DD155517A1 - METHOD FOR TREATING AND RESERVING RELAXATION GASES - Google Patents

Abstract

The process for the treatment and reuse of flash gases is used in the operation of methanol synthesis plants and also in the simultaneous operation of these with other chemical syntheses. The goal of highly effective use of the primary energy carriers used and the task of processing them to a higher utility value, are solved by a substantial use of materials, the methanol synthesis plant is combined with a gas separation plant and consumers of the products of the gas separation plant in a special way. The technology according to the invention makes it possible to save large quantities of oil and natural gas.

Description

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VEB Leuna-Werke Leuna, 15 "11" 1980

"Walter Ulbricht"

LP 808? , Title of the invention

Process for the treatment and reuse of flash gases

Field of application of the invention

The process can be used in the chemical industry in the operation of integrated methanol synthesis plants and also in the simultaneous operation of methanol synthesis plants and "other chemical syntheses, in particular of ammonia syntheses _s hydrogenation processes and / or other Be carriers of hydrogen and / or carbon monoxide or · carbon dioxide carrier for the purpose of extensive material economic use of high-quality primary energy ", such as natural gas or naphtha _s petroleum or · the technological reasons accumulating expansion gases · possibility _2, the method into existing chemical complex operation to insert ·

Characteristic of the known technical solutions

It is generally known that the ₉ in chemical syntheses _s, for example, at a synthesis of ammonia and / or methanol

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Synthesis of forcibly produced purge gases in. The heating gas passed and used for underfiring in the generally after the Ste amre formirtgver driving η working synthesis gas production (Schmidt: process of gas treatment, VEB Deutscher Verlag for basic industries, Schmidt: technology of gas production, Bd »II - Gasification _s VEB German publishing house for basic industry, Falbe: chemical raw materials from coal, Georg Shieme publishing house - «Stuttgart).

These methods have the disadvantage _s that gas generator units are operated, of which a relatively large capacity only the production of fuel gas is used © Furthermore, it is to the disadvantage that the high-quality primary energy sources used for this ₉ Heizgaserzeugung _9, for example, of natural gas or naphtha with the gasification efficiency and this proportion verlorengeht® in gas production as waste heat Finally, it is particularly disadvantageous that the _$ techno "are material economically exploited logically related janfallenden Purgegase ©

It is also well known in the treatment and re-use of purge gases of ammonia synthesis that you add the resulting in the ammonia purge gases consisting of hydrogen, nitrogen, argon, methane and ammonia, a hydrogen recovery plant, there removes the ammonia, the hydrogen γοη separates the residual components and reused it as synthesis hydrogen for ammonia synthesis. The resulting residual fraction, which still consists of nitrogen, argon and methane, is then passed into the heating gas and generally in the primary reformer of the S te amre forming deposit burned «The calorific value of the separated hydrogen equivalent amount of heat is covered by the use of natural gas ( Air and Refrigeration Technology 16 (1980) 1 _$ S * 15-19).

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In extension of such hydrogen recovery plants it is also known to subject the resulting residual fraction to further separation and to extract from it the noble gases argon, if necessary, also krypton and xenon (Ind. Eng, Chern, Process Des. Develop 12, 3 (1973). , S * 217-220).

These procedures already have the advantage of _$ that the gas generator units γοη only for the production Ammonialcsynthesegas, but are not used to Heizgasproduktion and the fuel source from which _s becoming used ₈ without exposure to the gasification efficiency of di ~ rectly as a fuel gas such as natural gas or naphtha also are in this case the expansion gases However, you have the decisive disadvantage in terms of material economy for ammonia production _? that they are not readily transferable and applicable to methanol synthesis plants, since completely different substances and conditions are required for the synthesis of the reaction components to methanol than in the synthesis to ammonia *

As a method for carrying out the hydrogen recovery from purge gases of the ammonia synthesis or «for the treatment of these gases cryogenic processes for the separation of gas-steam mixtures are known ₉ which are cooled under pressure ₉ partially liquefied and expanded in a separator« Without a foreign cooling takes place (DD -PS 47120) or with external cooling (The oil and gas journal _T March ^ (1979) »S, 182) are returned after the separator both incurred phases and thereby made necessary for the equilibration adjustment © The process without forced cooling has the disadvantage in that it is only applicable to gas mixtures in which the low-boiling component hydrogen is not more than approximately 65 % . "The external cooling processes are applicable only to the parabolic gases of NH ^ synthesis.

As a further method for carrying out the hydrogen recovery from purge gases of the ammonia synthesis or © for the treatment of

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These gases are adsorptive known processes ₉ (US = OPS 40 0770780) "These processes have the Bach part ₉ that hydrogen yields of only max © 80 % can be achieved ©

In addition, the Wasserstoffrückge · = · winnung from hydrogen-rich gas mixtures are for performing bzw® for treating these gases permeation known, these methods have the disadvantage ₉ that the hydrogen-rich gas mixtures must be at high pressure available and the hydrogen fraction not nearly with the pressure can be obtained ₉ with the hydrogen-rich gas mixtures of the system must be supplied (DD-1054-29) <s

All methods for carrying out the hydrogen recovery have the further common part ₉ that for the application in the treatment of the expansion gases of the methanol synthesis no instructions are given for technical action »

In other known methods for purifying gases and vapors or, for decomposing gas mixtures by pressure swing adsorption is indicated _f that the components carbon monoxide and carbon dioxide can be separated from hydrogen (DE-OS 2 _c 629 "4-5O)" For the special treatment of expansion gases of the methanol synthesis and the reuse of the decomposition products within a chemical operating complex, however, are not mentioned as solutions *

Finally, it is known to supply the Eestgase of methanol synthesis of extensive material use. »For the synthesis of the simultaneously operated methanol synthesis j ammonia synthesis with simultaneous operation of synthesis plants for the production of methanol and ammonia and a Restgaszerlegungsanlage, which is operated with the residual gases of ammonia synthesis and residual gas separation plant connected in series in this order

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and the residual gases of the methanol synthesis optionally after methane removal and purification used as synthesis gas for ammonia synthesis (DD-PS 84-629) * The method has the disadvantage that it can be used only in methanol syntheses _$ in which a relatively small amount of residual gases is obtained * The methanol technologies put into practice generate a relatively large amount of residual gas,. which would also require a relatively high effort for the decomposition of methane If one would not carry out this relatively high expenditure, the ammonia synthesis would be burdened by a very large amount of methane as inert gas, whereby the process in its entirety becomes uneconomical. "

The process has the particular disadvantage that it can not be used in integrated methanol plants and that no solutions are given to cover the residual gas withdrawn from the heating gas balance.

Object of the invention

The aim of the invention is to provide the high-quality fuel source for methanol synthesis or _e technological reasons accumulating expansion gases economically highly effective reuse and to ensure their use extensively in chemical plant complexes "The solution is to se applicable to new as well as existing methanol synthesis plant is in *

Explanation of the essence of the invention

It was therefore the task _$ to recycle the forcibly incurred in the implementation of the methanol synthesis flash gases to a higher utility value and supply after their on ^ processing a largely economically effective Hutzen «For this purpose, the expansion gases are decomposed into their components and the products obtained during the decomposition largely as reaction components to supply suitable chemical processes «

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With the solution of? Task should be the deficiencies and imperfections of the known solutions to be eliminated. "In particular, the hydrogen recovery to the Pargegasen of ammonia syntheses to the treatment and reuse of the expansion gases of methanol syntheses transferred ^ the relatively high cost of removing the methane contained in the expansion gas reduced and the fuel gas demand of Complete system ·

Thus, the expansion gases of the methanol synthesis preferential "·· consist of hydrogen carbon monoxide, carbon dioxide, nitrogen, argon _s methane and traces of methanolg higher alcohols, dimethyl ether and amines _{e In} contrast, the purge gases of ammonia synthesis from hydrogen _$ nitrogen argon, methane and Ammonia together © This means that the technological measures for decomposition of the expansion gases are different from those for decomposing the purge gases «

Furthermore, in the synthesis of methanol, the components hydrogen 5 carbon monoxide and carbon dioxide are synthesized to methanol · In the inert gases nitrogen, argon and methane inhibit the reaction process «In the ammonia synthesis, hydrogen and nitrogen to ammonia synthesized carbon monoxide and carbon dioxide are highly active contact poisons« argon and methane occur As inert gases on "Due to these essential technological" deviations in the syntheses, the further use of the fractions obtained in the treatment of the expansion gases of the methanol synthesis is essentially different from the further use of the products obtained in the purge gas decomposition of ammonia syntheses.

Finally, in general in the synthesis process of the methanol synthesis technologically conditioned often hydrogen amounts are present ^ not; Participate in the methanol synthesis and therefore have to be relaxed · A recirculation of the recovered hydrogen to ¹ methanol synthesis would reinforce this negative effect even * A decomposition and Stoffwirtschaft-

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The use of the expansion gases of the methanol synthesis in analogy to the known processes in ammonia synthesis is therefore not possible without additional inventive work.

Features of the invention

The object is achieved by a process for the treatment and further use of flash gases j forcibly incurred in the Durciaführung the methanol synthesis and consist essentially of hydrogen ₉ carbon monoxide _s carbon dioxide ^ nitrogen, argon $ methane and traces of methanol ^, higher alcohols ^, diethyl ether and amines If appropriate in conjunction with a simultaneously operated ammonia synthesis and / or hydrogenation processes according to the invention solved in that the resulting flash gases are largely used material economy * For this purpose, the methanol synthesis plant with a gas separation system and consumers of the products of the gas separation plant combined so far that the expansion gases of Gas separation unit are fed and separated there a highly concentrated hydrogen fraction, withdrawn and used to carry out chemical synthesis and / or hydrogenation _e separation of the highly concentrated hydrogen fraction is undertaken so that the same .Prior _s, "intermediate" and / or ßestfraktionen§ preferably ^ of carbon monoxide carbon dioxide * consist of nitrogen, argon and methane, extracted, stripped off and this in the production of synthesis gas for methanol synthesis and / or in the Processing of the synthesis gas to methanol and / or other consumers, possibly also used as heating gas. By the thus largely material use of the use of expansion gases are the entire process of Ifethanolanlage, in particular the reformer withdrawn considerable amounts of fuel gas According to the invention by direct combustion of the methanol synthesis primary energy source and / or any fuel gas used and / or compensated by external heat input,

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The separation of the highly concentrated hydrogen fraction carried out in the gas separation plant and the recovery of the precursor, intermediate and / or residual fractions are advantageously carried out according to the principles of pressure swing adsorption or permeation or low temperature treatment or a combination of these gas separation principles, if appropriate with simultaneous use of chemical laundry, carried out ·

The requirements for the products of the gas separation plant depend on the production profile of the chemical industry complexes. gig ".

Thus it is with the simultaneous further use of a highly concentrated and high-purity hydrogen fraction and a residual gas fraction which essentially still hydrogen § carbon monoxide carbon dioxide ^ nitrogen § argon, and methane contains ^ favorable if the Entspaanungsungsgase one preferably by the pressure swing adsorption process or the permeation process working gas separation plant decomposed into these fractions

In addition, if a simultaneous reuse of carbon dioxide is given ^ so it is particularly favorable ^ to perform the decomposition of the flash gas in a gas separation plant, which worked with a combined cryogenic ~ pressure swing adsorption _P or low-temperature permeation process In this case, the Hestgasfraktion contains essentially only the components Hydrogen ₉ carbon monoxide, nitrogen, argon and methane »

Is the simultaneous re-use of carbon dioxide and a highly concentrated hydrogen "fraction and a Eestgasfraktion, which still contains substantially hydrogen, carbon monoxide, nitrogen, argon and methane, provided and you need the highly concentrated hydrogen fraction with technical purity, it is particularly favorable to carry out the decomposition of the expansion gas in a gas separation plant operating according to the pure low-temperature method.

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The process is also advantageous if, in the simultaneous further use of carbon dioxide, a highly concentrated iind high purity hydrogen fraction and a Re stgasfraktion the flash gases first fed to a chemical laundry, bfrit there from carbon dioxide and then by means of a Druckwechseladsorptionsverfahrens or a Permeationsverfahrens in the highly concentrated and high purity . Hydrogen fraction and the residual gas fraction, which still contains substantially hydrogen, carbon monoxide, nitrogen-argon and methane, are decomposed. The intended for further use carbon dioxide is then recovered by the regeneration of the washing liquid of the chemical laundry _s in which the carbon dioxide is released won

In practice, chemical washing using monoethanolamine or hot potash solutions has proven to be particularly effective for carbon dioxide recovery *

When the gas separation plant is operated to simultaneously recover the high concentration hydrogen fraction, the carbon dioxide fraction and the residual gas fraction by the cryogenic process or by a combined cryogenic pressure swing adsorption or cryogenic permeation process, it is particularly advantageous to pressurize and extract the carbon dioxide by means of physical scrubbing make reduced temperatures · Since the gas separation plant u _e * according to the invention a combined with a methanol synthesis plant, it is to make a particular advantage ^ the physical washing using methanol, "the carbon dioxide is produced by heating and expansion of the loaded with carbon dioxide Methanoles' the methanol is for renewed pressure increase and cooling used again as washing liquid «

The highly concentrated hydrogen fraction can be recovered with high purity and moderate yield in the gas separation plant

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and be deducted for further use _s when the decomposition of the expansion gases takes place in a Bruckwechseladsorptionsanlage * It does not matter whether the carbon dioxide according to the invention from the flash gases before entering the pressure swing adsorption was removed and recovered or nothing Pur the process step of pressure swing adsorption, the adsorbent so determined that the hydrogen is separated from the residual components under pressure without participation in the adsorption process. "The residual components are adsorbed under pressure from the adsorbent and desorbed by depressurization. This process step within the overall process is particularly advantageous because the high purity with which the hydrogen In the further use ¹ leads to a reduction in the burden of inert gases or * contact poisons. "A post-purification of the hydrogen thus obtained is not required because the hydrogen fraction with the same Pressure is obtained and used further, with which the expansion gases are supplied to the gas separation plant, this process step is optimally integrated into the process according to the invention in terms of energy economics.

If it is necessary for operational reasons, to win the highly concentrated hydrogen fraction with particularly high yield and technical quality in the gas separation plant and deduct for further use, it has proved to be beneficial that the decomposition of the expansion gases carried out by means of a cryogenic plant before the separation process of the hydrogen, the carbon dioxide is first removed by a chemical or »physical scrubbing from the flash gas» The flash gas is then cooled under pressure, partially liquefied, introduced into a separator and thereby into the highly concentrated technical hydrogen fraction and a residual gas fraction in the contains hydrogen, carbon monoxide, nitrogen, argon and methane, separated ^ the hydrogen fraction is removed under pressure from the separator ^ the residual gas fraction from the waste

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scheider relaxed _s heated both fractions and further. Use deducted * This process step within the Ge β amtverfahrens is particularly advantageous if the components contained in the expansion gases of the methanol synthesis hydrogen and carbon dioxide largely a material economy use while the hydrogen is used with technical quality _e By recovering the hydrogen under pressure the process is very energy-economically integrated into the process according to the invention »

In order to obtain also the carbon monoxide contained in the flash gases to the methanol synthesis, it has also proven favorable than "^ if the residual gas fraction obtained in the separation in the separator of the cryogenic system, which also hydrogen enthält§ ₈ carbon monoxide, _nitrogen? Argon and methane substantially by further partially liquefied, flashed and separated, and further worked up by rectification, into a carbon monoxide-enriched fraction which is largely depleted of nitrogen, argon and methane, ₉ and disassembled into a waste fraction, all fractions heated and stripped for further use

The further use of the fractions obtained in the gas separation plant is essential for the economy of the overall process, with their extensive use of the material being dependent on the production profile of the chemical industry complexes.

Thus, it has proved in the presence of only a methanol synthesis advantageous to zuzumisehen the recovered carbon dioxide fraction the synthesis gas for the methanol synthesis for material use «Thus, in general, the production capacity of the methanol plant can be increased with the same use of primary energy sources or * the use of primary energy sources be lowered with the same production capacity

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Very particularly effective, the material economic nutating gained in the gas separation plant highly concentrated "trated hydrogen fraction has proven when the methanol synthesis plant is installed in a chemical industrial complex, operating in the same time an ammonia synthesis and / or Hy" · drierprozesse _"e

The highly concentrated hydrogen fraction is then supplied, for example, to the ammonia synthesis and synthesized together with nitrogen, which is optionally obtained in an air separation plant or else provided by increased supply of air into an existing reformer, to form ammonia. As a result, in addition to reducing the use of primary energy sources, it is possible to minimize investment expenditure.

The highly concentrated hydrogen fraction is then surückgeführt for example, in methanol synthesis · The necessary for carrying out the methanol synthesis amount of carbon monoxide and / or carbon dioxide is then recovered in the gas separation plant for the expansion gases of the methanol synthesis and / or supplied from external equipment _o If coal or naphtha as Primary energy sources used for the synthesis of gas generation, is also a return of the hydrogen fraction to methanol synthesis without simultaneous supply of carbon monoxide and / or carbon dioxide economically feasible All measures lead to an increase in methanol production with the same use of primary energy sources or «reducing the use of primary energy sources with the same production capacity «

The highly concentrated hydrogen fraction is then also fed, for example, to hydrogenation processes for further use in the textile industry »

A complex utilization of the expansion gases of the Methanoisynthese is achieved, if in addition to the re-use of high-

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concentrated hydrogen and carbon dioxide fraction in the gas separation plant obtained Eestgasfraktion and / or waste fraction as fuel gas in the Eeformer synthesis gas production for methanol synthesis and / or as a heating gas elsewhere in the chemical industry complex and / or optionally as a means for other consumers used

The economy of the complex utilization of the expansion gases of the methanol synthesis is particularly good if the obtained in the further workup of the residual fraction, carbon monoxide enriched and largely depleted by the inert nitrogen, argon and methane fraction synthesis gas for methanol synthesis and / or other consumers, For example, an oxo-synthesis can be used to increase the production of methanol with the same use of primary energy sources or reduce the use of primary energy sources while maintaining the same production capacity. "

Due to the extensive use of the exhaust gases of the methanol synthesis, the fuel gas balance of the total system _{f of} the Eeformer for.Geynthesegaserzeugung, considerably influenced «> For the purpose of extensive use of domestic fuels and saving of natural gas, petroleum and / or naphtha, the process shows particularly high economic Effects ", when the amount of heating gas withdrawn from the overall process is compensated by a fuel gas produced from coal ·

The withdrawn amount of heating gas can also be compensated by supplying external heat, which is produced, for example, in nuclear fission processes.

The system solution disclosed by the inventive method is of particularly high economic importance. "It will be shown for the first time, as in a chemical industry.

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Complex large quantities of high-quality primary energy sources ₉ such as crude oil and natural gas ₅ require more and more effort to develop and extract them on a global scale, whose limited world reserves are only sufficient for a few decades and are imported by the consuming countries in large quantities In this case, the special economic effect _{9 occurs} that the heat balances of the entire system can be covered by the domestic fuel coal or other fuel gases * Surprisingly, however, _t known cases for complex solution of the extremely complicated task on the special appli - tion cases Modified process steps and equipment are used ₆

embodiments

The invention will be explained in more detail below with reference to five examples and the associated drawings. "All the examples assume that equal amounts of primary energy sources, such as process natural gas or lignite coke, are used for the comparative technologies."

Example 1 describes the known simultaneous operation of an integrated methanol plant and an ammonia plant with the known technology of ^ recovery from the purge gas of HH ^ synthesis »The synthesis gas is produced by means of natural gas after the steam reforming process«

In Example 2, the technologies known from Example 1 are combined according to the invention with a gas separation plant operating according to a mixed cryogenic pressure swing adsorption process. The CO ₂ -tetrahydrofluorine obtained in the gas separation plant is admixed with the synthesis gas for the methanol synthesis; The heating of the reformer is effected by means of a heating gas produced by gasification of carbon monoxide.

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Example 3 describes the e ^ invention proper combination of the known technologies of Example 1 for the simultaneous production of methanol and ammonia with an operating according to the cryogenic process gas separation system _a The gained GC ^ e? and CO fractions are added to the synthesis gas for the methanol synthesis. The heating of the reformer takes place by means of a heating gas produced by gasification of carbon coke.

Example 4 describes the known technology for producing methanol in an integrated unit. The gasification of brown coal coke according to the Winkler method is used for the production of the synthesis gas. »The expanding flue gas is passed on to other consumers. If there is no need for such heating gas, the flue gas must be flared off «

In Example 5, the methanol production process known from Example 4 is combined with an adsorptive gas separation plant. The Hg fraction extracted therein is mixed again with the synthesis gas for the synthesis of methanol. The amount of heating gas equivalent to the hydrogen fraction is determined by gasification for synthesis gas production If such a fuel gas requirement is not present, this proportion of gas generation _{0 is} eliminated

The exemplary embodiments of the present invention describe the essential basic application possibilities for the material use of the expansion gases of the methanol synthesis. In addition, within the process according to the invention, there are further possible combinations of the products of the gas separation plant resulting from the respective technological energetic and economic Derive conditions or other company-specific requirements

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For example, u «a _e

- technology, the gem _e Example 4 as described for methanol production with a working according to the cryogenic process gas separator are combined, and thereby in addition to the ^ - be recovered for further use and / or a CO fraction - "fraction, optionally, a CC ^

.- the gem _e ^ Example 2 gained - "faction in the stoichiometric ratio to the findings (^" - fraction are mixed with the synthesis gas for methanol synthesis

- that the like CO 3 fraction would be passed on to other consumers _? if the inert gases still contained in the C0 fraction in the recirculating exhaust gas of the methanol synthesis accumulate unacceptably high

- the very small amount of purge gas of HH, which may be produced in Examples 2 and 3, may also be supplied to the gas separation plant for the expansion gas of methanol synthesis or to a separate recycling plant

· The «happy« example 5 won ^ fraction can also be forwarded to other Hg consumers if a different fuel is used as the primary energy source ·

example 1

Referring to FIG ₀ 1 and «2 a methanol plant are known per kt with a power of CA® 100 / a methanol (Fig * 1) and an NEW-district, c © with a capacity of ca _e 45 kt / a Mi ^ (Figure" 2) operated simultaneously

According to Fig. 1 in the known methanol plant through the line 1 ca _e 10 _s 6 «10 ^ v? (N) Al Prozesserdgasj through the line 2 ca _e 1.5 "10 ^ m ^ (N) A natural gas as fuel gas and the Lei

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• 5% ca 25 v / h steam is fed to the reformer 4 operating at about 2.5 MPa. »This produces about 43 β 1CK nr (N) / h of methanol synthesis gas _§ consisting of about 74% H ₂ , 17% CO ₅ 6% CO ₂ , 2.5% CH ₄ and 0 _§ 5% N ₂₅ which, after its compression through line 5, is fed to methanol synthesis 6. Here, the reaction of H ₂ with CO and CO _{2 takes place} according to known equilibrium reactions

2H ₂ + CO

3 H ₂ * CO ₂ ® » CH ₅ OH + H ₂ O

The inert gases contained in the synthesis gas methanol N ₂ and not participating in the reaction components H ₂ , CO and CO ₂ are withdrawn through the line 7 as Kreislaufentspannungsgas from the methanol synthesis plant 6 «The withdrawn amount is about 14 _o ΛΟτ nr (N) / h and consists of about 85 % H ₂ , 4 % CO, 3% CO ₂ , 7 % CH ₂ and 1% N ₂ and essentially traces of water, methanol, higher alcohols and methyl ether * = * standing methanol is relaxed through the line 8 through the relaxation 9 and the line 10 in the separator 11 to a pressure of about 0.3 MPa »This takes place a separation of the methanol in the line 8 still dissolved gases, which are used as product vent gas derived essentially with the components H ₂ , CO, CO ₂ , N ₂ , Ar, CH ^, CH ₅ OH through the line 12 and the Kreislaufentspannungsgas the line 7 werd'en · Through the line 13, both gases as expansion gases of M ethanol synthesis · the reformer 4 supplied for heating purposes

The methanol obtained in the separator 11 is fed as crude methanol through the line 14 of the distillation unit 15 and withdrawn from there as pure methanol through the line 16 · The amount of methanol withdrawn through the line 16 is about 12.5

In the known ammonia plant operated at the same time, approximately 3.25 × 10 ⁵ m ⁵ (N) / h of process natural gas are passed through line 17, through line 18 approximately 2 ₉ 2 _β 10 ³ m ⁵ (N). / h natural gas as fuel gas and through the line .19 ca _e 8 t / h water vapor

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supplied to the working at a pressure of about 4 MPa reformer 20 * where about 16 _§ 8 · 1Cr m ^ (F) AM ^ SYN "are produced, synthesis gas _S consisting of about 57% H ₂₉ 13% CO, 22% Np, O5I% Ar, 0.3% CiI ^ and 7§6% CO ₂ * which are fed through the line 21 of the synthesis gas purification and compression 22 * Here, a CO conversion and methanation, a COq "> and sulfur!. Cleaning and a compression, so that by the line 23 15 * 5 "10 nr (N) / h purified and compressed NHv synthesis gas ₉ consisting of about 74 % H ₂ ^ 24% N ₂₉ radical Ar + CH ₄₅ of NH ^ synthesis 24 The resulting KS ₃ is, through the line 25 through the relaxation 26 and the line 27 in the working at about 1 _§ 3 MPa'Abscheider 28 relaxed "There is a separation of the NH, ~ line 25 still dissolved Gases, which are used as product vent gas essentially with the components H ₂₁ , N ₂ , Ar _? CEL and NEW are withdrawn through the line * The recovered liquid MH, is 5? 7 t / h and is through the line 30 of further use trains «leads ·

In order to avoid the accumulation of inerts in the HEU synthesis, line 31 gives O $ 75 »10 ^ mr (N) / h. Withdrawn recycle gas from the NEW synthesis 24, mixed with the Oj, 25 »10 ^ nr (lO / h Produktentspana.ungsgas the line and as purge gas ₉ consisting of about 60 % H ₂ , 20% N ₂ , 13 % CH, , 5.5 % .Lr and 1.5 % NH, fed via the line 32 of the H ₂ recovery system 33 "Here, the separation of the purge gas takes place in a ΚΗ, -Praction, which through the line 34 ·» a Hg-Eraktion which are withdrawn through conduit 35 and a residual fraction which is withdrawn for further use by conduit 36. The H ₂ fraction withdrawn through conduit 35 is about 0.5 · 10 -Nr (N) / h H ₂ and consists of about 90 % H ₂ , balance N ₂ S Ar and CH ₄₀ It is recycled to the NH ^ synthesis 24 as NH ^ synthesis gas * The withdrawn residual fraction in the amount of 0.5 »10 · ⁵ Hr ^ (N ) Zh is supplied through line 36 to the reformer as heating gas and burned there

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To compensate for the amount of Hg withdrawn in the Ho ^ recovery plant 33, the eductor 20 is supplied with 0.15 ₀ 10 * m (M) / h of natural gas through the line 37 and burned,

Thus, a total of about 5.6 * Eridgas were required for the NH 4 synthesis

Both processes together require 13 _¥ 85 · 10 * Br (N) / h of process natural gas and 3j85 · Λ € τ m ^ (N) / h of natural gas as fuel gases

Methanol production is 12.5 t / h and ammonia production is 5 $ 7 t / h.

Example 2

According to FIG. 3, the plants for the simultaneous production of methanol and ammonia described in Example 1 are combined according to the invention by a gas separation plant 38 with == ¹ operating according to a mixed cryogenic pressure adsorption process with == ^{1. The} same amounts of natural gas are used as in Example 1 used as process natural gas, ie _, 10.6 ± 1Crnr (10 / h) of the process gas of methanol synthesis and 3 × 25 Br (IT) / h pro-

5 natural gas of the ammonia synthesis, for a total of 13 _s 85o10 et The use of natural gas for combustion gases _s d »h» 1 ^ 5 · ΙΟ- ⁵ m ^ (lT) / h of the methanol synthesis and 2 «35 _# 10 ^ nr (F) / h of the total ammonia synthesis _$ 3 _? 85 ₉ 10- ^ iir (lT) / h and the amount of gas corresponding to the calorific value of the expansion gas component withdrawn for use in the material economy are replaced by a fuel gas produced from coal.

Through line 1, 13 $ 85 * 10 ⁵ m ⁵ (N) / h of process natural gas and line 3 33 t / h of water vapor are fed to the Eeformer 4, which operates at about 2 _t 5 MPa. 55 · 5 · 10 methanol synthesis gas consisting of about 74- ° / ° H ₂ , 17 $ 6% CO ₂₉ 25% CH ^ and 0 ₉ 5% H ₂ , which are fed after their compression through line 5 of methanol synthesis 6 »

20 ~ 2 2 6 3 18

From the methanol synthesis 6 are through the line 7 16 _$ 8 © 1Cr ητ (N) / b. Ereislaiifentspannungsgas, consisting of about 84 % H ₂₉ 4 _S 5% CO ^ 3.5% CO ₂₅ 7% CH ₄₉ 1% N ₂ as well as essentially traces of water ^ methanol ^ higher alcohols and dimethyl ether withdrawn from the methanol resulting from the synthesis 6 is relaxed through the line 8 via the relaxation and the line 10 in the separator 11 to a pressure of about 0 _f 3 MPa, wherein the separation of methanol still dissolved gases takes place «These are derived as product vent gases through the line 12 the Kreislaufentspannungsgas the Line 7 u & cL together with this through the line 13 of the operating according to a mixed cryogenic pressure swing adsorption operated gas separation plant «

The accumulating in the separator 11 methanol is as crude methanol through the line; 14 fed to the distillation unit 15 and withdrawn from there as Hein methanol through the line 16. "The amount of methanol withdrawn through line 16 is ca", 16 _t 6 t / h «

The expansion gases supplied to the gas separation unit 38 are first subjected to a methanol wash under pressure and at about 213 ° C., thereby preferably scrubbing out the CO ₂ contained in the expansion gas together with other trace contaminants. The supply of the required methanol takes place from the conduit 14 the line 39 · Through the line 40 are O ₅ 5 m ^ (N) / h CO ₂₉ which occur in the regeneration of methanol * the methanol synthesis 6 fed «, The CO _{2 of the released} expansion gases are then within the gas separation unit 38 by pressure swing adsorption into a highly concentrated EU fraction and into a residual gas fraction Separate About 11, _t 2 ^? 10 ^? After their compression, nr (N) / h H ₂ are fed through line 41 to NH ₂ synthesis 24. At the same time, from an air separation plant 42 about 3 * 9 & 10 ^ nr * (N) A high purity N _{2 are introduced} through line 43 of FIG NBU

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Synthesis 24 is fed to the reaction of the supplied H ^ and the added Np to ML-, _o. This results in 5 * 7 t / h Mi ^ ₈ This is through the line 25, the relaxation $ 26 the line 27 »the separator 28 and the line 30 deducted for further use *

The very small amounts Kreislaufentspannungsgas the synthesis 24- and product exhaust gas of the separator 28 are withdrawn through the lines 29 and 31 and fed via the line 32 to the reformer 4 and burned there * If necessary, these can also be passed through the roof ·

The resulting in the gas separation plant 38 in the pressure swing adsorption residual gas fraction, which preferably consists of CO ₉ ^ ₉ CH ^ and small amounts of H2 _s is supplied via line 44 to the reformer 4 and burned there To compensate for the separated in the gas separation unit 38 hydrogen and the Heat balance of the fuel gas in the reformer 4 are fed from the air separation plant 42 through the line 45 4,6 »10 ^ m ^ (li) / h O2 of the operating according to the Winkler method coal gasification plant 46, 18 _? Fuel gas produced and fed via line 47 to the reformer 4 and burned ©

In this combination according to the invention, the total process requires 13j85 _ö 10 ⁵ m ^ (N) A of Proseßerdgas and 18 _t 5 ο 1o \ ⁵ (N) / h fuel gas from coal, which requires about 15 t / h lignite coke v / earth"

Example 3

According to FIG. 4, the systems for the simultaneous production of methanol and M 2 described in Example 1 are combined according to the invention by a gas separation plant 48 operating according to the cryogenic process. Analogously to Example 2, the same amounts of natural gas _{9 are used} as process gases as in Example 1.

22 - 2 2 6 3 18

used natural gas ^, d * h ₀ 10 _? 6 "10 * ar (N) / h Process natural gas for the synthesis of methanol and 3 ₉ 25 ο ΙΟ * 'm *" (N) Zh process ammonia ammonia total 5 13 $ 85 «10 * m *" (N) Zh · The use of natural gas Combustion gases, d _e h "1.5 _ö 10 *" m ^ (N) / h of methanol synthesis and 2-35 · 10 * "m * (N) A &amp; ammonia synthesis, in particular

2 2

in total, 3.85 "* 10 · ⁷ nr (N) Zh as well as the amount of gas corresponding to the heat value of the flash gas component removed for use as fuel are replaced by a fuel gas produced from coal ©

Through line 1, 13 $> 85 · 10 * nr (N) / h of process natural gas and line 3 33 t / h of water vapor are fed to the reformer 4 · operating at about 2.5 Ii · approximately 55 * 5 »10 * nr (N) / l methanol synthesis gas consisting of about 74 % EU, 17 % CO ₅ 6 % CO 2, 2.5 % CH ₂ J. lind. 0 _s 5 % N ₂ , which are fed to the methanol synthesis 6 after their compression through the line 5 "From the methanol synthesis 6 through the line 7 15 s 10- ^ Hr (N) Zh Kreislaufentspannungsgasj consisting of about 82 % H _2t 4% CO, 3% CO ₂ ^ 9% CH 2 and 2% N ₂ and essentially traces of water, methanol, higher alcohols and dimethyl ether withdrawn. The methanol formed in synthesis 6 is passed through line 8 via the expansion 9 ". and the line 10 in the separator 11 to a pressure of about 0 ₉ 3 MPa relaxed j wherein the separation of the methanol still dissolved gases takes place «These are derived as product exhaust gas through line 12 _f the recirculation vent gas line 7" and in common with this through the line 13 of the operating according to the cryogenic gas separation plant 48 auführc

The resulting methanol in the separator 11 is fed as eoh methanol through the line 14 of the distillation unit 15 and withdrawn from there as pure = methanol withdrawn through the line 16 The withdrawn through the line 16 amount of methanol is about · 17.8 t / h *

23- 22 63 1 8

The flash gases supplied to the gas separation unit 48 are first subjected to methanol scrubbing under pressure and at about 21 $ K , thereby preferably scrubbing out the COO contained in the flue gas together with other trace impurities. The required methanol is supplied from the conduit 14 via the line 39 _β through the line 40 are 0 ^ 54 "10 ^ m ^ (N) / h CO ₂ , resulting from the regeneration of the methanol, the methanol synthesis supplied 6 The released from CO ₂ relaxation gases are then within the gas separation unit 48 on cooled and separated by partial condensation and, if appropriate, rectification into at least one gas phase and one liquid phase. One of the gas phases consists of 11 _S 5 .10 nr (N) / h of highly concentrated Hp At the same time, about 4 * 10 ^ nr (N) / h of highly pure N _{2 are passed} through the line 43 de from the air separation plant 42 m ^ synthesis 24 fed there, together with the H ₂ from the line 41 to ML, synthesized «This produces ca _e 5» 85 t / h HEU · The ammonia is through the lines 25 via the relaxation 26, the line 2 ?, the separator 28 and the line 30 withdrawn for further use «

The very small amounts Kreislaufentspannungsgas and Produktentspaiumngsgas from the lines 29 and 31 are supplied via the line 32 to the reformer 4 and burned there.

In the gas separation plant 48, about 0 _s 54 ♦ 10 * irr (N) / h of a CO fraction are obtained during the low-temperature decomposition and fed to the methanol synthesis 6 via the lines 49 and 50. In principle, it is also possible. _{s feed} the CO fraction from line 49 via line 51 to other consumers, for example an oxo synthesis, "dia" in the gas separation unit 48 at the low temperature decomposition residue fraction ₅ which preferably consists of CO and CH ₂ in admixture with N ₂ and Ar, is fed through line 44 to the reformer 4 and burned there «

24 - 2 2 6 3 18

To compensate for the separated in the gas separation plant 48 H ₂ and CO = quantities and the heat balance of the fuel gas in the reformer 4 are from the air separation plant 42 through the line 45 ca _e 4 _f 7 «1O ⁵ m ⁵ (N) / h O _{2 of} the after operating the Winkler method coal gasifier 45 is supplied., there ca _o 25 _s made 5 * 10 No (N) / h fuel gas and supplied through the line 47 to the reformer 4 and burned · In this inventive combination of the overall process requires 13j85 _θ 10 ^ ar (N ) A process natural gas and 23 _? 5 «1O ^ BT (N) Zb. Fuel gas from coal, for which approx. 15.3 t / h lignite coke is needed «. The methanol production is 1? $ 8 t / h and the ammonia production 5 _S 85 t / h »

Example 4

According SIg ^ 5 are in a self-operated integrated Me THANOL synthesis anl age with the same performance., As mentioned in Example 1 (ca "100 kt / a of methanol), by the conveying member 52 30.4 t / h lignite char line _s 9? 35 * 10 ⁵ ni ⁵ (lT) / h Op and line 54 29 t / h of steam supplied to the generator 55 operating according to the Winkler method «This results in about 42 _S 2 ₉ 10 * ar QO / h raw synthesis gas ₉ consisting of approximately 43.5 % H ₂ , 30 _f 4 % CO ₉ 23.8 % CO ₂ and 23 % Ng »Ar and GH ^. A partial flow of 20 * 10 ^ m ^ (F) A of this synthesis gas is supplied through line 56 to conversion 57 where the CO is converted there. Through line 58, 25 # 10 ^ Br (N) / h of converted gas is discharged of -54.9 % H ₂ , 4% CO, 39.3% CO ₂ and 1.8% N ₂ , Ar and CH ₂ ^ the conversion 57 «

Another partial stream of 22 ^ 2. 10 ^ iir (N) / h of the crude synthesis gas are admixed through line 59 to the converted synthesis gas of line 58 and the mixture is fed via line 60 to methanol scrubber 61. In this scrubber, the CO _{2 is} reduced to the required level for synthesis of 7.3 %, as well as the remaining traces

-25 - 22 63 1 8

This results in 34 _ö 1CK mr methanol synthesis gas with a composition of 67.5 % 22 _S 7% COj 7 * 3% GO ₂ and 2 _S 5 % N ₂ , Ar and CH ^, which after its compression through the line 62 of the methanol synthesis 6 is fed β

The inert gases contained in the synthesis gas methanol Ήη ₉ Ar and CH ^ and the not participating in the reaction components H ₂ J CO and CO ₂ are withdrawn through the line 7 as Kreislaufentspannungsgas from the methanol synthesis 6 »The« pulled off «amount is about 5 * 5 β 1CK nr (N) / h and consists of about 59 * 1 % H ₂ , 15.4 % CO ₉ 18.2% CO ₂ and 7.3% N ₂ , Ar and CH ^ and essentially traces of Water, Methanol, Higher Alcohols, and Dimethyl Ether "The methanol formed in Synthesis 6 is released through line 8 via the flash 9 and line 10 into the separator 11 to a pressure of about 0§3 MPa Separation of the still dissolved methanol in the gases, which are derived as product exhaust gas substantially with the components H ₂ , H ₂ , Ar, CO ₉ CH ^ ₉ CO ₂ and CH ^ OH through the line 12 and the recirculation vent gas line 7 are supplied the line 13, both gases as expansion gases of Me ethanol synthesis flared off »If required by heating gas, these expansion gases can also be fed to a heating gas network» The amount of methanol withdrawn through line 16 is about 12 _? 5 t / h · The consumption of lignite coke is about 30.4 t / h ·

Example 5

Referring to FIG 6, the same quantities _e lignite, O _0, and water vapor are used as in Example 4 in accordance with the invention equipped methanol synthesis plant, d _o h. the generator 55 operating according to the Winkler method, 30.4 t / h lignite coke, line 52 9.35 c 1p ⁵ m ⁵ (N) / h O ₂ and the line 53 29 t / h of water vapor by the conveying member 52

- 26 - 22 6 3 18

supplied »This produces about 42.2. 10 * m ^ (N) / h crude syn theses gas consisting of approximately 43.5% H ₂ , 30.4% CO, 23.8 % CO ₂ and 2 % 3 % No ₃ Ar and CH ,, A partial stream of 17 »9» 1Cr rP (ß} / h of this crude synthesis gas is introduced through line 56 of conversion 57 and there converts the CO. "Through line 58 22.4 _β 1Cr m * (N) / h leave converted gas containing 54 _? 9 % H ₂ , 4 % CO, 39 $ 3 % CO ₂ and 1 _f 8% N ₂ , Ar and ClL ₊ the conversion 57e

Another partial flow of 24.3 & 1Cr ⁵ m ^ (N) / h of raw synthesis gas are mixed through line 59 to the converted synthesis gas in line 58 and fed via line 60 to the methanol wash 61 «In this washing are the CO ₂ to to the required content of 7 _$ 9 % for the synthesis and the sulfur compounds still present in traces * This results in about 3 ^ · 1CK nr (N) / h of methanol synthesis gas with a composition of 64.9 % H ₂ , 24.5% CO, 7 _f 9 % CO ₂ and 2.7 % ^ ₂ * Ar and CH ₂ ,, which is supplied after its compression through the line 62 of the methanol synthesis 6 * In addition, the synthesis 6 highly concentrated hydrogen is fed, which with the inventive For this purpose, the recirculating exhaust gas withdrawn through the conduit 7 from the synthesis 6, together with the product exhaust gas of the conduit 12 through the conduit 13 as expansion gas of the methanol synthesis of the after pressure change Ad The amount is about 5.9 · 10 * nr (N) / h and consists of about 59.1 % H ₂ , 15.4 % CO, 18.2% CO ₂ and 7.3 %. N ₂ , Ar and CH ₂ , as well as essentially traces of water, methanol, higher alcohols and dimethyl ether * In the gas separation unit 38, the decaying gases are separated into a highly concentrated hydrogen and a residual gas fraction. * About 2 _S 7. 10 * nr (N) / h H ₂ are withdrawn from the gas separation plant 38 and fed through line 41 of the methanol synthesis »

The resulting in the synthesis of methanol is through the conduit 8 via the relaxation 9? the line 10 is expanded into the separator 11, via the line 14 in the distillation 15th

-27- 226318

introduced and withdrawn from there as Eein-methanol through line 16 * The withdrawn through line 16 amount of methanol is about 13 ^ 6 t / h ©

The residual gas fraction accumulating in the gas separation plant 38 _? which preferably consists of N * ₅ CO CO _{2 2} $ Ar, CH ^ and small amounts of EU, is fed via line 44 flared If necessary, fuel gas, this fraction may also trains a Heizgasnetz "leads are. In this example, the amount of methanol recovered is about 13.6 t / tu The consumption of lignite coke amounts to about 30 _? 4 t / ho

In the following table, the performance parameters of the methanol synthesis plants and the ammonia plants are compared with the technologies explained in more detail in Examples 1 to 5 . known G echnologies blank with the embodiments of the invention (Examples 2, 3 "and 5) achieve the following effects _s in which the expansion gases are burned the methanol synthesis (Examples 1 and 4)?:

Embodiments according to Examples 2 and 3 with respect to Example 1:

With the same use of process natural gas, the production of methanol is increased by more than 30% or more than 40%, with virtually constant ammonia production.

- no natural gas is used as fuel gas ^ the natural gas is supplied to a substantial material use ·

- The required heating gas is produced from a solid fuel «

"Nearly no purge gases are produced in ammonia production, which significantly increases the economy of ammonia production."

~ 28 -

2263 1 8

· - ♦ Specific leaning gas per tonne of methanol is reduced by 10 "or" 25 % "© This increases the efficiency of methanol production,»

- · It eliminates the entire stages of gas production and purification for the production of ammonia synthesis gas and the hydrogen recovery plant for the purge gas decomposition of the ammonia synthesis gases »

Embodiment according to Example 5 over Example 4:

· »With the same fuel consumption as well as the same capacity of gas production * and« purification plant, the methane production is increased by »9 % «

22 63 1

Table: Comparison of the codes for the technologies explained in more detail in the examples to 5

Dim e 5, 1 S 0 1 2 example 4 " » I 85 • 0 ι 15.85 5 4 2) O Pro 2 natural gas sat. I 55, »85 15.85 ^} 30, O 9 Natural gas as fuel gas II IH » 5 0 15.0 ¹⁾ " 50.4 ² 29 55 7 ² ^ Lignite = coke II M 0 5 33.0 15.0 ¹⁾ 29.0 9 process steam I 45 ₅ 7 55.0 9.55 2 oxygen I 14 12 3 _$ 9 ^{3) 4} * ⁷ -. nitrogen I "Β! 55.5 4.0 ⁵⁾ 34.0 5, 6 Methanol synthesis gas I * M 16.8 55.5 5.5 2, Relaxation of the gas of the methanol synthesis I  κ M 11.2 ⁵⁾ 15.0 »· 434 Products of the gas separation plant: ^H 2 I 15, ι, - 11.5 ³⁾ W 3, CO I i 12 0 * 5 5.1 0.54 _ mm co ₂ Ee st I i 5, ; 2.52 15 3 purge gas of HKU synthesis II 1, 16 ₉ 6 to * 12.5 Methanol production II 5.7 17.8 _ O, Ammonia production III 1 ₅ 01 5.85 0.44 specific discharge gas quantity 0.843

It means: Dimension I Dimension II Dimension III

10

t / h.

m ³ (N) / t CH ₅ OH

Footnote 1) for fuel gas

2) for Proseßgas

3) for Mz synthesis

4) for CKOH synthesis

Claims (1)

30 - 22 6 3 18 invention claim 1 "Process for the treatment and reuse of flash gases, which inevitably .Account in the implementation of a methanol synthesis and consisting essentially of hydrogen, carbon monoxide, carbon dioxide, nitrogen, argon, methane and traces of methanol ₉ higher alcohols, dimethyl ether and amines, optionally in combination with a simultaneously operated ammonia synthesis and / or hydrogenation processes, characterized in that the resulting expansion gases are largely used material economy _f by the methanol synthesis plant is combined with a gas separation plant and consumers of the products of the gas separation plant, to the expansion gases are fed to the gas separation plant, there a highly concentrated hydrogen ~ Fraction separated, withdrawn and used to carry out chemical syntheses and / or hydrogenation processes, in the separation of the highly concentrated hydrogen fraction at the same time before ~ § intermediate and / or Bestfraktio obtained, withdrawn and used in the production of the synthesis gas for the synthesis of methanol and / or in the processing des.Synthesegases to methanol and / or other consumers, possibly also as heating gas _s and wherein the deprived by the material economy of the expansion gases the overall process Heating gas by direct combustion of the primary energy carrier used for the synthesis of methanol and / or a loading. variable fuel gas and / or is compensated by the supply of external heat. 2 »Process according to item 1, characterized in that the gas separation plant is operated by the adsorption process, preferably by the pressure swing adsorption process and / or the low temperature process and / or the Penneationsverfahren, optionally with the simultaneous use of a chemical laundry. 2263 1 8 5β The method according to item 1 and 2, characterized in that the expansion gases in the after the adsorption process, preferably after the pressure swing adsorption or Penneationsverfahren gas separation plant into a highly concentrated hydrogen fraction and a residual gas fraction, which is still substantially hydrogen, carbon monoxide, carbon dioxide , Nitrogen, argon and methane, disassembled and the fractions obtained are withdrawn for further use * 4 «method according to item 1 and 2, characterized in that the expansion gases in the after the adsorption process, preferably after the pressure swing adsorption process or the permeation process and the cryogenic process gas separation plant each in a carbon dioxide fraction, a highly concentrated hydrogen fraction and a Sestgasfraktion , which still contains carbon monoxide, nitrogen, argon and methane, decomposed and the fractions obtained are withdrawn for further use » 5 "process according to item 1 and 2, characterized in that the expansion gases in the operating according to the Tiefftemperaturver» drive gas separation plant in o'e a carbon dioxide fraction _§ a highly concentrated hydrogen fraction and a residual gas fraction, which is still substantially hydrogen, carbon monoxide ., Contains nitrogen argon and methane, decomposes and the fractions obtained are withdrawn for further use _o 6 * Process according to item 1 to 3, characterized in that the after the adsorption process, preferably the pressure swing adsorption or the permeation process according to point 3 working gas separation plant is preceded by a chemical wash in the Eegeneration of the washing liquid, a carbon dioxide «fraction won and -32- 22 63 1 8 is withdrawn for further use and the freed of carbon dioxide expansion gases for further decomposition according to the adsorption process or the permeation process according to item 5 are supplied. 7 «method according to point 2 and 6, characterized in that is used as the washing liquid for the chemical laundry according to item 6 monoethanolamine or a hot potash solution · Process according to item 1 ₉ 2, 4 and 5 $, characterized in that the recovery of the carbon dioxide-irrigation in the gas separation plant operating according to the adsorption or permeation and cryogenic processes according to item 4 or according to the cryogenic process according to item 5 by a physical wash the expansion gases are preferably carried out with methanol under pressure at reduced temperatures and subsequent heating and expansion of the methanol. 9 · Process according to item 1, 2, 4 and 8, characterized in that for obtaining the highly concentrated hydrogen Frak-. According to point 3 or "point 4, the gases released from carbon dioxide according to point 6 or" 8 under pressure of a pressure swing adsorption plant, where the water pressure under pressure without participation in the adsorption of the remaining components separated ,? For this purpose, the residual components are adsorbed and desorbed by lowering the pressure and both fractions are removed as recovered highly concentrated and high-purity hydrogen fraction and residual gas fraction which essentially still contains hydrogen, carbon monoxide, nitrogen, argon, methane and possibly carbon dioxide, for further use. 10 · Method according to item 1, 2, 5 and 8, characterized in that to obtain the highly concentrated Was se rs to ff fraction according to point 3, the relaxation gases freed of carbon dioxide according to point 6 or * 8 cooled under pressure, partially - 35 ~ 2 26318 liquefied, introduced into a separator, while in a highly concentrated technical hydrogen fraction and a residual gas fraction separated, withdrawn as recovered highly concentrated technical hydrogen fraction under pressure from the separator, the residual gas fraction, which is still substantially hydrogen, carbon monoxide, nitrogen, argon and methane contains, released from the separator, both fractions are heated and withdrawn for further "use" Method according to items 1, 2, 5 and 8 to 10, characterized in that the residual gas fraction expanded out of the separator in the cryogenic decomposition according to item 10 is purified by further partial liquefaction, expansion and separation or by rectification into carbon monoxide enriched and the inert nitrogen, argon and methane largely depleted fraction and a waste fraction decomposed, all fractions are heated and withdrawn for v / eiteren use · 12 «method according to item 1 to 11, characterized in that the obtained in the gas separation plant according to any one of items 1 to 11 carbon dioxide fraction is mixed again with the synthesis gas for the synthesis of methanol · 13 · Procedure according to point 1 to 12 _p . characterized in that the obtained in the gas separation plant according to any of items 1 to 11 highly concentrated hydrogen «fraction of ammonia synthesis and / or methanol synthesis and / or hydrogenation processes, wherein the amount of nitrogen required for carrying out the ammonia synthesis optionally in an air separation plant and / or by Adding more air to an existing reformer and the amount of carbon monoxide and / or carbon dioxide required to carry out the methanol synthesis by establishing a suitable operating system for the synthesis gas - 34 - 2 2 6 3 18 production and / or in the gas separation plant and / or in external plants. Method according to point 1 "to 13 _", characterized in that the residual gas fraction and / or waste fraction obtained in the gas separation plant according to any one of items 1 to 11 are supplied as fuel gas, preferably to the synthesis gas production for the synthesis of methanol and / or according to their use value to other consumers. 15 »Process according to items 1 to 13, characterized in that the carbon monoxide-enriched fraction obtained in the gas separation plant according to item 11 is supplied to the synthesis gas for the methanol synthesis and / or according to its use value to other consumers« 16 * Procedure according to items 1 to 15? characterized in that the amount of fuel gas withdrawn from the overall process by the material use of the expansion gases is compensated by a fuel gas produced from coal * 17 «method according to item 1 to 15s, characterized in that the material consumption of the flash gases withdrawn from the overall process amount of heating gas is compensated by nuclear heat * These include 4-sheet drawings.