EP3016924A1 - Process and reactor system for synthesis of methanol with cycle gas and purge gas recycling - Google Patents

Abstract

The invention relates to a reactor system (50) for synthesis of methanol-containing product (108) using a starting material (SM1) comprising a gas having a carbon content (101) and hydrogen content (103). The reactor (10) has a gas inlet (21) and a product outlet (23), with a process stage (200) designed for separating a product gas mixture (PGM) into a proportion of the methanol-containing product (108) and a cycle gas component (CG) disposed at the product outlet (23). This also provides a purge gas component (PG). The reactor system (50) further comprises a cycle gas recycling system (262), in order to be able to recycle the cycle gas component (CG) in the direction of the gas inlet (21). A recycle line (250) is provided, and is connected to the process stage (200) and an inlet stage (253) such that at least a portion of the purge gas component (PG) can be recycled to the inlet stage (253), in order to be conducted back through the reactor (10). A measuring device (254) designed to ascertain the current carbon content is used. A control device (110, 255) serves to set the ratio of the carbon content and the hydrogen content.

Description

 METHOD AND REACTOR SYSTEM FOR SYNTHESIS OF METHANOL WITH CIRCULAR GAS AND PURGACE RECYCLING

The present application relates to methods and reactor systems for providing methanol. In particular, it is about the catalytic

Methanol synthesis.

Carbon dioxide C0 ₂ (usually called carbon dioxide) is a

chemical compound of carbon and oxygen. Carbon dioxide is a colorless and odorless gas. It is a natural component of the air with a low concentration and is formed in living beings in cell respiration, but also in the combustion of carbonaceous substances with sufficient

Presence of oxygen. Since the beginning of industrialization, the C0 ₂ share in the atmosphere has increased significantly. The main reason for this is the

Man-made - so-called anthropogenic - C0 ₂ emissions. The carbon dioxide in the atmosphere absorbs part of the heat radiation. This property makes carbon dioxide a so-called greenhouse gas (GHG) and one of the contributors to the global greenhouse effect.

For these and other reasons is currently in

researched and developed a wide range of research in order to find a way to reduce anthropogenic C0 ₂ emissions. Especially in the

Connection with energy production, often caused by burning fossil energy sources, such as coal, oil or gas, but also with other combustion processes, such as waste incineration, there is a great need for the reduction of C0 ₂ emissions. More than 20 billion tonnes of CO ₂ are released into the atmosphere through such processes every year.

Among other things, the principle of climate neutrality is sought by pursuing approaches that attempt to compensate for the associated with C0 ₂ emissions energy production in one place by generating alternative energy in other places. This approach is strong

schematized in FIG. 1 shown. Issuers of greenhouse gases (GHG), such as industrial companies (eg car manufacturers) 1 or power plant operators 2, invest or operate eg. For example, wind farms 3 at other locations in the context of balancing projects in order to generate energy without GHG emissions. In purely mathematical terms, this can result in climate neutrality. Numerous companies are trying to buy a "climate-neutral vest" in this way.

It can be stated that the renewable forms of energy in a purely economic view not with the fossil energy forms

can compete.

It has been shown that the regenerative forms of energy can be combined with fossil energy forms particularly advantageous to z. B. to achieve better efficiency. Details of this can be found, for example, in the following parallel applications of the present applicant:

- published international application WO2010069385A1;

 - published international application WO2010069622A1;

 - published European patent application EP2226290 A2.

Such a combination makes it possible to produce hydrocarbon-based energy sources in corresponding silicone-fire plants. These silicon-fire systems are particularly suitable for synthesizing methanol.

Numerous methods and reactors for the production of methanol are known. The following are corresponding exemplary

Patent applications and patents called: EP 0 790 226 B1;

 - WO 2010/037441 AI;

 - EP 4 483 919 A2. In synthesis plants for the production of hydrocarbon-based fuels, such as methanol, mostly large, complex and very expensive synthesis reactors are used. Also, the raw materials are sometimes very expensive if you want to produce methanol regenerative. There is therefore a need to provide synthesis reactors which enable a more efficient synthesis of methanol.

In particular, it is also about existing facilities

Make refitting more efficient or design new equipment more efficiently from the start.

An advantageous plant for methanol synthesis is the international patent application PCT / EP2010 / 064948 of the present applicant to

remove. This system is characterized by a particularly favorable

Circular gas ratio (P / E) and therefore has numerous environmental and economic advantages over other known reactors for

Methanol synthesis.

It therefore raises the task of a methanol synthesis reactor plant and a corresponding method even more efficient and

make more economic sense to further improve the production of methanol. Particular attention is paid to the aspect of

Environmental compatibility. In addition, a suitably designed

Be scalable reactor plant to reactors and plant components of different capacity and size can be realized.

According to the invention, a reactor system for providing a methanol-containing product is provided. In addition, a method for using or operating such a reactor plant is proposed. According to the invention, a carbon-containing gas fraction, preferably carbon dioxide, is used as the carbon source. The carbon-containing gas fraction is reacted with a hydrogen portion in the presence of a synthesis reaction catalyst to convert these gases to the methanol-containing product.

Preferably, carbon dioxide is removed from a combustion process or an oxidation process of carbon or hydrocarbons by C0 ₂ separation. C0 ₂ but z. B. also come from a sewage treatment plant, a biogas plant or a separation stage, which separates the C0 ₂ share of naturally occurring raw gas. C0 ₂ can be provided, for example, via a longer pipeline, a local gas line or even in steel cylinders or tanks. The hydrogen can over a longer pipeline, a local

 Gas line or even in steel bottles or tanks are provided. Preferably, however, the hydrogen is produced locally by means of electrolysis of water or provided by a sewage treatment plant or a biogas plant. Alternatively, the hydrogen may also be generated by an oxidation reaction of elemental silicon or other elemental metal.

Carbon dioxide as a carbon source can be removed according to the invention also from raw gas, which depending on the natural gas source about 10%

Can have carbon dioxide content. Carbon dioxide can z. B. also originate from processes of Kalkbrennens or calcination to soda.

According to the invention is a constant as possible, more stable (d .h. Not fluctuating) and long-term plant operation of a corresponding

Achieved by a uniform feed and through the use of a software-based, computer-controlled process control by means of a corresponding system control.

The invention is used in a reactor plant or for use, which is designed specifically for the synthesis of a methanol-containing product. The synthesis is carried out using a starting material containing a gas Carbon content (preferably carbon dioxide) and hydrogen content. The reactor of the reactor plant has a gas inlet and a

Product gas outlet, wherein a process stage is arranged at the product gas outlet. This process stage is designed to produce a product gas mixture that is at the

Product gas outlet is provided, in a purge gas, in a

 (liquid) portion of the methanol-containing product and to separate into a circulating gas component. The reactor system further comprises a cycle gas recirculation to lead back the cycle gas fraction and combine with the starting material before the resulting mixed gas can be fed to the gas inlet.

The number of cycles determines the economy of

Methanol synthesis. The mixture of the starting materials (feed gas) has process-related to a hydrogen excess. This excess must be removed from the process (eg by blowing off) to maintain process pressure. The surplus, which is blown off, is called purge gas (exhaust gas) and is flared so far mainly in large plants, unterfeuert and in very small systems of small quantities due to the environment

delivered. Another excess gas is C0 ₂ , which, unreacted dissolved in the crude methanol leaves the synthesis loop. The unreacted C0 ₂ is released so far in three streams:

 - Gas in the purge gas for blowing off, flaring or underfiring;

 - Gas in the so-called solvent gas for blowing off;

dissolved in crude methanol according to the pressure in the

 Low pressure and fed to the raw methanol of the distillation.

The reactor system of the invention is characterized in that it comprises a return line, the so with its line input to the downstream process stage and with its line output with a

It can be connected to the input stage of the reactor system so that at least part of the purge gas can be returned to the input stage in order to be passed through the reactor again. However, since the composition of the purge gas is very different from the desired make-up gas composition, it is necessary to reduce the amount of at least one of the feed gases hydrogen and Adjust carbon dioxide accordingly. The reactor plant therefore according to the invention comprises a measuring device which is arranged in the region of the input stage for determining the instantaneous carbon dioxide fraction. In addition, it comprises control means, which are arranged in the region of the input stage for predetermining the carbon dioxide proportion and / or the hydrogen content.

The process control in the reactor plant is such that the

Purgegas a carbon dioxide content, a hydrogen content and a

Includes carbon monoxide. Due to process fluctuations, the ratio between the carbon dioxide content, the hydrogen content and the carbon monoxide content at the outlet of the reactor is variable. The control means together with the measuring device are able to compensate for these process fluctuations by regulating the fresh carbon dioxide content and / or the fresh hydrogen content on the input side of the input stage.

In order to control the process fluctuations control, the measuring device must be able to determine the carbon dioxide content in the gas flow of the return line quickly and reliably. The invention is here in preferred embodiments to a

 Thermal conductivity sensor, as measured by conductivity measurement of the

Carbon content (carbon dioxide and carbon monoxide together) can be reliably determined and distinguished from the hydrogen content, such as

Studies have shown. In preferred embodiments, the thermal conductivity sensor directly determines the thermal conductivity of the purge gas, taking advantage of the fact that for a given temperature, gas molecules have the same mean kinetic energy. That Carbon dioxide and hydrogen of the gas stream have the same mean kinetic energy (e.g., at one

Measuring point after a static mixer). Therefore, a hydrogen atom with the relative mass 1 has a much greater velocity than the carbon dioxide with the relative mass 44. Because of this higher molecular velocity, hydrogen transports energy faster than carbon dioxide, that is, the thermal conductivity is greater. The thermal conductivity of carbon dioxide is more than 10 times lower than the thermal conductivity of hydrogen. This difference becomes one in preferred embodiments Thermal conductivity sensor determined.

The inventive recirculation design for the purge gas is characterized in that a simple, robust and fast control is provided, the

 - works without (absolute) quantity determination of the volume flows,

 - without the complex calculation of a volumetric flow adaptation

 manages,

- provides a simple C0 ₂ analyzer, and the

- Compared to previously known solutions a modified circuit of

Volume control of the feed gases H ₂ and C0 ₂ provides.

By the invention, the synthesis of methanol in comparison to the prior art could be further improved by the one hand the

Process efficiency (power consumption, consumption of raw materials, etc.) has been improved and on the other hand, the previously partially customary flaring or blowing off the purge gas was completely or largely prevented.

According to the invention is preferably in all embodiments, a (control technology) controlled Purgegasrückführung used.

In all embodiments, in addition, the so-called solvent gas can be recycled in order to achieve a further improvement. The reactor system according to the invention is controlled and the individual processes are "linked" with each other so that

 the total yield and quality (such as purity) of the

 maximum possible content of methanol-containing product,

- and / or the C0 ₂ - (total) emission in the form of purge gas and possibly solvent gas is as minimal as possible,

 - and / or stable and long-term plant utilization is achieved,

 - and / or the product specific investment and operating costs of the

Reactor plant to be as minimal as possible. Preferably, regenerative electrical energy is used to operate the reactor system in all embodiments.

With a reactor system of the invention methanol is produced as a storable and transportable energy form. That is, renewable energy is chemically transformed into an uncritical and relatively simple storage and transportable (liquid) form of energy.

The production of methanol can be shut down at any time or even interrupted. The procedural plant components for

 Production of methanol can be relatively easily and quickly shut down or shut down. Here, according to the invention, the decision sovereignty is the responsibility of the operator of the reactor plant. Methanol can serve as an energy buffer. For example, methanol can be stored in order to be able to provide additional electrical energy in the event of peak energy demand in the electrical grid. If necessary, methanol can either be incinerated in thermal power plants, or electric energy can be generated in fuel cells (eg direct methanol fuel cells, MFC).

If necessary, the methanol can be catalytically converted into a cracking gas of hydrogen and carbon monoxide before combustion. This results in advantages in certain implementation processes.

Preferred embodiments of the invention are based on the hydrogen production by means of electrical energy, which is generated as far as possible renewable and comes for example from wind, water and / or solar power plants. Hydrogen, the z. B. produced by electrolysis or by the use of elemental silicon and water, so does not need stored or highly compressed or liquefied refrigerated and transported over long distances, but serves as an intermediate, preferably at the location of its production directly the the aforementioned reaction for the production of methanol is supplied. Depending on the embodiment of the invention, an energy-converting process in which regenerative energy is converted into electrical energy is followed, for example, by material-converting (chemical) processes, namely the intermediary provision of hydrogen and the conversion of the hydrogen together with a carbon carrier (here in the form of Carbon dioxide) to methanol.

[00038] In consideration of corresponding energy-technical,

plant technical and economic requirements, together with the demand for careful use of all material, energy and economic resources, a new energy technology solution is provided according to the invention.

Further advantageous embodiments are given in the description, the figures and the dependent claims.

In the drawings, various aspects of the invention are shown schematically. shows a scheme that illustrates the principle of climate neutrality by investing in, or operating offsetting projects; shows a diagram showing the basic steps of the method, according to one of the above-mentioned international

 Patent applications, respectively, a corresponding Silicon-Fire system reproduces;

 shows a diagram representing the basic steps of the method according to the invention, or a corresponding Silicon-Fire plant;

 shows a side elevational view of an exemplary reactor of the invention;

 Fig. 3 shows a schematic view of a reactor plant of the invention, e.g. a reactor according to FIG. 4 can be used;

shows a schematic view of the high-pressure region of another reactor plant according to the invention, wherein z. B. a reactor of FIG. 4 can be used. The term energy source is used here for liquids that z. B. can be used as fuel or fuel. This refers in particular to methanol 108 or to products containing methanol 108. The term "methanol-containing product" is used here because the product which is provided at the outlet 201 of a reactor system 50 does not consist of one hundred percent methanol rather, a so-called

physical mixture of methanol and water, referred to herein as methanol-containing product 108. By a subsequent distillation process can then be recovered if necessary pure methanol.

Here, as the process direction, the direction from the input side E to the output side A, i. the flow or flow direction SR in the interior of a reactor 10 and the reactor system 50 is designated. Details are shown in FIG. 5.

As a low pressure area, the pressure range between 1 bar and 30 bar is referred to here. As a high-pressure area, the pressure range between 50 bar and 100 bar is referred to here. With reference to the reactor plant 50 of the invention, as shown in FIG. 5 and 6 are shown by way of example, e.g. the input side of static mixer 257 (i.e., supply line 258 to static mixer 257) in said low pressure region. Also, the return line 250 is in the low pressure region, if the return line 250 couples the purge gas PG before the static mixer 257. The gas inlet 21, the reactor 10, the gas outlet 23 and the recycle gas 262, however, are in the aforementioned high-pressure area.

As a static (gas) mixer 257 here a passive mixing element is referred to the gases with respect to temperature and / or concentration

homogenized. Such static (gas) mixers are well known in process engineering.

As (gas) compressor (eg, the compressors 260, 263) is here called a compressor that compresses gases, ie, the pressure of the gas increases when flowing from the input side of the (gas) compressor to the output side. Such (gas) compressors are in process engineering well known.

As a heater / heat exchanger 267 here an element or an assembly is referred to the / can heat or cool the gas stream as needed. Since the heater / heat exchanger 267 is used in the high-pressure region of the reactor system 50, a high-pressure heater / heat exchanger 267 is used. The figures schematically indicate that the heater / heat exchanger 267 comprises a heating / cooling loop 285. This heating / cooling loop 285 may be e.g. be flowed through. Such heaters / heat exchangers 267 are well known in the process engineering.

As a final cooler 269 here an element or an assembly is referred to, the / a high pressure gas cooling down. In all embodiments, this is preferably a high-pressure gas cooler. In the figures, it is schematically indicated that the end cooler 269 a

 Cooling loop 286 includes. This cooling loop 286 may be e.g. be passed through water to escape the high-pressure gas process heat. Such high pressure gas coolers are well known in the process engineering. As a high-pressure separator 270, an element is referred to here, which receives a product gas mixture PGG and separates into gas and liquid. The gas is released either via the output 274 as a recycle gas KG or via the output 277 as purge gas PG. A level gauge 272 together with an actuator S4 form a level control that controls this operation as needed. This level control maintains the liquid level at a predetermined level in the high pressure separator 270. The high pressure separator 270 and the liquid level are sized to provide sufficient time to blow off / discharge the crude methanol while leaving no foam or mist on the gas side. The level control is preferably autonomous in all embodiments and does not control any other operation in the reactor plant 50. The purge gas PG is discharged as surplus at the pressure hold controller 280 / S6. Such high-pressure separator 270 and the

peripheral equipment parts 272, S4, 280, S6 are in process engineering

well known. As a low-pressure separator 271 here an element is referred to, which receives a liquid and separates C0 ₂ gas from this liquid. The C0 ₂ gas is released via the outlet 278 as the release gas LG. One

Level gauge 273 together with an actuator S5 form a

Level control that controls this process as needed. Such

 Low-pressure separator 271 and also the peripheral system parts 273, S5 are well known in the process engineering.

Another element of the methanol synthesis is the synthesis reactor 10. Details of a suitable reactor 10 are the above-mentioned international patent application PCT / EP2010 / 064948 of the present

Applicant to take. However, other known synthesis reactors 10 can also be used. The invention is not only suitable for use in small or medium-sized systems but it can also be used in large

(industrial) plants are used.

Fig. 2 shows a schematic block diagram of the

Building blocks / components, or process steps, of a complete system 100 according to one of the international patent applications mentioned above. This overall plant 100 is designed so that a method of providing the methanol-containing product 108 can be carried out. The corresponding procedure is based on the following basic steps.

There are z. For example, carbon dioxide 101 is provided as a carbon source and hydrogen 103. The required for providing the hydrogen 103 DC electric energy El is here as far as possible generated by means of renewable energy technology and the entire system 100 is provided. Particularly suitable as renewable energy technology are solar thermal systems 300 and photovoltaic systems 400, which are based on solar modules. For example, hydropower can also be used. It is also possible to provide a combination of several plant types 300 and 400. A solar thermal system 300 may comprise a device 301 which makes it possible to convert heat into direct current (El (=).) Water electrolysis 105 is used as shown in FIG DC electric power El performed to produce the hydrogen (gas) 103 as an intermediate of water 102.

In FIG. 2, an overall system 100 is shown. In the overall system 100 shown, an economically and ecologically optimal combination of a regenerative power supply (by the systems 300 and / or 400) and a conventional power supply, here represented by a part of a network 500, is preferably realized. The entire system 100 therefore provides the regenerative electrical energy El largely directly

according to their attack for chemical reactions (here the electrolysis reaction 105) to use and thus chemically bind and store. Another portion of the required energy is obtained here, for example, from the interconnected network 500. This proportion is converted into direct current (energy) E2. For this purpose, a corresponding converter 501 is used, as shown in FIG. 2 indicated in schematic form. The corresponding system components or components are also referred to here as energy supply system 501.

By means of an intelligent system controller 110 may, for. B. the

Energy supply of the entire system 100 of FIG. 2 controlled and regulated. The plant controller 110 of FIG. 2 may be used in all embodiments with the plant controller 110 of FIG. 5 designed / realized as a common control. However, these controls 110 can also be designed / implemented separately in all embodiments. In principle, the respective currently available excess energy portion E2 is taken from the interconnected network 500, while the other

Energy share (here El) as far as possible from a plant-related

Solar power plant 300 and / or 400 (and / or from a wind power plant and / or from a hydroelectric power plant and / or from a wastewater treatment plant and / or from a biogas plant). Here, it is preferable for an intelligent reversal of the previous principle, in which the

Energy fluctuations of renewable energy systems 300, 400 are intercepted by switching on and off conventional power plants. It therefore needs to operate a total system 100 no additional power and

Frequency control capacities for regenerative power plants in the Verbundnetz 500 vorzuhalten. This principle allows the operator of a total plant 100 to include additional technical and economic parameters in the control of the overall plant 100. These parameters are so-called input quantities II, 12, etc., which are included in decisions by the controller 110. A part of the parameters can be specified within the controller 110 in a parameter memory 111. Another part of the parameters can come from the outside. Here, for example, price and / or availability information can be received from the operator of the interconnected network 500.

In Fig. 3, a further overall system 700 is now shown schematically. A part of this total plant 700 corresponds to the entire plant 100 according to FIG. 2. In this respect, reference is therefore made to the preceding description of the corresponding elements.

It is preferably in all embodiment, as described, produced by a water electrolysis 105 high purity hydrogen 103, which is converted to methanol 108 here. The energy comes from the

Embodiment of FIG. 3 wholly or substantially (preferably more than 80%) from renewable energy sources 300 and / or 400 (or from other renewable energy sources).

It can be provided in all embodiments, a number of control or signal lines, as shown by way of example

Lines 112, 113 and 114 are shown. These lines 112, 113 and 114 control energy or mass flows of the entire system 100 or 700.

In the plant controller 110 of FIG. 2, Fig. 3 and / or FIG. 5, so-called software-based decision-making processes are implemented. One

Processor of the controller 110 executes control software and makes decisions based on parameters programmed decisions. These

Decisions are translated into switching or control commands which, for example, via control or signal lines 112, 113, 114

Control / regulate energy and mass flows cause. For example, electrical signals sl, s2 control actuators Sl, S2, as shown in Figures 2, 3 and 5 indicated. This also applies to the other signals and actuators.

According to a particularly preferred embodiment of the invention, carbon dioxide 101 is used as a gaseous carbon source, as indicated schematically in Figures 2, 3 and 5. Preferably, in all embodiments, the carbon dioxide 101 is derived from a combustion process or an oxidation process via C0 ₂ deposition (eg, a Silicon Fire

Flue gas cleaning system) taken. However, the carbon dioxide 101 can also be separated off from crude gas and provided or originate from one of the other sources mentioned above. The carbon dioxide 101 can also come from other sources. Preferably, the carbon dioxide 101 is provided via a pipeline, a conduit, a steel bottle or a tank.

The DC power El is used in the illustrated embodiment to perform a water electrolysis to produce hydrogen 103 as an intermediate. The electrolysis system, respectively

Performing such an electrolysis, is shown in FIG. 2 and FIG. 3 by the

105. The carbon dioxide 101 is with the

Hydrogen 103 brought together. This happens in an input stage 253, as shown in FIG. 5 shown by way of example. The corresponding (mixed) gas is referred to herein as the starting material AS. The starting material AS becomes the reaction

(Methanol synthesis in a reactor 10) brought to the gaseous

Starting materials 101, 103 to convert to a methanol-containing product 108, which according to the invention in all embodiments both recycle gas KG led in a circle and purge gas PG and optionally also release gas LG is led back / be. The synthesis reaction is carried out in the reactor 10. The removal, respectively the provision of the methanol-containing product 108, is shown in FIG. 2 and FIG. 3 by the reference numeral 107. In Fig. 5, it is shown that the methanol containing product 108 is provided at an exit 201 of the (downstream) process stage 200.

In the following, further basic details of the process, a reactor plant 50 of the invention and the corresponding overall plants 100 and 700 will be described. These basic details of the method may be used / employed in all embodiments of the invention. The reactor plant 50 of the invention is preferably in all

Embodiments of a part of the entire plant 100 or 700. In order to produce hydrogen 103 as an intermediate product, a water electrolysis using DC El, as mentioned. The required hydrogen 103 is in an electrolysis plant 105 through the

Electrolysis of water H ₂ 0 prepared according to the following equation: H ₂ 0 - 286.02 kJ = H ₂ + 0.5 0 ₂ . (Reaction 1)

The required (electrical) energy El for this reaction of 286.02 kJ / mol corresponds to 143010 kJ per kg of H ₂ . The synthesis of the methanol-containing product 108 (CH ₃ OH + water) can be carried out in the reactor 10 / reactor system 50 of the entire system 100 or 700 after the exothermic reaction between carbon dioxide 101 (C0 ₂ ) and hydrogen 103 (H ₂ ) as follows C0 ₂ + 3 H ₂ = CH ₃ OH + H ₂ 0-49.6 kJ (methanol-water mixture, vaporous)

 (Reaction 2)

Reaction 2 gives the stoichiometry for the methanol synthesis. From a purely mathematical point of view, the starting material AS1 at the inlet 21 of the

Reactor 10 ideally a composition with 3 moles of H ₂ per mole of C0 ₂ . In practice, the composition should be approx. 3.05 to 3.10 moles of H ₂ per mole of C0 ₂ , since it must have a slight excess of hydrogen 103. Preferably, therefore, all embodiments of the invention operate with about 3.05 to 3.10 moles of H ₂ per mole of CO ₂ .

The resulting heat of reaction of 49.6 kJ / mol = 1550 kJ per kg of methanol = 0.43 kWh per kg of methanol 108 is from the corresponding

Discharged reactor 10. For this purpose, the reactor 10 may include a fluid space 14 (see, eg, FIG. In this preferred case, the actual reaction area (s) inside the reactor 10 are surrounded by a reactor jacket and cooled by a fluid (preferably water). In Fig. 4 are a corresponding fluid supply 16 and a

corresponding fluid removal 17 shown. Typical synthesis conditions in the synthesis reactor 10 are about 50 to 150 bar and about 250 ° C to 270 ° C. The pressure is preferably between 50 and 100 bar. The heat of reaction may, for. B. to other system elements, such as to an evaporator of a distillation column (which may be downstream of the process stage 200) or to other downstream plant areas "passed".

The (methanol) synthesis is according to the invention in all

Embodiments using a catalyst in the / the

Reaction area / reaction areas of the reactor 10 carried out so that the reaction product liquid methanol 108 (or methanol-water mixture) is formed.

If the entire plant is 100 or 700 near a C0 ₂ - source, can be dispensed with a liquefaction of C0 ₂ for transport. Otherwise, it is relatively easy according to the prior art to liquefy the C0 ₂ and to bring over long distances to a total system 100 or 700.

In FIG. 2 and FIG. 3 is based on the dashed arrow 112

indicated by the controller 110 that the controller 110 can regulate the energy flow El. The arrow 112 represents a control or signal line. Other possible control or signal lines 113, 114 are also shown. The control or signal line 113 controls, for example, the C0 ₂ amount that is available for the reaction 106 in the reactor 10. If, for example, less hydrogen 103 is produced by the electrolysis 105, proportionally less C0 ₂ must be supplied. The optional control or signal line 114 may regulate, for example, the amount of H ₂ via an actuator Sl. Such a regulation makes sense if there is a hydrogen buffer, which can be taken from hydrogen 103, even if at the moment no hydrogen or less hydrogen by the electrolysis 105th (or by the use of elemental silicon) is produced. Additionally or alternatively, an optional control or signal line 113 may control the C0 ₂ amount via an actuator S2. Preferably, in all embodiments of the invention, two actuators Sl, S2 followed by a static mixer 257 used to a process technically correct mixture of the components of the gaseous

Starting material AS ready to be able to steep. The provision of the

Stoichiometrically correct mixing of the components 101 and 103 takes place, for example, using the controller 110 and a suitable measuring device 254 (preferably 3.05 mol to 3.10 mol of H ₂ per mol of CO ₂ as starting material AS

pretend).

Investigations have shown that it is particularly economical and environmentally sound sense if the entire system 100 is designed or controlled that between 15% and 40% of the methanol 108 from

regenerative energy is generated while further methanol for the

100% supplement of other hydrocarbons (e.g., methane gas) is provided. However, the present invention is independent of the type of energy used.

Particularly preferred is an embodiment of the operating concept of the entire system 100 or 700, which provides the reference of low-cost electrical energy in the low load periods from a network 500 (as shown in Fig. 2).

Preferably, in all embodiments, a reactor 10 or a reactor unit 50 is used, which at the outlet (at Produktausiass 23) a methanol-containing material with a high methanol concentration (preferably a methanol-water mixture in the ratio 1: 1 (molar); 29.5 wt.% Water in crude methanol).

4, an exemplary reactor 10 is shown in a schematic representation. The reactor 10 has z. B. two input-side gas inlets 21, two output-side product outlets 23 a preferably a fluid space 14. The fluid space 14 serves in a preferred mode of operation of the

Reactor 10 to create an isothermal environment. For this purpose, a fluid (e.g., water or gas) may enter the fluid space 14 through a fluid supply 16. A fluid discharge 17 is provided on the fluid space 14 to remove the fluid. Depending on the situation can be cooled or heated.

[00079] Preferably, in all embodiments, a controller (which, for example, may be embodied as part of the (plant) controller 110) is provided

Reactor 10 is used which initially applies warm fluid to the fluid space 14 during the "start-up" of the reactor 10 to initiate the synthesis reaction, followed by the introduction of a cooled fluid to remove heat of reaction resulting from the exothermic synthesis Depending on the capacity of the reactor 10, reaction heat may be supplied by means of a fluid in the fluid space 14 and the synthesis reaction may proceed in the endothermic region.

Preferably, in all embodiments of the invention, the starting material AS and / or AS1 is preheated (eg by the

Heater / heat exchanger 267) and introduced into the reactor 10 at elevated pressure. The pressure and the temperature depend on the type of catalyst. The temperature can range between 100 and 350 degrees Celsius and the pressure between 15 and 150 bar. Preferably, the temperature is in the range between 200 and 280 degrees Celsius and the pressure between 50 and 100 bar.

With reference to FIG. 5 and 6, important aspects of the invention will now be explained. The invention is used or used in a reactor system 50, which is shown in FIG. 5 is shown schematically. The reactor plant 50 is designed specifically for the synthesis of a methanol-containing product 108. The synthesis reaction 106 is carried out using a starting material AS1 which contains a gas having a carbon dioxide fraction 101 and a hydrogen fraction 103. The reactor 10 of the reactor system 50 has a gas inlet 21 and a Product outlet 23, wherein at the product outlet 23 a process stage 200 is arranged. This process stage 200 is designed to separate a product gas mixture PGG, which is provided at the product outlet 23, into a purge gas component PG, into a portion of the methanol-containing product 108 and into a recycle gas component KG. The reactor system 50 further comprises a cycle gas recirculation 262 in order to recirculate the recycle gas component KG and to combine it with the starting material AS before the resulting mixed gas (here called AS1) can be fed to the gas inlet 21. The reactor system 50 of the invention is characterized in that it comprises in all embodiments in addition to the recycle gas 262 a return line 250, the so with its line input 251 to the process stage 200 and with its line output 252 to the input stage 253 of the reactor system 50th is connectable, that at least a portion of the purge gas PG is attributable to the input stage 253 to be passed through the reactor 10 again. The reactor system 50 includes a measuring device 254, which in the area of the input stage 253 for determining the current

Carbon (dioxide) proportion is arranged. It comes preferably one

Control device 255 is used, which may be part of the (plant) controller 110. The control device 255 or the (plant) control 110 is designed to specify the carbon dioxide content and / or the hydrogen content and therefore controls / controls the input stage 253.

[00084] In all embodiments, the control device 255 or the (plant) controller 110 preferably controls the actuator S1 and / or the actuator S2.

The process control in the reactor system 50 is carried out using the control device 255 and / or the (plant) controller 110 so that the purge gas PG mainly only a carbon dioxide content and a

Includes hydrogen. In addition, the purge gas portion PG may include a small amount of carbon monoxide. Due to process variations in the reactor system 50, the ratio between the carbon dioxide content, the hydrogen content and the carbon monoxide content at the outlet 23 of the reactor 10 is variable. The controller 255 and / or the (plant) controller 110 are / are together with the measuring device 254 capable of this

To compensate for process fluctuations by controlling the fresh carbon dioxide fraction 101 and / or the fresh hydrogen fraction 103 on the input side E of the input stage 253 / t.

The reactor 10 is, as described, filled with a catalyst for the catalytic conversion of the carbon dioxide content and the

Hydrogen content to the product gas mixture PGG is used. By the

Control device 255 and / or the (plant) controller 110 is a desired stoichiometry of the carbon dioxide content and the hydrogen content of the

Predetermined starting material AS1, which in all embodiments per mole

Carbon dioxide portion 101 preferably 3.05 to 3.10 moles of hydrogen has 103 shares. It should be noted here that depending on the catalyst, e.g. Also, a small excess of the hydrogen content 103 may be possible. In this case, the control device 255 and / or the (plant) controller 110 predefines a correspondingly adapted nominal stoichiometry. However, the kinetics of methanol synthesis 106 always requires a slight excess of hydrogen 103.

The conversion to the methanol-containing product 108 is incomplete because the reaction 106 is limited by a thermodynamic equilibrium. The conversion of the reactants (i.e., the proportion of carbon dioxide 101 and the proportion of hydrogen 103 in the starting material AS1) is not completely in the direction of the products (methanol and water). This necessitates a so-called circulation mode of operation in which reaction gas leaving the reactor 10 at the outlet 23 (referred to herein as the product gas mixture PGG) is fed back to the inlet 21 by means of a recycle gas recirculation 262. In each case, feedstocks (reactants) are discharged at the outlet of the reactor 10, but the proportionate amount thereof is always lower as the cycle ratio is increased. The recirculating gas recirculation 262 preferably comprises in all embodiments a compressor 263 (also referred to as a recirculation gas compressor) which is used to reduce the proportion of circulating gas KG, which is recirculated through the recycle gas 262, from that of the recirculation gas

Pressure level at the outlet 23 to the higher pressure level at the inlet 21 to bring. The use of the recycle gas 262 increases the conversion of the reactants. Without such recycle gas 262 would be on the outlet side 23 together with the product 108 and feedstocks

(Reactants), which in most cases ecologically and economically does not make sense.

In the final cooler 269, the reaction products methanol and water are almost completely removed from the gas mixture at the outlet 23 by condensation. It will only be the remaining gaseous

Components returned to the circulation gas KG. A measure of the quantity is the volume of the gas. Thus, cycle gas ratio (P / E) 4 means that 4

Volume units of the incompletely reacted gas with 1 volume Make-Up Gas AS (so called in this method, the fresh gas mixture) is mixed. This cycle gas KG then passes through the reactor 10 again and is also converted in this way to methanol (and water).

 In addition, the equilibrium and kinetics of the reaction 106 for the product 108 are favorably influenced by the dilution of the reactants in the reaction gas. At the outlet 23 of the reactor 10, a product gas mixture PGG is output. The synthesis reaction 106 requires a minor one

Hydrogen excess. This is enriched in the circulation. The pressure in the reactor 10 would increase steadily without pressure. The pressure-holding regulator 280 / S6 at the outlet 277 of the high-pressure separator 270 therefore blows off the excess gas (purge gas PG). That At the high-pressure separator 270, purge gas PG is discharged as a result of the process. The purge gas PG comprises in the present process management essentially carbon dioxide, hydrogen and a low carbon monoxide content, the ratio between the

Carbon dioxide, the hydrogen and the carbon monoxide component is variable. This variability results from a whole series of parameters, such as pressure fluctuations, saturation of the catalyst 60, degree of consumption of the catalyst, temperature fluctuations, etc. in the reactor system 50. The amount of purge gas per se is not a (strongly) variable variable.

In the following, further details of the reactor system 50 will be described. As shown in FIG. 5, the input stage 253 of FIG Reactor 50 have a fresh gas supply 264 for hydrogen gas 103 and carbon dioxide gas 101. The two output lines of the

Fresh gas supply 264 each have an actuator Sl or S2 to the

Volume proportions of the fresh gases 103 and 101 pretend. These

Actuators S1 and S2 are preferably controlled in all embodiments by the control device 255 and / or by the (plant) controller 110.

In the case of FIG. 5 embodiment shown includes

Reactor 50 a flow control 265 to determine the flow rate can.

In the case of FIG. 5 embodiment, both the

Measuring device 254 and the flow control 265 on the supply line 256 to the static mixer 257 to. The control device 255 or the

(Plant) control 110 give corresponding control signals sl and s2 to the actuators Sl and S2, as shown in FIG. 5 schematically by dashed

Signal lines shown.

The two fresh gases 103 and 101 are fed via a supply line 258 in the static mixer 257, so as to obtain a homogenized mixture of the fresh gases 103 and 101. Preferably, the

Return line 250 in all embodiment before the static mixer 257 (as shown in Fig. 5). However, under certain circumstances it can also start between the static mixer 257 and a subsequent fresh gas compressor 260 (not shown).

In the case of FIG. In the exemplary embodiment shown in FIG. 5, both the return line 250 and the supply line 258 are in FIG

Low pressure area in front of the control device 255. This is preferably the case in all embodiments.

[00096] It is important to note here that the recirculation line 250 purge gas PG with relatively low pressure (preferably at all

Embodiments in the low pressure range between 5 bar and 30 bar) to the input stage 253 supplies. Therefore, the purge gas PG is preferably in Low pressure range fed in front of the fresh gas compressor 260. at

Solutions that feed the purge gas PG to the fresh gas compressor 260 would require a separate purge gas compressor (not shown) to feed the purge gas PG at a correspondingly higher pressure.

In a particularly preferred embodiment, as shown in FIG. 5, the controller 255 is disposed between the static mixer 257 and the fresh gas compressor 260 to flow directly in the flow of the

homogenized feed gas mixture EGG (i.e., in the flow of feed line 256) to perform the required measurement (s). The electrical signal sl of the measuring device 254 drives preferably at all

Embodiments, the actuator Sl (the mass flow controller) of the

Hydrogen flow on. In this case, the signal value of the starting material AS without the purge gas recirculation 250 serves as a setpoint.

In all embodiments, preferably the

Volume control of the entire feed gas mixture EGG by a

Flow control 265 (eg in the form of a flow controller), which is arranged downstream of the measuring device 254 in the flow direction SR. The signal s2 of

Flow control 265 preferably drives actuator S2 (the mass flow controller) of the carbon dioxide flow in all embodiments.

With this arrangement, the proper composition and proportion of feed gases 101, 103 and PG are ensured, regardless of whether the purge gas recycle 250 is running at part load or full load, or even off.

After the static mixer 257 follows in the flow direction SR considered the already mentioned fresh gas compressor 260, the

Feed gas mixture EGG brings from the low pressure area into the high pressure area. The output line 261 of the fresh gas compressor 260 is merged with a line 266 of the recycle gas 262. To the problem-free

Merging the lines 261 and 266, respectively, to allow the gas on the output side of the fresh gas compressor 260 and the cycle gas KG, the cycle gases KG on the pressure of the gas in the Output line 261 of the fresh gas compressor 260 are brought. Therefore, the cycle gas recirculation 262 comprises a cycle gas compressor 263. The combined gas (EGG plus KG), which is now guided in the direction of the gas inlet 21 of the reactor 10, as the actual starting material ASl

designated. The actual starting material AS1 is already in the

suitable high pressure range to feed the reactor 10 can. However, in order to also be able to specify the optimum temperature of the starting material AS1, a heater / heat exchanger 267 follows on the input side of the reactor 10. This heater / heat exchanger 267 heats the starting material AS1, as required.

In the area downstream of the recycle gas compressor 263, in all embodiments, an actuator S3 and a flow control 268 may be provided

be arranged. The flow control 268 controls the actuator S3 by means of an electrical signal s3.

The downstream process stage 200 preferably comprises the following elements in all embodiments. The (gas) outlet 23 feeds a final cooler 269. Behind this final cooler 269 are a

High pressure separator 270 and a low pressure separator 271 in series

arranged. After each of the separators 270, 271 may be an associated

Actuator S4, S5 follow as shown. Each of the actuators S4, S5 is controlled by a level indicator 272, 273 (LIC, Level indicator controller). That the level gauge 272, 273 together with the respective actuator S4, S5, a level control. The corresponding electrical signals are referred to here as s4, s5.

[000103] The total amount of crude methanol is included in the

Low pressure separator 271 delivered. The methanol content (residual methanol) of the cycle gas KG is only determined by the pressure and temperature of the final cooler 269.

In simplified terms, the corresponding circulating gas stream is as follows: outlet 23 final cooler 269 high-pressure separator 270 outlet 274 circulating gas compressor 263 line 266 heater / heat exchanger 267 inlet 21 reactor

Raw methanol is withdrawn as follows: outlet 23 final cooler 269 high-pressure separator 270 outlet 275 low-pressure separator 271 outlet 276 outlet 201. After the outlet 201, a line, a tank or a distillation stage can follow.

From the Hochdruckabscheider 270, the purge gas PG can be removed via an output 277, as already described.

Part of the C0 ₂ is not reacted in the methanol synthesis in the reactor 10. This unreacted C0 ₂ from the synthesis cycle is in the

Raw methanol very soluble. Part of this unreacted C0 ₂ leaves the synthesis cycle in dissolved form. When the crude methanol is expanded in the low-pressure separator 271, part of the CO _{2 is released in} gaseous form as the release gas LG, depending on pressure and temperature. From the low-pressure separator 271, optionally, this dissolving gas LG can be removed via an outlet 278.

It is - depending on the pressure - more or less rewarding to supply this release gas LG the purge gas PG and lead together to the input stage 253 back. At low pressure in front of the static mixer 257 (up to about 15 bar) can be given an economy for the return of the release gas LG. At higher pressure before the static mixer 257 (e.g., at 20 bar), the effect of economy is not so significant.

Higher pressure here means a higher suction pressure for the fresh gas compressor 260, which is thus significantly smaller and consumes less energy. This effect predominates when considering the economic feasibility of an optional release gas recirculation. By a Lösegasrückführung the C0 ₂ emissions are reduced to the outside and is thus an ecological argument. Therefore, this release gas recirculation can be optionally provided for all embodiments.

If one provides a Lösegasrückführung, the pressure of the Niederdruckabscheiders 271 at the output 278 should be set slightly higher are considered to be the pressure of the fresh gas AS in front of the static mixer 257 in order to be able to incorporate the gas flow of the release gas LG into the purge gas return line 250. According to the invention, the purge gas PG and possibly also the release gas LG is fed via the return line 250 back to the input stage 253. In the in Fig. In the embodiment shown in FIG. 5, only purge gas PG is fed back to the input stage 253 and the release gas LG is delivered via a line 279.

The provision of purge gas PG can be controlled in all embodiments via a pressure display controller 280 and a corresponding actuator S6, which is controlled with an electrical signal s6. At the output 281, a flow control 282 may be arranged with a further actuator S7 to deliver purge gas PG, if necessary, instead of leading back according to the invention.

If the release gas LG is to be discharged from the reactor system 50, in all embodiments, a pressure display controller 283 and a corresponding actuator S8, which is controlled by an electrical signal s8, can be used (see FIG. 5). If the solute gas LG is to be recycled together with purge gas PG in case of need, an optional connection line 284 is arranged according to the invention, the dissolving gas LG e.g. can be taken at a point after the actuator S8 and introduced into the area where the line input 251 of the return line 250 attaches. In Fig. 5, the optional connection line 284 is indicated by a dotted arrow. This release gas recirculation is optional.

[000114] As shown in FIG. 6, merging the

Feed gas mixture EGG and the cycle gas KG also take place before the compressor 263. In the in Fig. 6 approach, the compressor 263 must be dimensioned slightly larger than in Fig. 5. The in FIG. 6 variant can be used in all embodiments of the invention.

In the cycle gas stream KG is always a certain amount of the feed gas mixture EGG (as a mixture of H ₂ , C0 ₂ and small amounts of CO) introduced, so that a synthesis gas mixture (starting material ASI called) is provided, which can be passed into the reactor 10. Eventually, the temperature of the starting material AS1 is raised by the heater / heat exchanger 267. Thus, always in the present methanol synthesis in the reactor 10, a portion of the feed gas mixture EGG as fresh gas (which also contains the recirculated purge gas PG and possibly also releasing gas LG) with the recycle gas flow KG, which does not contain fully reacted products together in the / the Reaction zone / s of the reactor 10 brought. Due to the frequency with which this loop is driven, the proportion of incompletely reacted gases becomes smaller and smaller, as it were. The number of revolutions of the circulating gas quantity is referred to as the recycle gas ratio KGV, as already mentioned.

[000116] Investigations have shown that due to the variations in the composition of the purge gas PG, no static solution is possible. Therefore, according to the invention, a controlled Purgegasrückführung to

Commitment. It has been shown that the carbon dioxide content in either

recirculated purge gas PG in the return line 250 and in the area after the actuator S2 or only in the region of the supply line 256 needs to be determined in order to enable a reliable control of purge gas return of the invention. Preferably, the carbon dioxide content in all embodiments in the supply line 256 is determined / measured.

It has also been shown that the carbon dioxide content can be determined reliably and quickly by relying on a conductivity measurement. Such a conductivity measurement using at least one

Conductivity sensor (as part of a measuring device 254 on the supply line 256) provides a reliable and reproducible indication that it is the

Control device 255 and / or the (plant) control 110 makes it possible to intervene in order to increase or decrease the proportion of the freshly supplied carbon dioxide gas 101 and / or the hydrogen gas 103 so that the predetermined desired stoichiometry of the feed gas composition AS1 can essentially be maintained , Furthermore, it has been found that the feed gases 101, 103 are very pure are and therefore have no or very low levels of unreactable interfering or even harmful components. Therefore, even in the purge gas PG despite concentration only very small amounts of these

Components available.

Since the composition of the purge gas stream PG is very different from the desired feed gas composition AS1, it is necessary to reduce the amount of fresh feed gases, ie. the carbon dioxide gas 101 and / or the hydrogen gas 103, adjust accordingly.

[000120] In the context of the corresponding regulation in all embodiments, this concerns processes which take place virtually in real time and which are continuous. The acquisition, evaluation and control of the volume flows and the current composition would be technically too expensive. Moreover, such a control process would be vulnerable and possibly unstable depending on the situation. In order to keep the technical effort and the cost justifiable, the invention makes its way over the already mentioned thermal conductivity measurement using at least one conductivity sensor 259. [000121] The very different thermal conductivity of the gases H ₂ and C0 ₂ is measured using a thermal conductivity detector (analyzer). Sensor 259) determines the gas stream to be analyzed with sufficient accuracy. The chromatographic splitting of the gas can be dispensed with. It has been shown that the very small amount of CO present in the purge gas PG is negligible in its effect on the measurement results. The CO content is recorded by measurement as C0 ₂ content. The measurement by means of a thermal conductivity detector 259 is possible here, since the heat conductivities of C0 ₂ and CO, due to the much higher molar mass of the light hydrogen

differ.

There are two basic embodiments of the invention that differ substantially in whether the analysis of the purge gas stream PG occurs in or on the recycle line 250, or whether an analysis of the instantaneous gas flow in the supply line 256 is made

Fresh gas compressor 260 feeds. In Fig. 5 is a preferred embodiment , which uses a measuring device 254 to conduct an analysis of the instantaneous gas flow in the supply line 256

perform. This analysis is thus carried out in the flow direction SR behind the point at which the purge gas PG is fed into the supply line 258. In the first-mentioned basic embodiment, by contrast, the analysis purge gas PG takes place in or on the line 250. It is also conceivable to combine the two embodiments in such a way that one

Conductivity measurements both in or on the line 250 and in or on the line 256 makes. Depending on the design, this additional technical effort allows even more precise and / or faster control.

[000123] The in Fig. The embodiment shown in FIG. 5 is preferred since it not only determines the influence of the recirculated purge gas PG (and possibly the dissolving gas LG) in real time, but also determines the actual composition of the fresh gases 101, 103 after the static mixer 257. This solution allows, as it were, an overall view with only one measuring device 254. This has the advantage, inter alia, that the reactor system 50 would also function if no purge gas PG were temporarily returned (eg during maintenance work). In this case, the control device 255 and / or the (plant) control 110, together with the measuring device 254, sets the correct composition (desired stoichiometry) of the fresh gases 101, 103. In this special case (if PG = zero), AS = EGG is considered very simplified.

In all embodiments, however, always the right one

Regardless of whether the purge gas recirculation is running at partial load or full load operation composition and the correct ratio of the feed gases secured.

The measuring device 254 is preferably at all

Embodiments arranged directly in the stream of the finished feed gas mixture EGG between the static mixer 257 and the fresh gas compressor 260, as shown in FIG. 5 shown. The electrical signal sl of the measuring device 254, for example, drives the mass flow controller S1 of the hydrogen flow. The setpoint is the signal size of the fresh gas H ₂ without

Purgegasrückführung. The volume control of the total fresh gas flow (H ₂ and C0 ₂ ) is preferably carried out in all embodiments by the flow controller 265, arranged in the gas flow to the measuring device 254. Its signal s2 drives, for example, the mass flow controller S2 of the C0 ₂ stream.

Investigations and calculations have shown that the

Purge gas loss actually has a small effect on the fresh gas requirement, if the purge gas PG as previously, for example, simply released into the environment. For example, in a reference system 50, approximately 1% of C0 ₂ and 3% of H _{2 would be lost} under design conditions in Purgegas PG. But the high prices of the pure feed gases 101, 103 and the complete avoidance of the exhaust gas losses and the exhaust emissions make the small additional

procedural and control technical effort of the present invention economically and ecologically sensible. An advantage of the invention is the avoidance of exhaust emissions.

A much greater advantage is the elimination of the need to interpret the cycle of methanol synthesis to very high conversions.

Typically, C0 ₂ utilization has heretofore been more than 98% designed to "lose" only about 2% of C0 ₂ in the process. If purge gas PG is recirculated according to the invention, reactor 50 can be designed to operate at substantially lower conversions This makes it possible to reduce the reactor volume of the reactor 10 and the associated circuit 262. This is particularly noticeable in the case of investment costs for the reactor 10, which must preferably be designed for high pressures in the range between 50 and 100 bar.

Likewise, this has an influence on the catalyst requirement, which contributes not insignificantly to the so-called consumption costs. [000129] The aspects of the various embodiments can be easily combined by making minor adjustments.

[000130] The following are further basic aspects

inventive method for providing methanol-containing products 108 described. The reactor 10 is particularly suitable for the synthesis of regenerative methanol CH ₃ OH from carbon dioxide C0 ₂ and hydrogen H ₂ , if the hydrogen H ₂ via the (endothermic) electrolysis of water with

regenerative electrical energy according to reaction 1, as already mentioned above, is generated.

H ₂ 0 - 286.02 kJ / mol = H ₂ + 0.5O ₂ . (Reaction 1) The exothermic methanol synthesis (Reaction 2, as already mentioned above) is represented by the empirical formula:

C0 ₂ + 3 H ₂ = CH ₃ OH + H ₂ 0-49.6 kJ (methanol gaseous). (Reaction 2) It must be emphasized that the reactor 10 in all

 Embodiments of course can also be used for other synthesis processes and that the synthesis can be operated with regenerative energy and / or with regenerative starting material AS, but also with fossil energy and / or with fossil starting material AS.

The use of the invention is particularly advantageous in connection with a process for methanol synthesis which operates at low pressures (eg 80 bar). [000135] The principle of the invention can also be applied to large systems

transfer . The linearity of the process plays a very important role in scaling up.

The synthesis gas from carbon dioxide and hydrogen or from a very small amount of carbon monoxide, and larger proportions of carbon dioxide 101 and hydrogen 103 can be implemented in a reactor 10 according to the invention using a suitable catalyst for each of methanol 108 and a methanol-containing product 108, such as described. Depending on the synthesis reaction z. Example, copper-based catalysts (eg., CuO catalysts), or zinc oxide catalysts (eg ZnO catalysts), or Chromium oxide-zinc oxide catalysts are used. All other known catalysts are suitable for use in a reactor 10.

Particularly suitable are fixed bed catalysts or fluid bed catalysts. The catalyst may also comprise a suitable carrier (eg carbon, silicate, aluminum (eg Al ₂ O ₃ ) or ceramic). Instead of the mentioned

"Metallic" catalysts can also be used an organic catalyst.

Reference number:

Automotive / Automotive 1

 Power plant operator 2

 Wind Farm 3

Reactor 10

 Fluid space 14

 Fluid supply 16

 Fluid removal 17

Gas inlet 21

 (Product) outlet / gas outlet 23

Reactor plant 50

Overall plant 100

 Carbon dioxide 101

 Water 102

 Hydrogen 103

 Providing carbon dioxide 104

 Performing an electrolysis 105

 Reaction 106

 Dispensing / Providing Methanol 107

 methanol-containing product 108

 (Plant) control 110

 Parameter memory 111

 Control or signal lines 112, 113, 114 downstream process stage 200th

 Exit 201

Return line 250

 Line input 251

 Line output 252

 Entrance level 253

 Measuring device 254

 Control device 255

 Supply line 256

 static (gas) mixer 257

 Supply line 258

 Thermal conductivity sensor 259

 Fresh gas compressor 260

 Output line 261

 Circulating gas recirculation 262

 Compressor / cycle gas compressor 263

 Fresh gas supply 264

 Flow control 265

Head 266 Heater / heat exchanger 267

 Flow control 268

 Final cooler 269

 High pressure separator 270

 Low pressure separator 271

 Level gauge 272

 Level gauge 273

 Exit 274

 Exit 275

 Exit 276

 Exit 277

 Exit 278

 Line 279

 Pressure hold 280

 Exit 281

 Flow control 282

 Pressure display controller 283

 Connecting line 284

 Heating / cooling loop 285

 Heating / cooling loop 286

Solar thermal plant 300

 Conversion of heat into direct current 301

Solar system (photovoltaic system) 400

Interconnected network 500

 Conversion of AC voltage to 501

DC (power supply system)

Silicon-Fire total plant 700

Exit side A

 Starting material AS

 Starting material AS1

 Entry side E

 DC power El

 DC power E2

 Feed gas mixture EGG

 Input quantities II, 12, etc.

 Kreisgas KG

 Cycle gas ratio KGV

 Dissolving gas LG

 Product gas mixture PGG

 Purge gas / excess gas PG

 Actuator / mass flow controller Sl, S2, S3, S4, S5, S6, S7, S8

Signal lines / electrical signals sl, s2, s3, s4, s5, s6, s7, s8

Flow direction SR

Claims

 claims:

1. reactor plant (50) for the synthesis of a methanol-containing product (108) using a starting material (ASl) containing a gas with carbon content (101) and hydrogen content (103), wherein the reactor (10) has a gas inlet (21) and a Product outlet (23), wherein at

 Product outlet (23) a process stage (200) is arranged, which is designed to separate a product gas mixture (PGG), which is provided at the product outlet (23), in a proportion of methanol-containing product (108) and in a recycle gas component (KG) wherein a purge gas component (PG) is provided by the process stage (200), and wherein the

 Reactor (50) comprises a cycle gas recirculation (262) to the

 Circulating gas component (KG) in the direction of the gas inlet (21) attributed, characterized in that the reactor system (50) comprises:

- A return line (250) which is connected to a line input (251) to the process stage (200) and a line output (252) with an input stage (253) of the reactor system (50) that at least a portion of the purge gas (PG ) to the input stage (253) is returned to be passed through the reactor (10) again,

- A measuring device (254), which is used to determine the current

 Carbon content in the input stage (253) is designed,

- A control device (110, 255), in the area of the input stage

 (253) for setting or adjusting the ratio of

 Carbon content and the hydrogen content is arranged.

2. Reactor (50) according to claim 1, characterized in that the

Reactor (10) with a catalyst for the catalytic conversion of

 Carbon content and the hydrogen content to the product gas mixture (PGG) is equipped, wherein by the control device (255) a desired stoichiometry of the carbon content and the hydrogen content in consideration of the purge gas content (PG) can be predetermined.

3. Reactor (50) according to claim 1 or 2, characterized in that the conversion to the methanol-containing product (108) only

incomplete and that the purge gas (PG) a Carbon dioxide content, a hydrogen content and a carbon monoxide content comprises, wherein the ratio between the carbon dioxide content, the hydrogen content and the carbon monoxide content is variable.

Reactor (50) according to claim 1, 2 or 3, characterized in that the measuring device (254) comprises a thermal conductivity sensor (259) to determine the instantaneous carbon dioxide content in the gas stream in the input stage (253) by a conductivity measurement.

Reactor (50) according to claim 4, characterized in that by the measuring device (254) the instantaneous carbon dioxide content in the gas flow of the return line (250) and / or in the gas flow of a supply line (256) to a compressor (260) of the input stage (253) determined is.

Reactor (50) according to one of the preceding claims 1 to 5, characterized in that the control device (110, 255) is designed for this purpose

 - If too much carbon dioxide in the gas stream of

 Return line (250) to increase the supply of hydrogen content (103), and

 - At a low carbon dioxide content in the gas stream of

 Return line (250) to reduce the supply of hydrogen content (103).

Reactor (50) according to one of the preceding claims 1 to 5, characterized in that the control device (255) is designed for this purpose

 - If too much carbon dioxide in the gas stream of

 Return line (250) to reduce the supply of carbon dioxide (101), and

 - At a low carbon dioxide content in the gas stream of

Return line (250) to increase the supply of carbon dioxide (101).

8. reactor system (50) according to any one of the preceding claims, characterized in that it comprises a static mixer (257) and downstream in the flow direction (SR) compressor (260) which are parts of the input stage (253).

9. Reactor (50) according to claim 8, characterized in that the

Conduit exit (252) of the return conduit (250) is fluidly connected to a supply conduit (258) of the static mixer (257) in an area in front of the static mixer (257).

10. Reactor (50) according to claim 8, characterized in that the

Line output (252) of the return line (250) is fluidly connected to an output line (256) of the static mixer (257) is connected.

11. Reactor (50) according to any one of the preceding claims, characterized in that the reactor system (50) by a

 Circular gas ratio (KGV) is characterized, which is smaller than 5, wherein the cycle gas ratio (PPS) is defined as the number of cycles of

 Circular gas (KG) through the recycle gas return (262).

Reactor (50) according to one of the preceding claims, characterized in that the return line (250) of the reactor system (50) is located in a low-pressure region whereas the

 Circulating gas recirculation (262) is located in a high-pressure area.

Use of a reactor plant (50) according to one of the preceding claims for the production of methanol, wherein preferably a portion of the energy requirement of the reactor plant (50) is provided by regenerative energy.

A method of providing a methanol-containing product (108) comprising the steps of:

 - Providing (104) a gas with carbon content (101) as

Carbon source, Providing a hydrogen portion (103),

 Providing a starting material (AS) comprising the carbon fraction (101) and hydrogen fraction (103),

 - Providing a Purgegasanteils (PG) by means of a

 Return line (250),

 - combining the starting material (AS) and the purge gas fraction (PG) so as to obtain a gas mixture (AS1, EGG),

 Introducing the gas mixture (AS1, EGG) into a reactor (10), wherein the gas mixture (AS1, EGG) in the reactor (10) passes through a reaction zone which is equipped with a catalyst,

 Providing a product gas mixture (PGG) at an exit side (23) of the reactor (10)

 Separating the methanol containing product (108) from the

 Product gas mixture (PGG), wherein the purge gas (PG) is obtained, and

- Introducing the purge gas (PG) in the return line (250).

15. The method according to claim 14, characterized in that a

 Circuit gas recirculation (262) is provided, wherein after the separation of the methanol-containing product (108), a gas mixture as recycle gas (KG) through the recycle gas return (262) is returned, and wherein the recycle gas (KG) with the gas mixture (EGG) is brought together before the resulting gas mixture (AS1) is introduced into the reactor (10).

16. The method according to claim 14 or 15, characterized by the following step:

 - Inserting a Hochdruckabscheiders (270) and a

 Level control (272, S4) to disconnect the

 methanol-containing product (108), wherein the

 Purge gas (PG) at the high-pressure separator (270) is obtained.

17. The method according to claim 16, characterized by the following step:

 - Inserting a low-pressure separator (271) and a

 Level control (273, S5) to a release gas (LG), the

Carbon dioxide contains, separate from the methanol-containing product (108). A method according to claim 17, characterized by the following step: - recirculation of the solvent gas (LG) together with the purge gas (PG).

Method according to one of claims 14 to 18, characterized by the following steps:

 Determining the thermal conductivity of the carbon fraction (101) before or after contacting with the purge gas (PG),

 - Determine whether the carbon content is too low or too high (101)

 is present,

 - Influencing at least one actuator (Sl, S2) to relatively

 considered to increase the carbon content (101) or the hydrogen content (103).

Method according to one of claims 14 to 18, characterized by the following step:

 - Introducing the gas mixture (AS1, EGG) in a static mixer (257) to homogenize the gas mixture (AS1, EGG), wherein the introduction takes place after the combination of the starting material (AS) and the purge gas (PG).

Method according to one of claims 14 to 18, characterized by the following step:

 - rules of gas composition by changing the

 Hydrogen content using a first actuator (Sl),

 - Measuring the amount of gas through a flow meter (265), and

 - regulating the amount of gas by changing the carbon content below

 Use of a second actuator (S2).