FR3107195A1 - Method and apparatus for the production of chemical compounds - Google Patents

Abstract

The method and apparatus according to the invention allow the production of chemical compounds without the use of catalysts. For this, the compression reactors are supplied with the reagents necessary for the desired products. In addition, the reaction conditions are controlled by means of an electronic control device. To do this, the compression reactors are in particular combined with an electronic machine, which makes it possible to influence the residence time in the reactors. In addition, it is planned to increase the pressures of the reactants using a compressor. In addition, operating conditions are recorded using appropriate sensors and / or analyzers. Figure for the abstract: Figure 12

Description

Method and apparatus for the production of chemical compounds

Detailed description of the invention

The use of flow reactors is common in chemical manufacturing because they are relatively inexpensive and easy to manufacture. For example, methane, ammonia, and methanol are commonly produced catalytically in fluid-flow reactors or tubes, particularly in fixed-bed, fluidized-bed, or fluidized-bed reactors. For example, methane is produced from CO, CO ₂ and H ₂ by the Sabatier process, the same is true for methanol or ethanol, but less hydrogen is added per carbon atom, and H ₂ and N ₂ are used to produce NH ₃ by the Haber Bosch process. All the above reactions have in common that they occur on a technical scale on solid catalysts. While zinc-containing catalysts are typically used for methanol production, iron-containing catalysts are used for the Haber-Bosch process, and nickel-containing catalysts are used for the Sabatier process. The use of flow reactors is common because they are relatively inexpensive and easy to manufacture. However, the purity of the CO, CO ₂ , N ₂ and H ₂ reagents is very demanding, otherwise the catalysts used will be poisoned. Therefore, these substances must be purified in a complex way before being introduced into the respective catalytic process. This applies in particular to CO and CO ₂ if they were formed during a process in which inorganic components such as calcium, sodium, vanadium, phosphorus, sulfur or the like were present. The disadvantage of this type of reactor is also its difficult controllability and its long start-up times, ie it cannot be operated dynamically. In addition, intermediate cooling is required due to the high heat of most reactions. If this is not done, only very low selectivities can be achieved. Also, due to the catalysts used, the reactors are only designed for one specific reaction and therefore can only be used for that one reaction. The so-called pulsed compression reactors represent another possible process control. This type of reactor is generally described, for example, in US 8,691,079 B2, US 2,814,551, US 2,814,552 and in "Pulsed Compression Technology: A Breakthrough in the Production of Hydrogen", M. Glouchenkov and A. Kronberg, WHEC 16/Jun 13-16, 2006". The basic idea is that the gaseous reactants are introduced into a reaction chamber via at least one inlet valve, this gaseous mixture is then compressed via a piston and thus heated. The reaction desired is triggered by the high temperature, then the pressure and thus the temperature drop again due to the movement of the piston and the products thus produced then leave the reaction chamber via at least one outlet valve.This process is repeated periodically, comparable to that of an internal combustion engine. The difference, however, is that in internal combustion engines the emphasis is on the energy supplied and the exhaust gases are released into the atmosphere, whereas in the reacts pulsed compressors, the objective is to obtain usable products. In this way, temperatures well above a thousand Kelvin and pressures of several hundred bar can be represented for a short time without the reactor components being subjected to too high a load, since the subsequent expansion of the gas leads to a cooling of the reaction mixture and therefore a reduction in the loading of the components. In order to utilize the energy dissipated during expansion, at least two reaction chambers are usually mechanically coupled such that expansion of one reaction chamber results in compression in the second reaction chamber. This can be achieved, for example, by a free piston arrangement (US8691079B2, "Pulsed Compression Technology: A Breakthrough in the Production of Hydrogen", M. Glouchenkov and A. Kronberg, WHEC 16/Jun. 13-16, 2006) . One can also imagine a connection of two opposite pistons, rotating in opposite directions, each closing a reactor chamber (US2814551). Also, reactors based on reciprocating piston engines that operate as reformers and are used to produce syngas (Lim, Emmanuel G. et al. "The Engine Reformer: Syngas Production in an Engine for Compact Gas-to -Liquid Synthesis"). The Canadian Journal of Chemical Engineering 94.4 (2016): 623-635). However, pulsed compression reactors have not been widely used for the following reasons:

1. Sealing the reactor enclosure to the outside is essential for toxic, flammable or explosive mixtures for safety reasons. However, as dynamic seals are used on the piston, it often happens that the success is not complete, which can lead to environmental risks.

2. Due to friction losses, the work of expansion is often insufficient to provide enough energy to compress the other piston. In document US2814551, it is described that in such a case, an additional gas, generally an inert gas, is injected into the reactor chamber to increase the pressure therein. In this way, the energy supplied for compression can be increased, but additional valves and compressors are required for this. 3.

3. The process is very difficult to control, because, for example, the frequency of the piston movements and therefore the residence time depend on the energy released in the reaction and therefore on the quantity of reagent supplied.

4. The device must be started pneumatically, which requires a large number of valves and complicated wiring.

5. Often relatively high temperatures and pressures must be achieved in order to obtain activation energies high enough to start the reaction. This can be disadvantageous with regard to the selectivity of the reaction.

6. Since the onset of the reaction cannot be directly controlled, but is only triggered by pressure and temperature, the reaction may already take place before the top dead center of the piston, which has as a consequence that it is on the one hand strongly mechanically stressed and on the other hand braked. This last point may cause it to not reach top dead center at all, and the pulsating compression reactor may shut down.

The invention disclosed in claims 1 and 10 is based on the problem of presenting a method as well as an apparatus producing hydrocarbons, in particular methane and/or alcohols and/or ethers, and/or ammonia.

The method according to the invention solves these problems according to the generic term of claim 1, and the apparatus according to the invention solves these problems according to the generic term of claim 10.

According to the invention, it is intended to supply compounds containing carbon, in particular gaseous or liquid compounds, and/or nitrogen to reciprocating compression reactors or to a rotary piston reactor. If hydrogenation is to take place, hydrogen is additionally supplied to the reactor chambers. Using an electronic control system that evaluates the sensors and calculates mathematical models and controls the actuators, the operating parameters of the reactors are determined and influenced in order to optimize the yield and/or the selectivity of at least a desired product. For this, the actual values obtained by the sensors and/or the analyzers are compared with the setpoint values recorded in the electronic control unit, and the operating parameters of the reactors are modified by suitable actuators in such a way that the actual values approach the setpoint values. Furthermore, according to the invention, provision is made for the maximum yield and/or the selectivity of at least one product to be used as the set point and for independent optimization of the operating parameters of the reactors to take place in the unit. electronic control. This is particularly useful when the quality or composition of reagents supplied fluctuates, and continuous optimization of operating parameters means that reactors continue to operate within their optimum operating range. That is, the electronic control unit continually relearns itself. This relearning is a priority in the field of neural networks or artificial intelligence, so it will not be discussed further here. Unlike the prior art, in which different reactors or catalysts have to be used for different products, the process according to the invention and the associated apparatus offer the advantage that the operating parameters of the compression reactors, such as the temperature of reaction, residence time, reaction pressure, reactant composition, valve opening and closing times, can be varied over a wide range, so a wide variety of products can be produced with the same device. In reciprocating compression reactors, at least two reactor chambers are cylinder-shaped and are arranged in line. An arrangement in two rows in the form of "benches" is also possible, the two benches being arranged inclined at an angle of 40° to 120°, preferably at an angle of 42° to 90°, extremely preferably according to an angle of 45° to 60° to each other. In both cases, i.e. in-line or V-design, all the pistons moving in the cylinders act on a common shaft, specifically a crankshaft, via a connecting rod in each case. That is, the design is in principle a reciprocating piston engine. A device, for example an electric machine (E-machine), is coupled to this crankshaft, by which the shaft speed and thus the residence time in the reaction chambers can be changed: If the residence time is to be increased, the crankshaft is braked using at least one device, if the dwell time is to be reduced, the crankshaft is accelerated using the device, or the braking torque of the device is reduced. The electrical machines used are, for example, collectors, such as single-phase direct current or alternating current motors, or rotating field machines, such as three-phase asynchronous machines, three-phase synchronous machines, single-phase asynchronous motors, single-phase synchronous motors. E-machines that can be used as both a motor and a generator are preferable, since they can supply energy to the compression reactor on the one hand, but also extract it from the other, so that an operation very flexible is possible. Furthermore, the energy to be dissipated during the deceleration can be converted into electricity when the electric machine is used as a generator and feeds into the electricity grid or is made available to other electrical consumers.

If an E-machine is used as the engine, starting the device is very easy, since the crankshaft is pulled for this case. In addition, reactions can be represented here in which the energy released by the reaction is not sufficient to ensure independent operation of the device. This is particularly the case for endothermic reactions. In this case, the device is driven by the electric machine. In order to reduce the cost of an E machine, when the output power of the compression reactors is high and the associated braking power of the crankshaft is high, it is possible to combine a small E machine (for starting and to compensate peaks of short duration) and a powerful eddy current or water brake, which takes over most of the braking power. In this case, the current efficiency is naturally much lower, but then high heat fluxes are produced, which can be used as process heat. In addition to the design described above as a reciprocating piston machine, a design as a rotary piston machine can also be implemented according to the invention. To do this, the rotor, like the crankshaft, is also coupled to a device, for example an electric machine, by means of which the rotational speed of the rotor of the rotary-piston machine and therefore the residence time in the chambers of reaction can be changed. Furthermore, as we have already described above, the production of electrical energy is thus possible. According to the invention, at least one of the resulting products has a calorific value of at least 12MJ/kg, advantageously at least 20MJ/kg, extremely advantageously at least 30MJ/kg. The proportion of at least one product having a calorific value of at least 12MJ/kg in the flow of material leaving the reactor is at least 5%, advantageously at least 10%, extremely advantageously at least 20 %. The process is advantageously suitable if the sum of the volumetric calorific values of the products is greater than the sum of the volumetric calorific values of the reactants. Products include aliphatic hydrocarbons (C ₂ H ₂ , CH ₄ , etc.), aromatic hydrocarbons, alkaloids, amino acids, fats, heterocycles, NH ₃ , alcohols (CH ₃ CH ₂ OH, CH ₃ OH, etc.), HCHO, C ₂ H ₄ , ethers (dimethyl ether (DME), diethyl ether (DEE), polyoxymethylene dimethyl ether (POMDME) etc.), amines, amides, urea, CS2, thiocyanates, carbamate, acids organic (e.g. acetic acid).

To this end, one, advantageously at least two, of the following compounds or their derivatives are introduced into the chambers of the reactor: N ₂ , H ₂ , CO, CO ₂ , aldehydes, in particular HCHO, alcohols, in particular CH ₃ OH and ethanol, sulphur, NH ₃ . If oxygen is added, less oxygen is always added than would be necessary for complete oxidation of the compound, according to the invention less than 80%, advantageously less than 40%, particularly advantageously less than 20% the amount of oxygen that would be needed for complete oxidation. CH ₄ can thus be produced from CO or from CO ₂ and H ₂ according to the following equations.

_H2 + _CO2 → CO + _H2O

_3H2 + CO → _CH4 + _H2O

To increase the yield, the unconsumed H ₂ and CO/CO ₂ are separated from the resulting product stream and recycled to the reactor. The same reagents are also used to produce methanol and ethanol, respectively, but less hydrogen is added per carbon atom.

CO + 2H ₂ → CH ₃ OH

CO ₂ + 3H ₂ → CH ₃ OH + H ₂ O

2CO + _{4H2 → CH3CH2OH} + _H2O

_{2CO2 + 6H2} → _CH3CH2OH + _3H2O

N ₂ and H ₂ are used to produce ammonia.

_N2 + _3H2 → _2NH3

CO ₂ and NH ₃ are added to the reactors for the production of ammonium carbamate.

_2NH3 + _{CO2 → H2NCOONH4}

Urea can then be produced from the ammonium carbamate formed.

H ₂ NCONH ₄ → H ₂ NCONH ₂ + H ₂ O

Acetic acid can be produced from the reactants methanol and carbon monoxide. The reaction pressure is at least 30 bar, preferably at least 50 bar, preferably at least 70 bar. The reaction temperature is between 100°C and 350°C, preferably between 150°C and 300°C, preferably between 150°C and 250°C.

CH ₃ OH + CO → CH ₃ COOH.

For the production of ethyne, methane is used as a reagent, the reaction temperature is at least 1500°C, preferably at least 1700°C, preferably at least 1800°C. To achieve high selectivity, the reaction temperature is turned on by opening the outlet valve before bottom dead center, i.e. before the end of the expansion time.

_{2CH4 → 2C2H2} + _2H2

Acetaldehyde is produced over ethyne and oxygen at reaction pressures of at least 8 bars, preferably 9 bars, preferably at least 10. The reaction temperature is at most 350°C, preferably 300°C, preferably at most 250°C. To increase yield, unconsumed ethyne is separated from the resulting product stream and recycled to the reactor on the reactant side.

2C _2H4 + O2 → 2CH ₃ CHO

Additionally, acetaldehyde can also be produced from ethanol and oxygen, and recycling unused ethanol back to the reactor compartment increases yield. The separation of the acetaldehyde from the water formed and the unused ethanol is carried out by subsequent distillation.

2C ₂ H ₅ OH + O2 → 2CH ₃ CHO + H ₂ O

Ethanol can also be produced from ethene and water in the process of the invention.

_{C2H4 + H2O → C2H5OH}

The reactants for the production of other products, such as HCHO, are CO and/or CO ₂ and H ₂ , for CH ₃ OH and CH ₃ CH ₂ OH, CO and/or CO ₂ and H ₂ , for DME, CH ₃ OH, for POMDME, CH ₃ OH and HCHO, for DEE, ethanol. In order to increase the yield of the reactions described above, provision is also made, according to the invention, to withdraw a partial flow of product downstream from the compartments of the reactor and to reinject it into the compartments of the reactor. The reaction conditions in the reaction chambers for starting the reaction are advantageously at least 50 bar, advantageously at least 60 bar, advantageously at least 70 bar. The reaction temperatures at the start of the reaction are between 200°C and 500°C, preferably between 250°C and 450°C, more preferably between 280°C and 400°C. In order to obtain sufficiently high yields in reactions whose yield is negatively influenced by the presence of oxygen, the oxygen concentration at the start of the reaction is at most 1%, advantageously at most 0.5%, extremely advantageously at most 500 ppm. This makes it possible to avoid or reduce the oxidation of the products and the reduction of their calorific value.

For safety reasons, it is advisable to feed reactive or combustible reactants, such as hydrogen, ethanol, CH ₄ or methanol, directly upstream of the reactor chamber inlet, i.e. that is to say downstream of the non-combustible reactants, such as CO, CO ₂ or N ₂ , or directly in the reactor chamber via a valve independent of the inlet valve. In this case, the inlets and outlets of the reactor are advantageously closed. This direct feed is also suitable for liquid reagents. The compression ratio of piston reactors is at least 1:8, preferably at least 1:15, most preferably at least 1:20. The residence time of the reactants in the reactor chamber is at most 10s, advantageously at most 1s, extremely advantageously at most 0.1s.

The crankshaft is surrounded by a "crankcase" which is fixed to the walls of the reactor by means of screws. The seals used at the joints are static seals, which provide a much better seal to the outside than the dynamic seals of the pistons. However, these dynamic piston seals at the reactor chamber sleeve remain a critical point, as reactants can enter the motor housing through them. In conjunction with the oxygen present in the environment, this can lead to the formation of explosive mixtures, such as gaseous oxygen, and consequently to an explosion or deflagration in the crankcase. If toxic reagents or products are involved, such as formaldehyde, they can escape into the environment, which should also be avoided. According to the invention, this is avoided by rinsing the casing with non-flammable and non-toxic or slightly toxic reagents, such as N ₂ , CO and/or CO ₂ , which are then introduced into the reactor chamber. Further improvement can be obtained if the sump or the reactants and products contained therein are depleted, so that a lower pressure than in the environment is established. At least one reagent and/or flammable or toxic product is then also introduced directly upstream of the reactor compartment, or more preferably directly into the reactor compartment by a valve independent of the inlet valve, advantageously with inlets and outlets of the reactor closed. In order to increase the pressure in the reactor chamber, it is useful to supply the reactants to the reactor chamber already at an elevated pressure. In the simplest case, this can be done through compressors, but a turbocharger arrangement makes more sense from an energy point of view, especially in the case of exothermic reactions: in this case, the enthalpy is extracted from the product stream heated by a turbine, which is arranged downstream of the reactor chambers, and transferred by a shaft to a compressor on the reactant side. The reactant side pressures and thus ultimately the pressures in the reactor chamber can be varied by appropriate measures, such as reactant and/or product side relief valves, variable turbine and/or compressor geometries . The device can be designed as a two-stroke, four-stroke or four + 2*X-stroke device. The following description relates to, but is not limited to, an exemplary reactor chamber and reciprocating engine design with the crankshaft mounted below the pistons.

Two-stroke device:

1. intake and compression (piston moves up).

2. main and thrust reaction (piston moves down)

For this construction, the valves can, but must not be completely omitted, since the piston alternately closes or releases the inlet and the outlet.

Four-stroke device:

1. intake (intake open, exhaust closed, piston moves down).

2. compression (inlet and outlet closed, piston moves down)

3. main reaction and expansion (piston moves down)

4. expulsion (exhaust open, intake closed, piston moves up)

This configuration requires inlet and outlet valves on the reactor chambers. These can be driven by at least one camshaft. In the engine sector, additional devices are known for varying the opening and closing times of these valves and which are also used here, such as piezoelectric actuators, hydraulic valve controls, adjustable camshafts, etc These measurements can be used to influence the reaction conditions in the reactor chamber. For example, it is possible to open the exhaust valve after the third cycle, even before the piston has reached bottom dead center, in order to lower the pressure and therefore the temperature in the reactor chamber faster than only the movement of the piston would allow it. In this way, it is possible to freeze the reactions and avoid unwanted side reactions. In addition, the inlet valve can be opened before the top dead center of the piston is reached in the extension stroke, especially before the bottom dead center of the piston is reached, so that the products return to the reactive side. As a result, a mixture of products and reagents is aspirated on the next aspiration, increasing product yield. A similar effect is obtained if the outlet valve remains open during the suction cycle, so that the products are sucked back into the reactor chamber.

Four-stroke device + 2*X:

It is an evolution of the four-stroke device. In order to increase the yield, the outlet valve is not opened in the fourth cycle, but at least one more compression and reaction cycle is connected.

1. intake (intake open, exhaust closed, piston moves down)

2. compression 1 (inlet and outlet closed, piston moves up)

3. main reaction 1 and expansion 1 (piston moves down)

4. compression 2 (piston moves up)

5. main reaction 2 and expansion 2 (piston moves down)

repeat the main compression and reaction cycle x times

6 +2*x: expansion (outlet open, inlet closed, piston moves up)

x is an element of the natural numbers, so it results in sum cycle numbers of 6, 8, 10, etc. It is often useful to add at least one reagent for the second main reaction. This can be done, for example, by opening the inlet valve or by directly adding at least one other reagent via an additional feed device into the reactor chamber. On the one hand, it is possible to feed one of the reactants which has already been fed into the first main reaction, which can, on the other hand, increase the yield and/or the selectivity. However, it is also possible to feed at least one reactant different from those of the first main reaction, which makes it possible to selectively produce a product different from that of the main reaction. The addition can be carried out, for example, by opening the inlet valve and sucking it into the reactor chamber or by directly adding at least one reactant via an additional feed device into the reactor chamber. Regardless of the number of cycles, the yield can be further increased by taking a partial stream of product downstream of the reactor chamber and returning it to the reactor chamber, especially from the inlet side, that is i.e. on the reactant side. The amount of product recycled in this way can be varied by means of suitable actuators, such as valves and/or blowers. This is particularly useful for equilibrium reactions and/or reactions with increasing volume, since the equilibrium can thus be shifted towards the product side. Another way to increase yield is to separate unconsumed reactants from the product stream and return them to the reactors.

The reaction can also be influenced by the temperature of the reactants introduced into the reactor chamber. For example, the yield of endothermic reactions or reactions with increased volume can be increased if the temperature of the reactants is raised before they enter the reaction chamber. This temperature increase can be achieved in an energy-efficient manner by thermally coupling the reactant flow to the product flow downstream of the reactor chambers and/or to the compression reactor coolant. Coolant is necessary to prevent overheating of the device. Also, for exothermic reactions, such as the production of methane from CO or CO ₂ and H ₂ , or the production of ammonia from N ₂ and H ₂ , cooling the reactants is useful. Since, as described above, the start of the reaction often cannot be triggered in a definite way solely by the pressures and temperatures prevailing in the reactor chambers and/or the temperatures would have to be increased to such an extent that it would a negative effect on the selectivity, according to the invention, additional energy is supplied to the reactor chamber in the short term in addition to the compression energy in order to exceed the activation energy and thus start the reaction. This can be done via at least one of the following methods or devices: Electric spark (including via a spark plug), corona discharge, microwave, and laser pulse.

To further increase the energy input into the reactor compartment, it is possible to use a separate small ignition reactor compartment, which is connected to the main reactor compartment via openings. In this chamber, a different gas composition is generally chosen from that of the main chamber of the reactor. Thus, for example, a flammable gas mixture containing oxygen can be supplied there, while the main chamber of the reactor contains no oxygen or at least much less oxygen. The gas mixture contained in the chamber of the ignition reactor is then ignited, for example by a spark plug. The resulting pressure wave and flame front migrate through openings into the main reactor chamber and initiate the main reaction there. In order to increase the process yield, the product or gas composition is measured downstream of the reactor chamber and the corresponding process parameters are regulated by an electronic control unit: The crankshaft speed is lowered, the reactant is increased (for reactions with volume reduction), reactant pressure is lowered (for reactions with volume increase), the amount of product returned to the reactant side is increased, the inlet valve is opened before the outlet valve is opened, causing the products to flow to the reactant side, the energy supplied to the reactor is increased (e.g. by increasing the ignition voltage), the number of cycles is increased, by especially above four. If the selectivity is too low, it is possible, among other things It is possible to increase the speed of the crankshaft, to reduce the number of cycles until ejection, to reduce the pressure of the reactant, to reduce the quantity of product returned to the reactant side, to close the inlet valve in the intake cycle before reaching bottom dead center, to open the outlet and/or inlet valve in the expansion cycle before reaching the bottom dead centre, to cycle the energy supplied to the reactor and/or to reduce the individual energy (for example, several laser pulses or ignition sparks).

If H ₂ is necessary for the reaction, it can be produced for example by electrolysis. In order to increase energy efficiency, it is advisable to use high temperature electrolysis, the thermal energy necessary for the operation of the electrolyser being at least partially supplied by thermal coupling to the flow of hot products. To do this, the water is evaporated using the hot product stream and fed to the electrolyser at at least 600°C, preferably at least 650°C, extremely preferably at least 700°C . If the thermal energy of the product flow is not sufficient, the water vapor can be thermally coupled to the flow of H ₂ and/or O2 leaving the electrolyser. In addition, additional heating is possible.

A reduction in investment costs on the side of the hydrogen electrolyzer can be achieved if CO and H ₂ O are introduced into the reaction chamber so that a water gas shift reaction occurs

CO + H ₂ O <----> CO ₂ + H ₂

According to the invention, this process makes it possible, for example, to reduce by approximately 1/3 the quantity of H ₂ to be produced by electrolysis during the methanization of CO or CO ₂ . In this process, the necessary hydrogen can already be added in parallel to the water. In order to increase the yield, however, it is advisable to add the hydrogen afterwards. The 4-stroke + x- operation is particularly advantageous here, i.e. the hydrogen is only added for the second or one of the following reactions, because in this way a separation of the reaction can be ensured. water-gas displacement and methanization. Another possibility is to spatially separate the water-gas shift reaction and the methanation, i.e. to let them take place in two different reactor compartments: The water-gas shift reaction takes place in a first reactor, the CO ₂ and H ₂ which are produced there as well as the necessary additional hydrogen are then routed to the second reactor in which the methanisation takes place. The main advantage of this process, i.e. the separation of the different reactions in the different reactors, is that one can set different reaction conditions in the different reactors through different process parameters, such as reactant temperatures, compressions, reactor pressures, valve actuation times (for inlet and/or outlet valves), times of additional activation energy delivered, and reactant pressures. Additionally, unwanted reactants and products can be separated from the first reactors between reactors, so that only the reactants desired for that reaction are fed to the second reactors. This method is particularly useful in the case of a V-shaped arrangement of the reactor compartments: the water gas displacement reaction can take place on one bench, for example, and the methanation on the other. Unused water can be separated between the two banks. Of course, the described process is not limited to the water and gas displacement reaction, but can be used for all reactions in which the end product is formed via intermediates.

This great flexibility in controlling the reactions clearly distinguishes the process according to the invention and the apparatus according to the invention from the prior art: unlike the reaction systems based on the catalyst, which can only be used for a very specific due to the catalyst used in each case, the process parameters as well as the reactants can be varied within a very wide range according to the invention, which allows the preparation of a wide variety of products from a wide variety of reagents. The selection of the desired product and/or the regulation of the process takes place, as already explained, with the aid of an electronic control unit.

For example, a first mode can produce methane from H ₂ and CO ₂ ,

_4H2 + _CO2 → _CH4 + _2H2O

in another mode, methanol

CO ₂ + 3H ₂ → CH ₃ OH + H ₂ O

and in yet another mode, dimethyl ether (DME).

2CH ₃ OH → CH ₃ -O-CH ₃ + H ₂ O

can be produced. Here, as described above, the different reactor chambers can be operated in the same mode or under different reaction modes or conditions. The different modes differ in the simplest case with respect to reaction conditions, but may also differ with respect to reactants.

According to the invention, the switching between the different modes as well as the control and regulation take place with the aid of an electronic control unit. At least one of the following variables serves as control variables for the control: Target product composition, Actual product composition, Target pressure curve in the reactor chamber, Actual pressure curve in the reactor chamber, Maximum target pressure in the reactor chamber, maximum actual pressure in reactor chamber, target pressure rise in reactor chamber, actual residence time in reactor chamber, target reactant pressure, target reactant temperature, target product temperature, composition of reactant set point, actual pressure rise in the reactor space, actual crankshaft or rotor rotational speed, set residence time in the reactor space, actual reactant pressure, actual reactant temperature, actual temperature of the product, actual composition of the reactant, set speed of rotation of the crankshaft or rotor, set residence time in the space of the reactant ur. At least one of the following variables, which can be adjusted by corresponding actuators, serve as manipulated variables: Product quantities delivered, product cooler power, product heater power, product pressure regulator, machine E, crankshaft or rotor speed, energy supplied/discharged by machine E, valve opening times (inlet valves, outlet valves), valve closing times (inlet valves, outlet valves) outlet), quantity of recirculated product, variation of the compression rate, variable geometry of the turbine, variable geometry of the compressor, quantity of product bypassed by the turbine, quantity of educt discharged towards the compressor, position of the throttle valve on the side of the reagent, position of the back pressure valve on the product side, activation time of the additional energy supplied by a spark plug, laser, microwaves or corona discharge, number of activations of the 'in additional energy provided by spark plug, laser, microwave or corona discharge per duty cycle, time and number of reactant feeds directly into reactor chamber with inlet and outlet valves closed . One way to further increase yield and selectivity is to provide downstream of the reactor compartments at least one catalyst suitable for the particular reaction. Since most of the reaction has already taken place in the compression reactors, it can be made much smaller than usual. Taking the example of the production of methane from H ₂ and CO ₂ and/or CO, a methanation catalyst must be installed downstream of the reactor chambers. Nickel, ruthenium, aluminum, cobalt or cerium can be used as active components. In the case of the production of NH ₃ from H ₂ and N ₂ , however, iron-based catalysts are used. If a turbine is located downstream of the reactors, the catalysts are advantageously located upstream of this turbine, since they are there at a higher pressure level.

Another advantage of the method and of the apparatus according to the invention is that the Die compression reactors can also be used as compressors to compress at least one product during manufacture: To do this, the piston does not just expel the products in the expulsion cycle, but transports them to a storage tank and/or a downstream process, in particular a process operating under pressure. That is to say that the products are both transported and compressed by the compression reactors in the ejection stroke, the compression reactors here functioning as piston compressors. In the best case, an additional compressor or blower can be dispensed with to transport and compress at least one product, or at least can be designed so that they are significantly smaller. In exothermic reactions, the energy needed for this purpose is provided by the chemical reaction, so no conversion to another form of energy, such as electrical energy, is necessary, so the yield is significantly higher than separately operated chemical flow or fixed bed reactors and compressors. If the energy of the reaction is not enough, the transport of the products or their compression can be carried out with the help of mechanical energy, which is transmitted to the crankshaft by the electric machine.

In the following, the apparatus according to the invention and the method will be explained with reference to figures.

There shows the apparatus according to the invention. The different reactor chambers (1) are arranged in series and housed in a common housing. Together they form a reciprocating motor (2). Via a shaft (5), the compression energy supplied by the reactors or to be supplied to them is transmitted to or from an electronic machine (4). The reactants (6) and (7) are introduced into the reactors, and the products (8) are discharged from the chambers of the reactor (1) and collected in a container (3). To prevent the device from overheating, it is cooled with a suitable cooling medium, such as water (not shown). In the event of formation of several products and/or incomplete conversion of the reactants, separation of the different products or separation of the reactants, e.g. by membrane processes, gas washing, extraction, rectification, adsorption , the condensation, is arranged downstream of the device (not shown here).

This becomes relevant, for example, when gases are introduced in the form of educts, which result from an oxidation reaction with air, as they do, for example, during the combustion of hydrocarbons. In this case, on the one hand CO and CO ₂ are formed, but on the other hand large quantities of N ₂ are contained which do not participate in the combustion. If this mixture is introduced into the reaction chamber with H ₂ , hydrocarbons are formed, such as methane, but also water and NH ₃ . This NH ₃ can be easily absorbed in the water supplying a countercurrent or cocurrent column at temperatures below 30°, preferably below 20°C, and extremely preferably below 15°C. This water is then evacuated and heated to expel the NH ₃ again, which "regenerates" the water so that it can once again absorb the NH ₃ . It is then cooled and returned to the product stream to absorb more NH ₃ . As the water produced in the reaction is also separated from the hydrocarbons in this way, it is removed, otherwise the amount of water transported in the loop would increase. The amount of heat required to desorb the ammonia can be applied by thermally coupling the desorption to the product stream upstream of the scrubber and/or to the reactor coolant. The apparatus can be used to produce methane as product (8) by adding CO ₂ and/or CO as reactants and H ₂ as reactants. For safety reasons, it is useful to purge the housing (32) as shown in Figures 3a,b,c with a non-flammable and non-toxic reagent, in this case CO ₂ (see below). Additionally, the production of ammonia is possible using nitrogen and hydrogen as reactants. In this case, it makes sense to purge the housing (32) with nitrogen. The simultaneous production of NH ₃ and CH ₄ is also possible, as already described above, by supplying the reactors with CO ₂ and/or CO as well as with H ₂ and nitrogen. The apparatus and method according to the invention are not limited to these compounds, but can be used in all reactions in which no solid reaction product is formed, in particular no abrasive reaction product. These include, as already described above, NH ₃ , HCHO, CS2, thiocyanates (including ammonium thiocyanate), dimethyl ether (DME), diethyl ether (DEE), CH ₄ , POMDME, alcohols (methanol, ethanol), ammonium carbamate, urea, acetaldehyde, acetic acid.

In the , a reactor according to the invention is shown according to the principle of four cycles or of four+2*X-cycles: At least two reagents (6, 7) are introduced into the reactor chamber (1) by at least one valve d admission (33). The reactants are sucked and compressed by a piston (34), which is connected to the crankshaft (37) by a connecting rod (35) and which moves up and down in a sleeve, then the products (8) are expelled. Reagents can be introduced into the reactor together via the inlet valve as shown in the . Especially in the case of reactive and explosive substances, such as H2, a direct feed into the reactor chamber, especially with closed reactor inlets and outlets, or at least an addition directly upstream of the inlet valve is advisable for security reasons (not shown here). Compression causes an increase in temperature and pressure, which causes the desired reaction. The onset of the reaction can also be triggered, or precisely controlled or regulated, by the addition of additional energy, for example in the form of a spark plug, a laser pulse, a corona discharge or microwave radiation (not shown here). To prevent leakage of reagents and products into the environment, the piston and the crankshaft are surrounded by a casing (32) which is sealed with respect to the environment by means of gaskets (36). In order to prevent large quantities of reagents and products from entering the housing beyond the piston, the latter is isolated from the sleeve in which it moves up and down by means of dynamic seals (39). Since it is nevertheless inevitable that reagents and products enter the housing (32), in the event of the presence of explosive or corrosive substances, provision is made, according to the invention, for the housing (32) to be rinsed with a reagent non-corrosive, non-flammable or non-explosive and that this reactant is then introduced into the reactor chamber (1) (not shown). The inlet and/or outlet valve(s) can be controlled by camshafts, hydraulically or piezoelectrically. The last two variants are particularly to be preferred, if one wants to represent a precise control of the reaction conditions and/or four+2*X- cycles, because the opening times of the valve can be chosen freely.

According to the method of the invention, the control and the regulation are carried out using an electronic control unit. As input variables for the control, at least one of the following variables is used: the composition of the product, the pressure curve in the reactor chamber, the maximum pressure in the reactor chamber, the pressure increase in the reactor chamber, crankshaft speed, residence time in reactor chamber, reactant pressure, reactant temperature, product temperature, reactant composition, reactant amount. Actuators or manipulated variables are at least one of the following: Fluid quantity, fluid cooler output, fluid heater output, fluid pressure controller, E-motor speed, crankshaft speed , energy supplied/discharged from the engine E, valve opening time (intake valves, outlet valves,), quantity of recycled product, variation of the compression ratio, variable geometry of the turbine, variable geometry of the compressor, quantity by-pass of the turbine, amount of product discharged after the compressor, position of the throttle valve on the product side, position of the back pressure valve on the product side, activation time of the additional energy supplied by spark plug, laser, microwave or corona discharge, number of activations of additional energy provided by spark plug, laser, microwave or corona discharge per duty cycle , time and number of foods tations of the reactant supplied directly into the reactor chamber with the inlet and outlet valves closed.

In particular, the pressure curve, the peak pressure and the pressure rise gradient in the reactor chambers were found to be important process variables. These variables can be determined using pressure sensors fluidically connected to the respective reactor chamber and the corresponding evaluation in the electronic control unit. In addition to their influence on the conversion to selectivity, these variables are also important to avoid the mechanical overload of the compression reactors. In order to avoid overloading, their values are limited using the electronic control unit. This is achieved in particular by reducing the quantities of reagent supplied and/or by lowering the temperatures and/or the pressures of the reagents and/or the compression ratio and/or by increasing the quantity of recycled product on the side of the reagents and/or by shifting the activation energy additionally provided by the spark plugs, for example, to later times. In this context, it is particularly important that the reaction is uncontrolled, very fast and early, especially if it occurs well before top dead center. These uncontrolled reactions can lead to detonations in the reactor chamber, which places a very high mechanical and thermal load on the components of compression reactors. In addition to the determination of this state by means of the pressure sensors described above, which are connected to the respective reactor chamber, it is also possible to determine uncontrolled reactions, such as impact, by means of noise sensors of structure, in particular using piezoelectric longitudinal elements, and acceleration sensors which are arranged outside the reactor chambers on the device according to the invention. Their signals are evaluated in an electronic control unit and compared with expected values. If an uncontrolled reaction is detected, the countermeasures already described above can be triggered via the electronic control unit.

In addition to preventing mechanical damage due to excessive pressures in the reactors or too large pressure gradients, the pressure and/or structure-borne noise and/or acceleration sensors described above can also be used to detect too slow a reaction or no reaction at all. In this case, the yield would drastically decrease and a large amount of unreacted reactants would reach the product side. In this case, the electronic control unit would increase the temperatures and/or the pressures and/or the compression ratio of the delivered product and/or the reactant and/or reduce the amount of product returned to the reactant side and/or reduce the additional activation energy provided by spark plugs, for example. for example, and/or the addition of reagent introduced directly into the reactor space with the inlet and outlet valves closed is shifted to earlier times and/or the number of activation events additionally provided, such as electric sparks, and/or the number of reactant additions made directly to the reactor space and/or the amount of additionally supplied activation energy is increased.

The problem of the reaction being too slow or the total absence of reaction arises in particular at the beginning of the compression reactors, because their components in contact with the reactor, and in particular the reactor chambers, are still cold at this time. there. This can lead to target reaction temperatures not being reached. To avoid this, when starting the compression reactors, it is provided, according to the invention, that they are operated in a dragging manner before all the reactants are introduced into the reactor chambers. As described above, this is achieved in the simplest case by means of an electric machine coupled to the crankshaft of reciprocating compression reactors. In addition, according to the invention, provision is made to preheat the cooling liquid and/or the lubricant of the reciprocating compression reactors before start-up. Further, until the desired operating temperature or product composition is reached, a valve located downstream of the reactor chambers and downstream of the product return line to the side of the line is closed and the line return of the products to the entrance, that is to say the side of the pipe, is open. Due to friction and the resulting frictional heat, the temperature in the reactor chambers increases, and the return of heated fluids to the inlet side further increases this effect. Independently or in addition to this, not all the reagents necessary for the desired reaction are added, but rather preferably inert substances, in particular reagents such as N ₂ or CO ₂ . This is particularly useful when explosive reagents are added in the reaction itself, as it helps flush the reactor spaces and remove any oxygen that may have entered during shutdown. It is particularly advantageous to add gases with a positive Joule-Tomson coefficient to the reactor compartments before the operating temperature is reached, because these gases increase the temperature by compression in the reactor compartments, which heats up the reactor compartments. reactor. The addition of gas with a negative Joule-Thomson coefficient, such as hydrogen, is suppressed during this operating phase. In addition, preheating of the reagents is possible. If the electronic control unit determines a temperature high enough for the reaction, it switches from heating mode to actual standard operation to produce the desired products. That is, all reactants are now added, the valve downstream of the reactor is opened, and the amount of product or reactants returned to the reactant side is adjusted to the desired product composition.

Crankcase bleeding is shown for a two-stroke unit in the , b, c, but is not limited to the latter: according to the invention, in the first stage ( ), the non-corrosive, non-flammable or non-explosive reagent (7) is introduced into the housing (32) via a valve or a valve. This flows along the piston into the reactor chamber (1). At least the second reactant (6) is added to the reactor chamber (1) or directly in front of it (not shown here). The upward movement of the piston compresses the reactants ( ) and triggers the reaction. It can be enhanced, or precisely controlled or regulated, by using an additional energy supply device (42), such as a spark plug, laser pulse, corona discharge, or micro radiation. -waves. In the next ejection step ( ), the products (8) are ejected from the reactor. Energy input in addition to compression energy and separate reactant input into the reaction chamber is not limited to two-cycle devices, but can also be used with four- and four+2 devices *X-cycles.

There shows a modification of the layout chosen in the to increase yield and/or selectivity. Here, a product stream is taken downstream of the reactors and this partial product stream (52) is added to the reactors (1) together with the reactants (6, 7). It can be transported by a suitable transport device (51), such as a compressor or a blower. It is also possible to control this flow of recycled products using appropriate control devices, such as valves or check valves (not illustrated). In order to further increase the yield or the selectivity, it may be useful to selectively eject the products (8a) from this stream via a separation device (53). In particular, if the product stream (8) still contains high quantities of reactants or undesirable intermediate or final products. For example, in the production of methane using CO and/or CO2 as well as H2, it is the water that is rejected from the cycle. Additionally, CH4 can be discarded so that only unused reactants and unwanted byproducts are recycled. When the compression reactors are put into operation, it is provided, according to the invention, that the valve (88) and possibly the valve (88a) are closed or at least that the flow passing through them is throttled, so that the amount of recycled product partial stream (52) is increased to heat up the compression reactors as described above.

There shows a similar design, but here the separator (53) is located in the main product flow, so that product separation is implemented for the entire product flow.

There shows a variant allowing the pressure of the reactant to be increased via a compressor (71). The compressed reagent (7) is then routed to the reactors. The second reactant (6) at least can be added to the reactant (7) upstream of the compressor (not shown), or added directly upstream of the reactors, or even added directly to the reactors by a valve independent of the inlet valve. The compressor (71) is connected by a shaft (73) to a turbine (72), by which the product flow (8) is expanded from a high pressure to a lower pressure. The energy released in this process is therefore largely used again to compress the reactants, which increases the efficiency of the process. The pressure of the reactant and thus the pressure in the reactor chambers can be varied by suitable devices, such as the blowing of the reactant from the high pressure side to the low pressure side of the compressor via a suitable control element (75) (compressor bypass ), blowing product from the high pressure side to the low pressure side of the turbine via a suitable control element (76) (turbine bypass), variable turbine geometry and/or variable compressor geometry. Additionally, to further increase the pressure, the compressor can be electrically driven and/or another compressor can be placed in the reactant stream. Furthermore, it is advantageous in this variant if the system design is such that the pressure on the discharge side is lower than that on the product side, since this allows the product which is returned to the discharge side ( 52) to flow to the exhaust side without transportation devices, such as compressors, blowers or pumps. The quantity can thus be varied or controlled by means of a variable throttle device (74) and an electronic control unit. According to the invention, provision is made for at least the temperature of a reactant or of the recycled product in the reactor to be controlled or regulated by means of an electronic control unit and coolers or heaters.

Figures 7 and 8 show a series connection of a plurality of reactors (1) and (1a). Here, the reactors (1) and (1a) may differ in their geometry, such as piston geometry, diameter and/or stroke, or in their operating parameters, such as temperature, pressure and/or energy additional provided. Thus, it is possible to treat an intermediate product (8b) which leaves the first reactors (1) with modified reaction conditions, to lead to the final product (8). Between the two reactors, another reactant (81) can be supplied and/or an intermediate product (8c) can be evacuated.

For example, methanol can be produced from CO ₂ and H ₂ in the first reactors (1),

CO ₂ + 3H ₂ → CH ₃ OH + H ₂ O

while in the second reactors (1a), dimethyl ether (DME) can be formed from methanol (8b) with removal of H ₂ O.

2CH ₃ OH → CH ₃ -O-CH ₃ + H ₂ O

Between the two reactors, an intermediate, in this case H ₂ O, is removed from the first reaction (8c). This shifts the balance to the DME side. This can be further improved if the water formed in the second reactor is removed from the product stream (8a) and this anhydrous product stream (52) is recycled to the reactor compartments (1a) ( ).

Another example of this process control is the production of hydrogen from methane. In a first reactor chamber, steam reforming takes place.

CH ₄ + H ₂ O → CO + 3H ₂

The resulting CO/H ₂ - mixture is then routed to the second reactor with the addition of water (81), where additional hydrogen is produced by the water-to-gas conversion reaction.

CO + H ₂ O ←→ CO ₂ +H ₂

The water gas shift reaction can be enhanced by removing the CO ₂ formed in the second reactor from the product stream and returning this product stream without CO ₂ (52) to the reactor compartments (1a) and/or or by discharging hydrogen (8c) between the reactors (1) and (1a) ( ).

The two rows of reactors can be constructed as separate independent units, i.e. separate piston machines, in the event that different residence times are to be achieved in the two rows of reactors. However, according to the invention, it is also possible to arrange the two rows such that their pistons act on a common crankshaft (37) via the connecting rods (35). This is particularly useful if the residence times in the two rows of reactors must be identical. For this, the two rows are arranged in a V with respect to each other, the angle of the two legs being marked "a" on the .

There shows a variant and a method of the apparatus shown in . In addition to the components already described in the , a device (90) for separating water (96) into hydrogen (93) and oxygen (9a) using electrical energy is also presented. This splitting of water is illustrated using an electrolyzer, although a high temperature electrolyzer can be used to improve yields. To increase efficiency, it can be thermally coupled to product flow (8) and/or reciprocating machine cooling (2) (not shown here). The water (96) required for this electrolyser can be provided by an external source. It is also possible to use the water formed as a product in the reactor chambers. In the case where the reactors drive an electrical machine functioning as a generator, the electrical energy thus produced can be supplied to the electrolyser to improve the overall efficiency.

The process according to the invention is described below using the example of a process for the production of CH ₄ -. The hydrogen (93) leaving the electrolyser is routed to the reactor chambers (1) with CO and/or CO ₂ (6), which allows the formation of CH ₄ and H ₂ O which leave the reactors (8). Then, the water is separated from the CH ₄ (not represented here) and at least the CH ₄ formed is collected. The oxygen (9a) formed by the electrolysis can be collected in a tank (91) and then be used for other processes (not shown here). The CO or CO ₂ necessary for the reaction can be obtained by the combustion of carbon, in particular compounds containing hydrocarbons. Ammonia can be produced in the same way as methane, but instead of carbon monoxide or carbon dioxide, nitrogen (6) is introduced into the reaction spaces with hydrogen (93). The parallel formation of methane and ammonia is also possible if the reactor compartments are supplied with both nitrogen and CO and/or CO ₂ as well as hydrogen. Downstream of the reactor compartments, ammonia is separated by absorption, adsorption or membrane processes. This parallel production of ammonia and methane illustrates the major difference between catalytic flow or fixed-bed reactors and the process according to the invention: Unlike flow and fixed-bed reactors, in which the two substances must be produced on two different catalysts with separate reactant feeds and therefore in two separate installations or stages, according to the process of the invention, this is carried out without catalyst and in a single apparatus. This significantly reduces space and installation costs. In all three cases, the oxygen content in the reactor chambers must be minimized at the start of the reaction in order to obtain high selectivities for the desired products methane and ammonia. The hydrogen (93) produced during the electrolysis can be temporarily stored in a tank (92).

In the , the control of the process according to the invention by means of an electronic control unit is illustrated using the example of the control of the crankshaft speed and thus of the residence time. Typically, this control unit evaluates corresponding sensors to determine reactant and product states, such as temperature, pressure, and flow sensors as well as structural noise, acceleration, or velocity sensors of the e-machine or crankshaft, in order to represent a closed control loop. In addition, the pressure curve and/or the rate of pressure increase and/or the maximum pressure in the reaction chambers can be detected by the control unit using pressure sensors. According to the invention, it is further envisaged to determine the composition of the product also by means of corresponding sensors, such as NH3, CO2, CO, CH4- sensors and/or by means of analyzers, such as phase chromatographs gas, IR, UV, FID, FTIR analyzers and/or mass spectrometers. If the yield thus determined is too low, the speed is lowered to increase the retention time. If, on the other hand, the selectivity is too low, the speed is increased and therefore the residence time is reduced.

As described above, other process parameters, such as amount of recycled product, reactant pressures, reactant temperatures, product temperatures, product pressures, varying compression ratios, timing additional activation energy is supplied, amount of additional activation energy supplied, number of additional activation energy supplied per cycle, amounts of reactants, when valves are set (for valves inlet and/or outlet), when the reactant is supplied directly to the reactor chamber, the number of cycles, the crankshaft speed, the speed of the electronic machine, the temperature of the recycled product, etc. (not shown here), in order to influence the reaction to the desired extent using the electronic control unit and suitable actuators.

There shows an apparatus according to the invention, which can be used in at least two different modes for the production of different products, and the associated process. The different reactor chambers (1) are arranged in series and housed in a common housing. Together they form a reciprocating motor (2). Via a shaft (5), the compression energy supplied by the reactors or to be supplied to them is transmitted to or from an electronic machine (4). Initially, the reagents (9) and (19) are brought to it by the open valves (13) and (14) and are evacuated from a container (10) by the valve (15). Valves (11), (12), (17), (16) are closed in this mode. In the second mode, the valves (13), (14) and (15) are closed and the valves (11), (12) and (16) are open. Thus, the reactants (6) and (7) are introduced into the reactors, and the products (8) are evacuated from the reactors (1) and collected in a second tank (3). To prevent the device from overheating, it is cooled with a suitable cooling agent, such as water. When several products are formed, a separation of the different products is arranged downstream of the apparatus, for example by membrane processes, gas scrubbing, extraction, rectification, adsorption, condensation (not represented here ).

This becomes relevant, for example, when gases are introduced as reactants resulting from an oxidation reaction with air, as occurs during the combustion of hydrocarbons in mode one. In this case, on the one hand CO and CO ₂ are formed, but on the other hand large quantities of N ₂ are also present, which do not participate in the combustion. If this mixture is introduced into the reaction chamber with H ₂ , hydrocarbons are formed, such as methane, but also water and NH ₃ . The separation of NH ₃ is state-of-the-art, so it will not be discussed further here. By way of example, a separation using water is described above, but the separation is not limited to this process. There also shows another possible incarnation according to the invention: In the first mode, at least part of the flow of products is stored in a container (10). The product is transported and compressed by the compression reactors, which operate as reciprocating compressors in the discharge cycle. The other components of the product, on the other hand, are released into the environment or into another container (not shown). The separation of gases and fluids being a prior art, reference is hereby made to these methods. In mode two, valve (17) is open and thus the mode one product is fed to the reactor as reactant in mode two. The control of the corresponding valves and the regulation of the entire illustrated process is carried out by an electronic control unit (not illustrated here).

Claims (10)

Process for the preparation of hydrocarbons, in particular aliphatic hydrocarbons and/or alcohols and/or ethers, and/or NH ₃ , characterized in that the necessary reagents are supplied to at least one rotary piston reactor or to at least two pulsating reciprocating piston compression reactors (1, 1a) mechanically coupled by a shaft (37), and the rotary piston or the shaft (37) of the reciprocating piston compression reactors is connected to an electric machine (4), and the actual values are determined by means of sensors and/or mathematical models using an electronic control unit and are compared with the set values stored in the electronic control unit, and the electronic control unit adjusts these setpoint values by modifying at least one, advantageously at least two, extremely advantageously at least three operating parameters, at least one operating parameter being the residence time of the reactants in the space of the reactor (1, 1a). Method according to Claim 1, characterized in that the reciprocating piston reactors are designed as two-stroke machines or four-stroke machines or four+2*X machines, where in the four+2*X operation , the third stroke of a four-stroke machine is followed by x number of compression and expansion cycles before the products are pushed out of the reaction space, where x is an element of the natural numbers. Process according to any one of claims 1 to 2, characterized in that at least one of the resulting products has a calorific value of at least 12MJ/kg, preferably at least 20MJ/kg, most preferably at less than 30MJ/kg. Process according to any one of Claims 1 to 3, characterized in that the pressure of the reactant upstream of the reactor chamber (1) is raised by means of a compressor (71) connected by a shaft (73) to a turbine (72) driven by the product flow (8). Process according to any one of Claims 1 to 4, characterized in that, downstream of the reaction chamber (1), a partial flow of product or at least one product or at least one reactant is withdrawn from the total flow and returned (52) to the reaction chamber. Method according to one of Claims 1 to 5, characterized in that additional energy, in particular in the form of electrical sparks, laser pulses or microwaves, is supplied to the reaction chamber (1, 1a) in the case of closed reactor inlets and outlets (in the case of four and four+2*X- devices: 33, 38) independently of the compression energy. Process according to one of Claims 1 to 6, characterized in that the hydrogen (93) and the oxygen (9a) are produced by the separation of water (96) using an electrolyser, the the hydrogen formed being fed into the spaces of the reactor. Method according to one of Claims 1 to 7, characterized in that at least two reactor spaces (1, 1a) are fluidly arranged one behind the other, so that at least one product of the first reactor space reactor (1) serves as a reactant for the at least second reactor space (1a). Process according to Claim 8, characterized in that at least one additional reagent (81) is introduced between the reactors (1) and (1a) and/or at least one product (8c) formed in the reactor chamber (1) is evacuated. Apparatus for carrying out the process described in claims 1 to 9.