Method of production of synthesis-gas and plant for realization of this method

FIELD: technology of processing hydrocarbon materials, production of synthesis-gas in particular.

SUBSTANCE: proposed method is carried out in plant including multi-cylinder four-stroke or two-piston air-injection internal combustion engine working in mode of chemical compression reactor. Proposed method consists in preparation of mixture containing hydrocarbon material, water vapor and oxygen-enriched air -fuel charge at excess-air-oxidizer coefficient of 0.3-0.58 for methane followed by preheating of fuel charge and delivery of it to engine cylinders; then additional heating is performed in compression stroke followed by ignition in top dead center due to self-ignition of additives introduced into fuel charge in form of liquid or gaseous agents whose ignition temperature is below that of fuel charge; as a result, engine is started as chemical compression reactor and partial oxidation of fuel in volume of internal combustion cylinders is performed; then, products formed during reverse stroke of piston are expanded and cooled and products of this process containing synthesis-gas are discharged to bottom dead center, after which they are cooled and cleaned from soot and are subjected to final cooling and conversion into methanol or dimethyl ether. Process of partial oxidation at attaining the working mode of operation by chemical reactor is maintained due to availability of residual gases in cylinders whose amount is controlled by re-adjusting of the valve gear, additional heating due to warming-up of engine and external control of fuel charge heating temperature. Proposed plant includes multi-cylinder four-stroke or two-piston two-stroke air-injection internal combustion engine working as chemical compression reactor; engine is provided with intake and exhaust valves and system for delivery of air, hydrocarbon material and additives, as well as heating and preheating systems including air heaters, heat exchangers and mixer; engine is also provided with synthesis-gas cooling system which also consists of heat exchanger and cooler; engine is provided with reversible motor-generator set generating the electric power for multi-stage synthesis-gas compressor and high-temperature filter rigidly connected with engine and used for cleaning the synthesis-gas from soot; engine is provided with cooler and drip pan. Working of engine in mode of chemical compression reactor and composition of synthesis-gas are controlled through control of oxidizer-excess coefficient and preheating temperature in heat exchanger at steady state conditions or temperature at starting air heater outlet. Invention makes it possible to increase specified productivity by 2.5-3 times at volume ratio of H2/CO of 1.4:2.

EFFECT: enhanced efficiency of production of methanol and synthetic motor fuels.

2 cl, 1 dwg, 1 tbl

 

The invention relates to chemical technology and specifically relates to the processing of hydrocarbon raw materials, in particular the production of synthesis gas from gaseous hydrocarbons, followed by his conversion to methanol or dimethyl ether.

A known method for production of synthesis gas from a hydrocarbon feedstock, comprising mixing the feedstock with an oxidant, oxygen or oxygen-containing gas or steam, the introduction of the mixture into the reaction zone at a temperature which is not less than 93°below the point of ignition of the mixture, the speed of turbulent flow in excess of the rate of leakage of flame, and the conversion of the mixture in the presence of a solid catalyst (SU 1831468, publ. 30.07.1993).

The described method requires the creation of a catalytic reactor special design and use of highly selective catalyst.

A method of obtaining a synthesis gas comprising a combustion mixture of hydrocarbons with air, oxygen-enriched, when α=0.5 to 0.8, or unenriched oxygen when α=0,827-1.2 and explosive partial oxidation of hydrocarbons in the volume of the cylinder of the internal combustion engine, the expansion and cooling of the products of the process when the movement of the piston to the bottom dead point, the output products of the process containing synthesis gas from the reaction of objimpl movement of the piston to the top dead point, the introduction of a new portion of the working mixture in the movement of the piston to the bottom dead point. The hydrocarbons used rich gas coke oven plants, containing primarily carbon monoxide, methane and ethylene fraction. In the cylinders of the internal combustion engine serves a mixture of air with the specified raw materials, and explosive partial oxidation is preceded by forced ignition of the mixture. The specific productivity of the process, the hydrocarbon feedstock is about 700 kg/m3·h (Kazarnovskaya AS and other Explosive methane reforming. M.: Proceedings of GIAP, 1957, TOP, s.89-105).

Obtaining synthesis gas is combined with electricity generation.

Use the specified method is not natural gas, and product processing - rich gas coke production, binds the production of synthesis gas for coke production. In addition, the implementation of the method using unenriched air α=0,827-1,2 in the products of the process, the content of CO21.5-2 times more than the hydrogen content does not satisfy the requirement of synthesis, and when α>1 hydrogen is absent. For example, when working on the raw air and α=0,827 the ratio of N2/WITH at 0.76 and in neither example does not reach values of 2.0 adopted for the synthesis of methanol.

When carrying out the procedure of air, oxygen-enriched, when α=0,5-0,8 oxygen content of 50% and 29% respectively specified, and the ratio of N2/Does not comply WITH the requirements of the catalytic synthesis (in some cases less than one). For α=0.8 content of CO2is the content.

As the closest analogue to the proposed method is a method for production of synthesis gas, comprising partial oxidation of hydrocarbon oxidizing agent in the internal combustion engine of the compression type when the oxidant excess coefficient less than 0.8, the flow to activate the working volume of the internal combustion engine of the initiators of partial oxidation. Initiators serves fewer than 10% of hydrocarbon raw materials, the compression ratio of the internal combustion engine select and/or adjust from 13 to 30 and surfaces of the internal combustion engine is made from materials and/or covered with materials that stimulate the process of partial oxidation (EN 21678080, publ. 27.05.2001).

As the closest analogue to the requested installation may be considered device - multi-cylinder internal combustion engine of the compression type, which contains the cylinder block, cylinders, each of which has a glow plug with adjustment of the heating heat exchanger, sosite the , the motor-generator and the turbine from the compressor (EN 2204727, 27.09.2002).

The disadvantage of this invention is that when the engine is started from a cold state, will need external heating fuel charge to temperatures that are generally unacceptable for industrial manufactured diesel engines. Glowing candles give a fairly limited effect when heated to the temperature specified in the data sheet for the product, and a higher heating drastically reduces the lifetime of their work. Therefore, these inventions do not allow in a wide range to support all of the cylinders of the engine the same conditions of inflammation, which is associated with frequent replacement, and the associated stop of the machine. In addition, individual adjustment of the heating temperature of candles associated with the use of fairly expensive device management and diagnostic process.

The technical objective of the claimed group of inventions implementing the use of existing mass-produced diesel engines for creation on their basis of generators of the synthesis gas, the set of essential features allow confident the launch and operation of the unit using a wide variety of hydrocarbon gases (natural gas, coal mine methane, petroleum gases) obtaining deballasting nitrogen synthesis gas simultaneously with the production of electricity. The claimed invention solves the problem of creating a method of producing synthesis gas suitable for further catalytic processing.

The use of the claimed method allows to obtain synthesis gas using a special installation, based on commercially available internal combustion engines, compression type, operating on the principle of a chemical reactor compression. The latter are the type of compression of the engine, i.e. ignition of the mixture of air and hydrocarbon compression with external mixture formation.

Using the method as hydrocarbons methane, ethane and other hydrocarbons produced, in particular, when the allocation of broad fraction of light hydrocarbons from petroleum gases, will improve the ecological situation in the areas of mining and processing of oil.

The relative performance of the claimed invention in 2.5-3 times higher than in the known method, and the volume ratio of H2/CO is 1.4:2. This is especially important because it is known that the efficiency of the production of synthesis gas largely determines the efficiency of production of methanol and synthetic fuels.

The process of partial oxidation of methane or other hydrocarbon gases in the engine cylinder inside the first combustion is extremely tempting, as this complex chemical process could be implemented in a single unit that acts as a compressor, compressing and heating the fuel charge, a chemical reactor in which the process actually occurs and the cooling device, in which the extension of the obtained product and simultaneously performed mechanical work.

High settings, which can be achieved in the chemical reactor compression (HRS), permit to obtain thermodynamically equilibrium composition of the synthesis gas in a very short time (10-3-10-4) C. When the amount of soot remains minimal.

There are several options HRS, which mainly differ in the ways ignition of the gas mixture. The main difficulty associated with the ignition of the gas mixture with a low coefficient of excess oxidant and which may be obtained acceptable composition of the synthesis gas. Typically, this zone is a slow burning, in order to maintain the chain reaction of combustion, a relatively high energy sources of ignition.

The goal of the project is achieved by the claimed group of inventions.

Method for production of synthesis gas is carried out in a setting that includes a multi-cylinder four-stroke or two-stroke engine two-piston fail internal SG is Rania compression type, operating as a chemical reactor compression. The method comprises preparing a mixture consisting of hydrocarbons, water vapor and air or oxygen-enriched air - fuel charge with air excess factor - oxidant 0,3-0,58 methane, further pre-heating the formed fuel charge, consistent flow into the cylinders of the engine, the additional heating it in the compression stroke of the piston, the volume ignition in the area of the top dead point due to spontaneous combustion of the added fuel charge additives in the form of liquid or gaseous substances with an ignition temperature below the ignition temperature of the fuel charge, which results in the starting of the engine as a chemical reactor compression and partial oxidation hydrocarbon mixtures - fuel charge in the volume of the cylinder internal combustion, subsequent expansion and cooling products, formed during reverse motion of the piston to the bottom dead point, the output products of the process containing synthesis gas, then cooling, cleaning soot from the final cooling and conversion to methanol or dimethyl ether, the process of partial oxidation at the exit of the chemical reactor compression operating mode support due to residual gas is in the cylinder, the number of which regulate the reconfiguration timing, additional heating due to the heat engine and the external regulation of the temperature of the heated fuel charge.

As liquid or gaseous additives with an ignition temperature below the ignition temperature is introduced into the fuel charge, use alcohol, motor fuel, hydrocarbon gases and other substances.

Device for producing synthesis gas, followed by his conversion to methanol or dimethyl ether includes multi-cylinder four-stroke or two-piston fail two-stroke internal combustion engine of the compression type, operating in a chemical reactor compression, containing a system of intake and exhaust valves, with the specified engine is supplied by the air supply system, hydrocarbons and additives, heating system, including pre-heat, air and hydrocarbon, consisting of a heater, heat exchanger and mixer, cooling the synthesis gas, consisting in turn of the heat exchanger and cooler, reversible motor-generator, generating electricity, supply multistage compressor synthesis gas, and is rigidly connected with the engine, high temperature filter synthesis gas from carbon black, refrigerator, drop the safety device, while the engine is running in the mode of a chemical reactor and compression mode control of his work, as well as the composition of the produced synthesis gas is performed to control the coefficient of excess oxidant and the preheating temperature in the heat exchanger in steady mode or the outlet temperature of the starting of the stove.

To identify the individual cylinders carry out additional possible flow directly into the zone of the intake valves of the necessary components for adjusting the moment of ignition of the mixture in each cylinder.

Such components, in particular, are natural and associated petroleum gas, methanol or Smetanina water related products by further processing of methanol or dimethyl ether in gasoline fraction.

The drawing shows a schematic diagram of the installation.

Preheated in the blower (1) and Doherty to the required temperature in the heat exchanger (2) the air in the mixer (3) is mixed with a hydrocarbon gas (natural and associated petroleum gas, coal mine methane) and is input to the diesel engine (4). The engine is rigidly, without slipping, is connected with the reversible motor-generator, for example, using the coupling (5). The electricity generated by them, nourishes the compressor (6) synthesis gas. Received in GHA synthesis g is C is cooled in the heat exchanger (2), cleaned from soot in high-temperature filter (8) and after the final cooling in the refrigerator (9) passes through the eliminator (10) to the input of a multistage compressor (7), which further squeezed up to the pressure required for the conversion of synthesis gas to methanol or dimethyl ether.

Used multi-cylinder engine four-stroke or two-stroke two-piston fail. The number of cylinders is determined by the capacity and performance of the unit. For example, the Kolomna plant produces diesel engines from 4 to 20 cylinders. From this number you select any calculation required.

Use an external device for implementing the claimed group of inventions (blower, heat exchangers, mixer), which is provided with an internal combustion engine operating mode HRS, and designed to perform the necessary procedures for the preparation of the fuel charge (mixture of hydrocarbon gases), heated air to flow into the cylinders of the engine. In them there is a mixture of components required, heated to a temperature that ensures the ignition of the mixture at the end of the compression stroke.

The amount of additional heating is determined by the compression ratio in the cylinders, the composition of the gas mixture, the presence of various additives, the value of the pressure at the inlet to the engine and other factors.

On large industrial the different multi-cylinder engines the temperature of the prepared mixture at the entrance to the individual cylinders may vary due to different distances from the entrance and heat loss in the suction manifold. The difference of these temperatures by 3-5°With the already significant, and the work cylinder will be different. Methane, the main component of the fuel charge, poorly mixed with air, and hit mixtures of different compositions in separate cylinders. To prevent the influence of these two factors on the composition of the produced synthesis gas is subject to special measures for the adjustment mode.

The timing in the internal combustion engine provides the torque required for opening and closing intake and exhaust valves. In our case, these points are chosen for safety reasons to ensure that the oxygen of the oxidant (air) was not included in the final synthesis gas.

Reversible motor-generator is rigidly connected with the engine, while the term "rigidly connected" means that the engine and generator interconnected by the clutch without slipping, have the same momentum.

A constant speed determined by the mains frequency of 50 Hz and can be 1500, 1000, 630, etc. depending on the selected synchronous generator and used by ice. The higher the speed, the greater the capacity of the unit, but there are limitations on the mechanical characteristics and the speed of chemical reactions. In all operating modes selected complex diesel generator operates with a constant number of revolutions.

Management of partial Oka the population of hydrocarbon gases is sufficiently thin, especially if it is carried out in the cylinders of a chemical reactor compression (modified internal combustion engine at high revs, when the whole cycle is 10-3C. Defining moment, depends on the completeness of the completion of the reaction, is the moment of ignition of the mixture in the cylinders. This is achieved through a complex of measures foreseen in the application and is called a regime of managed C.

Value α and t° depend on the composition of hydrocarbon gas that is running the installation, and in each case are determined by calculation and experiment. The total range of t° 70°, 250°C. the invention solves the problem of creating a method of producing synthesis gas suitable for further catalytic processing.

The use of the claimed method allows to obtain synthesis gas using this setup, based on commercially available internal combustion engines, compression type, operating on the principle of a chemical reactor compression. The latter are the type of compression of the engine, i.e. ignition of the mixture of air and hydrocarbon compression with external mixture formation.

Using the method as hydrocarbons methane, ethane and other hydrocarbons produced, in particular, when the separation of the NII broad fraction of light hydrocarbons from petroleum gases, will improve the ecological situation in the areas of mining and processing of oil.

The relative performance of the claimed invention in 2.5-3 times higher than in the known method, and the volume ratio of N2/CO is 1.4:2. This is especially important because it is known that the efficiency of the production of synthesis gas largely determines the efficiency of production of methanol and synthetic fuels.

The process of partial oxidation of methane or other hydrocarbon gases in the cylinder of the internal combustion engine is extremely tempting, as this complex chemical process could be implemented in a single unit that acts as a compressor, compressing and heating the fuel charge, a chemical reactor in which the process actually occurs and the cooling device, in which the extension of the obtained product and simultaneously performed mechanical work.

High settings, which can be achieved in the chemical reactor compression (HRS), permit to obtain thermodynamically equilibrium composition of the synthesis gas in a very short time (10-3-10-4) C. When the amount of soot remains minimal.

Start HRS, the governance regime of its operation and the composition of the produced synthesis gas is carried out with p the power factor adjustment excess (deficiency) of oxidizer and the preheating temperature in the heat exchanger (2) in steady mode or the outlet temperature of the starting heater (11) at the time run.

Operational impact at the time of start-up and adjustment process HRS in steady mode is performed depending on the composition of hydrocarbon gases by the influence of the moment of ignition of the gas mixture. For this purpose, can be used the waste of the primary production of methanol, gasoline or other products having a lower ignition temperature than the gas that allows, especially in transient conditions, clearly record the moment of ignition of the fuel charge, and this in turn determines how the composition of the synthesis gas, and the process of soot formation and the amount issued by electric power.

Run the unit with a reversible motor-generator from the electrical network allows for the transition to nominal mode to maintain momentum due to the frequency constant, without any additional devices, and provide power to the compressor from its own energy source.

To solve problems, work-related HRS in mode C in the claimed group of inventions is used, for example, chemical reactor compression on the basis of engine D-245 Minsk motor plant, which to a large number of launches, including long, were tested in various modes of operation.

On installing trabot what are the modes start-up and operation on methane associated petroleum gas with a high content of NGL (wide fraction of light hydrocarbons) with different values of and, the preheating temperature of the mixture, feed additives, used to start and to control the process.

Thus, in accordance with the stated group way of working multi-cylinder modified four-stroke or two-piston fail two-stroke internal combustion engine of the compression type in the mode of a chemical reactor compression is that pre-heated in an external device of the fuel charge consisting of a mixture of hydrocarbon gases with air or oxygen-enriched air with an air excess factor of 0.3 is 0.58 for methane in the range from intensive soot formation in the zone of slow combustion of hydrocarbon mixtures with air prior to the beginning of explosive combustion, depending on the composition of the hydrocarbon gas, sequentially fed into the cylinders of the engine in which the compression stroke is additional heating and volumetric ignition in the area of the TDC due to spontaneous combustion of the additional additives in the fuel charge the required quantity of liquid or gaseous substances having a lower ignition temperature in relation to the main structure that allows at low temperature is Oh preheating to start HRS and implement the process of partial oxidation of hydrocarbon gases, when leaving the unit on the operating mode is supported by warming the engine and the influence of the residual amount of the synthesis gas in the cylinders defined by the reconfiguration timing, thus eliminating the necessity of filing additional substances, and the resulting synthesis gas at reverse motion of the piston extends, which is accompanied by a sharp cooling ("freezing") of its composition and the performance of mechanical work.

After running HRS at low temperature heating fuel charge due to the additional supply of gaseous or liquid materials with low ignition temperature in relation to the main flow begins intensive heating of the walls of the cylinder and piston, which in itself already allows to reduce the heating temperature of the fuel charge by reducing losses, but the main contribution comes from the hot synthesis gas remaining in the cylinders, which also has a lower ignition temperature. The amount of this synthesis gas is determined by preliminary adjustment of the intake and exhaust valves for accurate fixing of the moment of ignition of the fuel charge in the steady state operation HRS.

HRS is rigidly connected to an electric generator, plugged in AC and supports a constant speed by frequency.

DL the identification of the individual cylinders, associated with deviations of the degree of compression, the temperature spread mixture at the inlet and the uniformity of its composition, additional feed directly into the zone of the intake valves of the necessary components for adjusting the moment of ignition of the mixture in each cylinder.

Thus, the method is as follows.

1. Pre-exercise the heated air in the blower.

2. Carry out heating of air (oxidant) in the heat exchanger to the desired temperature, for example up to T=180-240°C.

3. Mix heated air (oxidant) with a hydrocarbon feedstock to α=0,3-0,58; and serves on the intake of the engine (diesel).

4. Add the water vapor and the mixture is reheated to T=180-240°C.

5. Consistently served the mixture (fuel charge in the cylinders of the engine (stroke volume).

6. Provide additional heating of the fuel charge in the compression stroke of the piston and the volume auto-ignition in the TDC area, which occurs due to the previously entered in the fuel charge additives substances (liquid, gaseous), which has an ignition temperature below the main part of the fuel charge, and obtaining the temperature of 1,800-2,100°C.

7. Starts HRS, and is thus the partial oxidation of the hydrocarbon gas.

8. Cool products, expanding them with DWI the attachment of the piston to BDC.

9. Eliminate products of the process containing synthesis gas from the engine cylinder during movement of the piston to TDC.

10. Carry out the cooling of the synthesis gas to T=100-240V°C.

11. Clean synthesis gas from the soot filter.

12. Cooled synthesis gas to T=30-40°C.

13. Carry out kompremirovannyj and the conversion of synthesis gas to methanol or dimethyl ether.

Examples of the method for production of synthesis gas by the claimed invention are shown in table No. 1.

Table 1
"Method for synthesis gas production and installation for its implementation"

The estimated composition and parameters of the conversion products on the tract at alpha=0,40
NameRaw synthesis gasThe synthesis gas before compressorThe synthesis gas before the high-pressure compressor synthesis gasThe synthesis gas at the entrance to the block of methanol synthesisExhaust synthesis gas
Composition, vol.%
N249,0552,6254,6354,9876,5
H224,0525,8126,7926,77 11,2
O20,260,280,290,000,0
H2O10,413,910,250,100,1
CO13,3014,2714,8114,527,2
CO22,40to 2.57to 2.67of 3.074,3
CH40,510,540,560,570,8
NH30,020,000,000,000,0
100,00100,00100,00100,00100,0
Molek. weight21,05021,27121,46925,69
Temperature, °370,004535140-150200
The output unit. kg/kg natural gas8,0957,6257,3877,3666,336
The heat of combustion of Nyssa is, kJ/nm344592231
Consumption kg/h113831071810384103548907

1. Method for production of synthesis gas installation, including multi-cylinder four-stroke or two-piston fail two-stroke internal combustion engine of the compression type, operating in a chemical reactor compression, and which includes the preparation of a mixture consisting of hydrocarbons, water vapor and air or oxygen-enriched air - fuel charge with air excess factor - oxidant 0,3-0,58 methane, further pre-heating the formed fuel charge, consistent flow into the cylinders of the engine, the additional heating it in the compression stroke of the piston, the volume ignition in the area of the top dead point due to spontaneous combustion of the added fuel charge additives in the form of liquid or gaseous substances with an ignition temperature below the ignition temperature of the fuel charge, which results in the starting of the engine as a chemical reactor is compressed the I and the partial oxidation of the fuel charge in the volume of the cylinder internal combustion subsequent expansion and cooling products, formed during reverse motion of the piston to the bottom dead point, the output products of the process containing synthesis gas, then cooling, cleaning soot from the final cooling and conversion to methanol or dimethyl ether, the process of partial oxidation at the exit of the chemical reactor compression operating mode support due to residual gases in cylinders, the number of which regulate the reconfiguration timing, additional heating due to the heat engine and the external regulation of the temperature of the heated fuel charge.

2. Device for producing synthesis gas, followed by his conversion to methanol or dimethyl ether, which includes multi-cylinder four-stroke or two-piston fail two-stroke internal combustion engine of the compression type, operating in a chemical reactor compression, containing a system of intake and exhaust valves, with the specified engine is supplied by the air supply system, hydrocarbons and additives, heating system, including pre-heat, air and hydrocarbon, consisting of a heater, heat exchanger and mixer, cooling the synthesis gas, consisting in turn of the heat exchanger and the cold is nick, reversible motor-generator, producing electricity supply multistage compressor synthesis gas, and is rigidly connected with the engine, high temperature filter synthesis gas from carbon black, refrigerator, drip pan, and engine starting mode of a chemical reactor and compression mode control of his work, as well as the composition of the produced synthesis gas is performed to control the coefficient of excess oxidant and the preheating temperature in the heat exchanger in steady mode or the outlet temperature of the starting of the stove.

3. Installation according to claim 2, characterized in that to identify the individual cylinders carry out additional possible flow directly into the zone of the intake valves of the necessary components for adjusting the moment of ignition of the mixture in each cylinder.



 

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