a pressure gauge 6, in the reactors for the main reaction 1.2.

The reaction product collects in the cooled loop of the Gasdosierhahnes 12. After about 30 minutes, the entire reaction product is in the loop. The gas metering valve 12 is changed over, the reaction product is heated and transferred to the gas chromatograph 13 for separation. Is in the reaction product, the concentration of benzene - 15 wt .-% and fission hydrocarbon - 8 Ma. %, then the pre-cooled and opened ampoule with the benzene-C is inserted into the input device 10 and the benzene-C is transferred into the mixing vessel 9 in the manner described. Subsequently, on the same »Veg, as much inactive benzene and TMB are added in the specified proportions until ready for metering into the reactors for the main reaction 150 / 4.1 product.

Continue wira as described procedure.

The separated components of the reaction product leave the gas chromatograph 13 in the order:

1. Split hydrocarbons

2. Benzen- ¹⁴ C

3. ^toluene-14 C

4. Xylene- ¹⁴ C

----- - - - tar

5. trimethylbenzene C

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Components 1 and 3 are fed into separate refrigerated collecting traps. Component 4 is not condensed out, but immediately for the purpose of hydrogenation to DMCH in the reactor for after-reaction 3 and then condensed out.

The unreacted benzene C and the TMB-C are not condensed out in cold traps, but returned directly via dxe heated capillary 15 to the new use (recycling) in the mixing vessel 9. There the existing difference amounts to Benzen and TMB are refilled to 15ОДІ. Then a new reaction separation cycle is initiated. In this second cycle, in addition to the component which is placed in the same cold trap as in the first cycle, the comonents 2 and 4 are collected in separate cold traps and component 3 is hydrogenated to MCH. Another third reaction separation cycle with the remainder of benzene-C and with the forming TMB-C is not worthwhile when using 370 MBq.

Achieved final results:

- mass yield based on theoretical quantities:

Toluen - 93 %

Xylene - 88 %

MCH - 88 %

DMCH - 86 %

- Activity yield based on used benzene-C

Toluene [ring CJ - 39

- 5

C / O

Xylene [ring ¹⁴ c]

MCH ^ Ring ¹⁴ cj - 7 %

DMCH- [ring ¹⁴ c7 - 27 %

Benzen- ¹⁴ C - 3 ¹⁴ C losses - 19

between 94 and 98 % and the C content in the MethylgrupDie radiochemical purity of the recovered preparations

between

pe ^ 1 %.

Embodiment 2

Preparation of 2-methylheptane

- 12- ¹⁴ cl

The preparation is carried out from 2-ethylheptan-2-ol-J 2 -Cf a two-step reaction, d. H. a dehydration with subsequent hydrogenation ,, The C-alcohol is obtained from acetone-I2-Cf and η-pentyl bromide via a Grignard reaction

tion.

With the aid of the arrangement according to the invention, the following procedure is followed:

The reactor for the main reaction 1 is reacted with 1 g of catalyst

of the type "JJ - Al 0_, grain size 0.4 - 0.7 mm and the reactor

for the main reaction 2 with 2 g of Ni catalyst 1, grain size 0.4 - 0.7 mm charged.

Activation of the catalysts:

Reactor 1: dehydration at 550 ° C

Reactor 2: dehydration at 250 ° C

Reduction at 450 ^° C

Thereafter, in the reactor 1, a temperature of 230-250 C and in the reactor 2 of 140-180 ⁰ C is set. The formation of catalysts is aerated with 2-3 pulses of 200 ^ 1

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Hexanol made. The dosage is carried out at atmospheric pressure with a HU passage of 3 l / h by means of microsyringe 7 in the evaporator block 17th

The reaction products splitting hydrocarbons, 2-methylheptane and other isomers are fed to a gas chromatograph 13 and separated there on a 3000 mm separation column 13a with 15 % dinonyl phthalate on porolite at 120 ⁰ C and 4 l / h H ₂ -Trägeraas 16 and with a Wärieldeitzelle 13b is displayed. The use of 2-methylheptan-2-ol ~ / 2-Cj occurs when the hexanol in the formation of a conversion <Z yields 93 % . The conversion is practically 100%, so that no recycling is required. To reduce the * C losses, a pulse of inactive 2-methylheptan-2-ol must be added at the end of the work.

In this application example, the reactor for after-reaction 3 is not needed. The 2-methylheptane I 2 -Cj is collected in a cold trap 14, all by-products reach a common collection trap. The H "0 of the dehydration remains on the separation column 13a. It must be removed by annealing at 150 C at the latest after 3 separating cycles.

Average yields are as follows: mass yield: 7S, 0 %

¹⁴ C activity yield: 80.3 %

Claims (3)

ППП 4 invention claim 1. Universally applicable arrangement for the production of C-isotope-labeled hydrocarbons, consisting of the main functional groups metering, reactor for the main reaction and gas chromatograph with cooling system, characterized in that the functional group metering additionally equipped with an input device for multi-component use products and in her a cool and heatable mixing vessel is arranged for reactants that the reactor for the main reaction is preferably downstream of another reactor or this reactor is designed for the main reaction so that it at least 2 different catalysts arranged in layers one above the other and that the cooling system of the 3rd main functional group is a reactor for after-reaction connected. 2. Universally applicable arrangement according to item 1, characterized in that in the connecting line between the cooling system and the reactor for after-reaction, a hydrogen supply line is integrated. LH 3. Universally applicable arrangement according to item 1 and 2, characterized in that the output line of the reactor for after-reaction rcit connected with cold traps and is integrated into the connecting line, which is arranged for the purpose of product recycling between the cooling system and the input device for multi-component use products heated. - For this 1 sheet drawing -