KR101206490B1 - Method for producing synthesis gas in a plant consisting of a compression-type internal combustion engine - Google Patents

Abstract

The present invention relates to syngas production. The process according to the invention for producing syngas is carried out by a plant equipped with a multi-cylinder four stroke or double piston two stroke compression type internal combustion engine. The method comprises the preparation of a mixture of hydrocarbonaceous raw material, steam and air or oxygen enriched air-filled fuel with an excess coefficient of air (oxidant) of 0.3 to 0.58 to methane, further heating of the formed fill fuel, its constant supply to the engine cylinder. Additionally in a packed fuel of liquid or gaseous material with a lower spontaneous ignition temperature relative to the main volume of the packed fuel, causing its further heating during compression into the cylinder piston, the start of operation of the chemical compression reactor and the partial oxidation of the hydrocarbonaceous mixture. Its volume ignition in the region of top dead center (TDC) following spontaneous ignition introduced-fuel filling in the volume of the internal combustion cylinder, followed by expansion and cooling of the process product formed during the movement of the engine piston to the bottom dead center, during the return strip, containing syngas Recovery of the process product, followed by cooling of the synthesis gas, Its purification from carbon black, its final cooling and its conversion to methanol or dimethyl ether.

Syngas

Description

Method for producing synthesis gas in a plant consisting of a compression-type internal combustion engine

TECHNICAL FIELD The present invention relates to chemical engineering, and more particularly to a process technology involving the continuous change of a synthesis gas obtained from a hydrocarbon feedstock, in particular a gaseous hydrocarbonaceous feedstock, into methanol or dimethyl ether.

For example, partial oxidation of methane (CH ₄ Various methods of preparing syngas from hydrocarbonaceous raw materials by + 0,5O ₂ + CO + 2H ₂ ) are known.

There is a method for producing syngas from natural gas based on different types of conversion, mixed gas comprising H ₂ and CO: non-catalytic partial oxidation described in foreign technical literature on oxygen conversion or engineering, catalysts in shaft reactors Autothermal reforming under steam, steam reforming in pipe heaters with heating tubes (gas generation method for synthesizing ammonia and methanol from hydrocarbon gas. Chem. Moscow, 1971, Calibrator AH Leibush).

The self-generating heat reforming of natural gas adding CO ₂ to produce gas for the synthesis of methanol is carried out by observation in the steps described below.

Carbonization of natural gas with H ₂ O,

Mix it with CO ₂ and heat the temperature in the heat exchanger back to 550-600 ° C. with the converted gas; And

In a shaft catalytic reactor, the gas-vapor mixture has a ratio of O ₂ : CH ₄ = 0,6: 1,0 to oxygen and CO ₂ : H ₂ 0: CH ₄ = 0,2: 0,9: 1,0 Additional conversions.

The reaction is carried out under a temperature of 850-95 ° C., nickel-containing catalyst (6% NiO to Al from O ₂ O ₃ to the operating agent). After the cooling of exhaust heat boiler, the gas-vapor mixture heat exchanger for heating the cleaning scrubber (water scrubber) for the converted gases and are CO ₂ is removed with the aid of a MAS (monoaethanolamine solution) supplied for compression and methanol synthesis do.

The problem with the method described above is as follows:

1. After self-generating heat reforming, the reformed gas contains an excess of CO ₂ (% by volume). Therefore, further removal of CO ₂ is required.

2. The reforming gas shows an increase in the H ₂ / CO (> 2.3) ratio which leads to an increase in the consumption of large amounts of hydrogen, consequently CO + H ₂ 0 per unit of product. Methanol synthesis requires a so-called “function” ratio of T = (H ₂ -CO ₂ ) / (CO + CO ₂ ) ＾ 2.05.

3. As a result of methanol synthesis, hydrogen becomes excessive and leads to explosion, resulting in increased energy and material costs.

Another method of syngas production with a low H ₂ / CO ratio for methanol synthesis is the non-catalytic partial oxidation of natural or other hydrocarbon gas (Directory of Nitrogen-Man, Chemistry, Moscow, 1986). Natural gas reacts with oxygen at high temperatures (1300-1500 ° C) in free amounts. The gas produced mainly consists of hydrogen and carbon oxides.

Hot combustion (1350-1400 ° C.) processes without catalyst are also possible. It is necessary to keep the O ₂ : CH ₄ ratio somewhat higher than the stoichiometry to maintain the self-generating heat process at such temperatures; As a result, the reaction product contains not only H ₂ and CO, but also water vapor (H ₂ O) and carbon dioxide (CO ₂ ). The ratio of H ₂ and CO in the syngas after non-catalytic partial oxidation of natural gas is about 1.7 to 1.8.

Changing the ratio of H ₂ / CO is possible by either an additional supply of H ₂ O or an additional supply of CO ₂ .

The final step in the non-catalytic partial oxidation of natural gas is the water-gas reaction equation below:

H ₂ 0 + CO = H ₂ + CO ₂ = Q ₃

At this time, the reaction occurs before the temperature of ~ 1200 ℃. At lower temperatures the gas composition will differ from the above scheme due to the slowing down of the motion. Independently of the composition of the original gas, only a small amount of methanol is present in the reaction product. During the partial oxidation process free carbon (black smoke) is released according to the following reaction:

2CO = C-CO ₂ + Q ₄

Thus, the composition of the gas produced, the H ₂ / CO ratio. The temperature and dark smoke emission boundaries are determined by the initial parameters.

Reaction of partial oxidation of natural gas is accompanied by an increase in volume; Thus, the use of pressure will prevent oxidation.

Since the temperature factor compensates for the negative pressure action with an increase in temperature (above 1200 ° C.), it can be measured without limiting the amount of methanol oxidation.

However, such noncatalytic partial oxidation has the following problems:

1. Increasing the consumption of oxygen for natural methanol (or natural gas) results in an increased cost compared to autothermic reforming. The device for oxygen production is expensive and 70% of the cost of methanol production. In addition, oxygen generation is power consuming.

2. Black smoke occurs during the process, which requires an additional purification step, which complicates the work in the subsequent engineering step.

All of this leads to high energy and material costs per unit of production.

There has been a need for a process capable of making carbon materials a liquid hydrocarbonaceous fuel which has been preferred for many applications such as internal combustion engines, reaction engines, and open cycle gas turbines for a long time. Thus, for example, US Pat. No. 3986349 discloses a process for coal to liquid hydrocarbonaceous fuel by gasification of coal to syngas, hydrogenation of the resulting syngas and extraction of liquid hydrocarbonaceous fuel from hydrogenated products. Described. Liquid hydrocarbonaceous fuels are used to generate energy by relatively clean combustion in gas turbines in open cycles.

Natural gas is found in large quantities in areas that are not suitable for development because of the lack of local gas markets or because of the high cost of gas transportation to long distance markets. An alternative would be production and processing for more cost-effective transport of natural gas to more practical liquid phase hydrocarbonaceous fuel production conditions or to liquid phase chemical production or local markets for local use. The process of treating light hydrocarbon garsons, such as natural gas, with heavier hydrocarbon liquids is somewhat known. The process generally employs an "indirect" process of methanol to a synthetic wax-bearing hydrocarbonaceous compound, where methanol is first treated and treated with a synthesis gas containing hydrogen and carbon monoxide and further processed by Fisher-Tropsch. The reaction is treated with a wax-bearing hydrocarbonaceous compound. The untreated syngas remaining after the Fisher-Tropsch reaction is generally fed back into the methanol via a methanation reaction by the catalyst and fed to the process inlet to increase the general efficiency of the process.

Often the treatment of methanol with syngas is by hot steam reforming, where methanol and steam endotherm react under a catalyst contained in many externally heated pipes installed in a large combustion chamber. That is, methanol is treated with syngas by partial oxidation when methanol exothermicly reacts with the treated oxygen. Partial oxidation using treated oxygen requires oxygen separation facilities with high compression capacity and at the same time significant power requirements. The production of syngas using such a plant constitutes a major part of the total cost of the plant for the treatment of methanol with wax-bearing hydrocarbonaceous compounds.

Autothermic reforming is a less expensive method of treating methanol to syngas. Self-generating heat reforming consists of a combination of partial oxidation and steam reforming. The endothermic heat required for the steam reforming reaction is caused by the exothermic reaction of partial oxidation. However, unlike the partial oxidation reaction described above, air is used as the source of oxygen for the partial oxidation reaction. In addition, the syngas produced during the self-generating heat reforming process contains a significant amount of nitrogen from the injected air. This means that it is not possible to send the untreated compound of the residual gas back to the cycle without the accumulation of unwanted excess nitrogen in the process. Furthermore, according to US Pat. Nos. 2552328 and 2686195, the production of nitrogen-containing syngas by means of self-generating heat reforming of partial oxidation with air in which further processing of the syngas is effected by the Fisher-tropsch reaction results in methanol. It is a useful method to obtain a synthetic hydrocarbonaceous liquid from the.

Patent 4833170 describes another example of self-generating heat reforming, in which light carbon in gaseous form reacts with air under conditions in which carbon dioxide and vapor react to produce syngas. Syngas is produced in the presence of cobalt-containing hydrocarbon synthesis catalysts, with the formation of residual gas vapors and liquid vapors containing heavier hydrocarbons and water. Heavier hydrocarbons are separated from water and extracted as product. The remaining gas forms catalytically carbon dioxide and nitrogen which will be combusted and separated with the supply of air. At least some of the carbon dioxide is returned to the reaction in the self-generating heat reforming step.

Known methods of hydrocarbon gas, such as those described in US Pat. No. 4833170, can be relatively effective in treating lighter hydrocarbon gases with heavier liquid hydrocarbons, but such treatments are attributable to the cost of energy and equipment for the compression of the emitted air. Not efficient The power for the compression of the exhaust air is a major part of the mechanical power required for the process, but many of this power is lost without doing anything as unused pressure energy in the remaining gas from the process. Exhausted air that requires compression remains substantially chemically inert as it enters the process and contains a significant amount of nitrogen that is first released from the process in the remaining gas. In addition, although the residual gas has significant characteristics as carbon monoxide, hydrogen, methanol and heavier hydrocarbon compounds as large chemical energy fuels, the residual gas is very dilute and has a low combustion specific heat to use high efficiency as a residual gas energy. It is difficult and expensive. Thus, it is clear that there is a need for a more cost effective hydrocarbon gas treatment method.

From U.S. Patent No. 1831468 (July 30, 1993), we can see how to produce syngas from hydrocarbonaceous raw materials-the process comprising hydrocarbonaceous raw materials and oxidants (gases containing oxygen or oxygen or Mixing) and conversion of the mixture obtained in the presence of a monolithic catalyst at a rate at which the rate of injection of the mixture into the reaction zone at least 93 ° C. below the spontaneous ignition temperature in the reaction zone exceeds the backflash rate. do.

The process requires the use of highly selective catalysts. The main drawbacks of this method are the high cost of the catalyst, the possibility of partial breakdown of the catalyst due to local overheating, and the possibility of producing black smoke.

From US Patent No. 5980782 in 1999, we present a CH in a reactor with a fluidized catalyst bed where gaseous compounds are preheated and injected into the reaction zone for a spontaneous ignition time, i.e., less than 9 msec. ₄ + O ₂ + H ₂ 0 mixing reforming method is known. The syngas produced is cooled and proceeds later.

The main drawback of this widely known invention is the use of catalysts.

burning oxygen-enriched air at α0.5 to 0.8, or a mixture of oxygen-deficient air and hydrocarbonaceous raw materials at α0.827-1.2, and explosive partial oxidation of hydrocarbons in the cylinder volume of the internal combustion engine, Expansion and cooling of the process product while the engine piston is moving, recovery of the process product containing syngas from the reaction while the engine piston is moving to top dead center, air-fuel mixture of a new part while the engine piston is moving to the bottom dead center It is also possible to produce syngas by injection of. Mainly coal-bearing mixed gases containing carbon oxide, methane and ethylene fractions are used as hydrocarbonaceous feedstocks. The air-fuel mixture together with the abovementioned raw materials is fed into the cylinder of the internal combustion engine, and active ignition of the mixture leads to explosive partial oxidation. The specific capacity in the treatment of hydrocarbonaceous raw materials is about 700 kg / m ³ * h. (Ya. S. Kazarnovsky et al., Explosive Methane Conversion, M. Papers of the State Institute of Nitrogen Industry and Organic Synthesis Produces (GIAP), 1957, V. VII, P. 89-105 (in Russian)). Syngas production is combined with the production of electrical energy.

Without the use of natural gas, the use of the treated product (coal production combined gas) combines the gas production and coal production facilities.

In addition, using air deficient in this method at α0.827-1.2 results in CO ₂ content in the treated product up to 1.5 to 2.0 times as much as CO, and the hydrogen content does not meet the synthetic requirements, At 1 hydrogen is not present at all. Thus, for example, when operating with depleted air and α 0.827, the H ₂ / CO ratio is 0.76, which does not reach an acceptable 2.0 value for methanol synthesis.

When the process is carried out with oxygen-enriched air at α0.5 to 0.8 (oxygen content 50% and 29% according to a above), the H ₂ / CO ratio does not satisfy the catalyst synthesis requirements (see In some cases), therefore, for α0.8 the CO ₂ content is the same as the CO content.

There is a method for producing syngas according to RU 2096313 (20.11.1997). At this time, no catalyst is used. The method is carried out as follows:

Hydrocarbonaceous raw material preliminarily mixed with air at α = 0.5 to 0.8;

The mixture is heated to a temperature of 200-450 ° C .;

The heated mixture is fed into the cylinder volume of the compression-ignition internal combustion engine at the piston moving to the bottom dead center

Partial oxidation of hydrocarbonaceous raw material is realized by compression of the mixture in the cylinder volume by a piston moving to the bottom dead center and spontaneously ignited and recovered at a temperature of 1300-2300 ° C. for a period of 10 ⁻² to 10 ⁻³ .

The oxidation treatment product is then cooled and expands as the piston moves to the bottom dead center,

Treated products containing syngas are recovered when the piston moves to the bottom dead center.

The above mentioned cycles are repeated at frequencies above 350 min ⁻¹ . The main drawback of RU 2096313 is the preheating temperature which is too high at the start. It is not allowed to use in continuous diesel engines.

The plant for applying the syngas production method is based on compression-ignition internal combustion, and the cylinder has a closed reaction volume in which the piston is located. The inlet and outlet valves are at top dead center and the inlet valve is connected to the oxygen mixture and hydrocarbonaceous raw material and their heating system, where the outlet valve is coupled to the oxidation product receiver. Through the connecting rod gear, the cylinder piston is connected to the drive actuator.

The above-mentioned system operates in a cycle at a piston movement frequency not less than 350 min ⁻¹ .

The low frequency of the cycle leads to a relatively low compression ratio that cannot provide spontaneous ignition of the gas mixture.

Another method of syngas production is disclosed in RU 2120913 (27.10.1998). Here, the partial oxidation of the hydrocarbonaceous raw material by oxygen air occurs in the cylinder volume of the internal combustion engine engine at the ratio α = 0.4 to 0.5. When the piston is at top dead center, a portion of the mixture of air and hydrocarbonaceous material is ignited and oxidized well in the ratio of oxygen content to hydrocarbonaceous material amount of 5-10% from the volume of the original mixture at α = 0.8 to 1.2. Exposed and separated. The well oxidized product is mixed with the original mixture in the working volume of the cylinder and the mixture is ignited. The treated product expands as the piston moves to bottom dead center and the treated product comprising syngas is extracted from the reaction zone as the piston moves to top dead center. The cycle then repeats. The efficiency of such a method of syngas production is such that part of the mixture of air and hydrocarbonaceous raw material is pre-ignited and easily oxidized at a ratio of α = 0.8 to 1.2 in the amount of oxygen to hydrocarbonaceous raw material in an amount of 5-10% from the original mixing volume. Separated from the main volume of the mixture when exposed and the piston is at the top dead center, then the portion is injected as a high energy jet into the main volume of the mixture and the mixture is concentrated and ignited within the operating volume of the cylinder It increases with the moment of exposure. The main drawbacks of this syngas production process are the low concentrations of hydrogen and the significant amount of black smoke.

The equipment making this method possible has a chemical compression reactor based on an internal combustion engine and includes a cylinder and a pre-ignition chamber. The cylinder includes a pistol and an injection valve through which a mixture of hydrocarbonaceous raw material and air is supplied to the cylinder and the preliminary ignition chamber. A discharge valve for discharging the treated product to the outside is installed inside the cylinder. The preliminary ignition chamber has a separate valve to supply air until a value of α = 0.8 to 1.2 is reached in the chamber. The volume of the pre-ignition chamber makes 5% of the volume of the cylinder when the piston is at top dead center.

During the syngas production process, the hydrocarbon and air mixture of a given composition is exposed to spark ignite in the pre-ignition chamber when the piston is near top dead center. A high energy jet is then injected into the cylinder's working volume for 1 ^{-3-10 -2} seconds at a speed of about 10 ^-3 m / sec. In the working volume of the cylinder, the original mixture is mixed with the dark oxidation product and ignited, and a partial oxidation process takes place. The treated product expands, cools, and hardens as the piston inside the cylinder moves to the bottom dead center. As the piston moves back to top dead center, the treated product exits the cylinder through the discharge valve. When the piston moves to the bottom dead center and the injection valve opens, fresh air is supplied to the cylinder and the preliminary ignition chamber. As such, work cycles of the plant and generation of syngas are achieved.

RU 2191743 describes a method of producing syngas in a particular plant.

The syngas production process involves mixing the hydrocarbonaceous feedstock with air, mixing it at a ratio that satisfies the oxidation excess coefficient α of less than 1, and partially by the air in the ignition and reaction zones of the mixture of air and hydrocarbonaceous feedstock. Forcing the oxidation, discharging the treated product containing syngas, cooling it, and injecting new hydrocarbonaceous raw materials and air. Wherein the hydrocarbonaceous feedstock and the air are heated at elevated pressure and a temperature of 50-100 ° C. lower than the spontaneous ignition temperature of their mixture, and partial oxidation of the hydrocarbonaceous feedstock is carried out in a fluid combustion chamber, together with such forced ignition The excess oxidation coefficient α = 0.6-0.7 occurs, and the flow combustion chamber is heated to a ratio up to a level corresponding to the value of α = 0.3 to 0.56 of the ratio of air to hydrocarbonaceous raw material. Cooling of the partial oxidation product discharged from the reaction zone is carried out at a rate no lower than 3000 ° C./sec. Facilities for syngas production include a chamber in which partial oxidation of hydrocarbonaceous raw materials occurs by air, a mixer, a system in which expansion and cooling of the partial oxidation product and discharge of syngas occur. It also includes a preliminary heating of hydrocarbonaceous raw material and air and a hydrocarbonaceous raw material flow regulator system. In addition, the partial oxidation chamber of hydrocarbonaceous feedstock contains an ignition jet, designed similarly to the flow chamber, with the inlet of which the mixer is coupled via an anti-backflash grate, and the hydrocarbonaceous feed pipe. And an air delivery pipe connected to the mixer, two delivery pipes latched with a recuperator fitting, the recuperator fitting attached to the outlet side from the flow combustion chamber, and another open end of the recuperator It is connected to a cavity of a heat exchanger produced by an enclosure that limits the area around the fitting. In addition, a hydrocarbonaceous raw tube heater and an air tube are located in the heat exchanger cavity. One end of the hydrocarbonaceous feed tube heater is connected to the hydrocarbonaceous feed flow regulator, and the other end is connected to the mixer via the aforementioned delivery pipe. One end of the air tube heater is connected to the air source and the other end is connected to the mixer via a delivery pipe. As such, the heat exchanger is provided with a sleeve to extract syngas from the cavity.

The device is very complex and does not allow the gas mixture to be heavily loaded with nitrogen like the original raw material.

The most similar is syngas production method comprising injecting a partial oxidation driver into the working volume of an internal combustion engine for partial oxidation and activation of hydrocarbonaceous raw materials by oxidant in a compression-ignition internal combustion engine at an oxidation excess coefficient of less than 0.8. . The driver is injected with a hydrocarbonaceous raw material in an amount of 10% sorry, the compression ratio of the internal combustion engine is selected and / or controlled from 13 to 30, and the working surface of the internal combustion engine is controlled by a material that activates the partial oxidation process. Covered and / or made (RU 2167808 27.05.2001).

RU 2204727 (27.09.2002) discloses a multistage cylinder four cycle internal combustion engine operating in a chemical compression reactor. Syngas here is produced in the compression cylinder of the internal combustion engine. Known multicylinder internal combustion engines include cylinder blocks, each cylinder having a heater plug with a heat control device, a heat exchanger, a mixer, a motor generator and a turbine with a compressor.

The drawback of the above-mentioned invention is that when the engine starts from cooling conditions, it is necessary to provide external heating of the filling fuel to a temperature which is not generally acceptable for commercial engines. The heater plug has a very limited effect when heated to a certified temperature in the device, and higher heating sharply reduces its personnel. Thus, the invention cannot provide equal ignition conditions in all engine cylinders in a wide range of frequent plug replacements and consequent stopping of the set. The individual adjustment of the temperature of the plug heating also requires the need for expensive control and diagnostic devices.

The engineering techniques of the claimed invention groups include the use of commercial diesel engines as the basis for syngas production.

The technical problem of the claimed invention group is the existing in-line diesel engine, which is used to generate the basic generator of syngas using the most diverse hydrocarbon gases such as natural gas, coal mine methane, and related petroleum gas with the continuous generation of power. Is to realize the availability of.

These engineering problems include the preparation of mixtures of hydrocarbonaceous raw materials, steam and air or oxygen enriched air-filled fuels with an air (oxidant) excess coefficient of 0.3 to 0.58 relative to methane, further heating of the formed fill fuels, their engine cylinders. Filled fuel of liquid or gaseous material with a lower spontaneous ignition temperature with respect to the main volume of the charged fuel, causing constant supply, its further heating during compression movement to the cylinder piston, the start of operation of the chemical compression reactor and the partial oxidation of the hydrocarbonaceous mixture Its volume ignition in the region of top dead center (TDC) due to spontaneous ignition additionally introduced therein-fuel filling in the volume of the internal combustion cylinder, followed by expansion and cooling of the process product, during the return strip, during the movement of the engine piston to the bottom dead center, syngas Recovery of the process product containing Cooling of the gas, its purification from carbon black, its final cooling, and its conversion to methanol or dimethyl ether, the entire operation being carried out to the remaining gas in the cylinder while reaching the chemical compression reactor (CCR) unit in the process of partial oxidation. Multicylinder four-cycle or double-piston operating in the manner of a chemical compression reactor, which is maintained by means of re-adjustment of valve regulation, additional heating due to engine preparation, and external control of filling fuel heating temperature. It is solved by a method for producing syngas in a device consisting of a two-cycle compression-ignition internal combustion engine.

The claimed method comprises an air supply and a hydrocarbonaceous feedstock system, a preheating of air and hydrocarbonaceous feedstocks, and a heating system consisting of an air-heater, a heat exchanger and a mixer, in turn producing a heat exchanger and a cooler, power To provide a multi-stage syngas compressor, and a syngas cooling system consisting of a reversible motor-generator that is tightly coupled to the engine, and also to a high temperature carbon black collection filter, cooler and drop catcher for syngas purification. The control of its operation at the start of the engine, and the control of the syngas composition produced, is a difference that makes it possible to control the excess coefficient of the oxidant and the preheat temperature in the heat exchanger or the start-up exhaust temperature of the air heater in the fitted manner. In a manner of chemical compression reactor having a system of inlet and outlet valves That, compressed multi-cylinder four-cycle or two-piston two-cycle may be carried out in a synthesis gas generation plant is configured to ignite an internal combustion engine.

Spirits, engine fuel hydrocarbon gas and other fuels may be used as liquid or gas elements having an ignition temperature below the ignition temperature that is guided into the fill fuel.

An additional supply to verify the operation of the individual cylinders may be provided (directly in the region of the injection valve) for the control of the ignition moment of the mixture in each cylinder.

In particular, such components are related products which process additional methanol or dimethyl ether into natural or related petroleum gas, methanol or water-methanol mixtures and gasoline residues.

1 is a flowchart of an apparatus for implementing a method for manufacturing a syngas according to an embodiment of the present invention.

Explanation of symbols on main parts of drawing

1 air injector 2 heat exchanger

3 mixer 4 diesel

5 clutch 6 compressor

7 multistage compressor 8 high temperature filter

9 chiller

1 is a flow chart of the apparatus.

Air heated in the air injector 1 and brought to the required temperature in the heat exchanger 2 is introduced into the hydrocarbon gas in the mixer 3 (natural, associated petroleum gas, coal mine methane). And are fed to the inlet of the diesel (4). The engine is rigidly coupled to a reversible motor-generator such as clutch 5 without slipping. The electric power generated thereby is supplied to the syngas compressor 6. The syngas produced in the syngas generator (SGG) is cooled in a heat exchanger (2), purified from carbon black in a high temperature filter (8), and finally cooled in a cooler (9), followed by a drop catcher ( 10), the syngas is fed to the inlet of a multistage compressor 7 which compresses to the pressure required to convert to methanol or dimethyl ether.

Multi-cylinder four-cycle engines or dual-piston two-cycle engines are used. The number of cylinders determines the overall power and capacity. Kolomna Engineering, for example, produces 4 to 20 cylinders of diesel. Any number of engines theoretically calculated can be selected within this range.

External devices are used to realize the claimed invention group (air blowers, heat exchangers, mixers), the external devices are provided with an internal combustion engine operating in CCR mode and are preheated air for supply to the engine cylinders. perform the process required to produce (fuel charge, a mixture of hydrocarbon gases). At the end of the mixing, the compression stroke of the necessary ingredients is heated to a temperature sufficient to spontaneously ignite the mixture.

The amount of additional heating is determined by the compressive strength in the cylinder, the composition of the vapor-gas mixture, the presence of various additives, the amount of injection pressure in the engine and other factors.

In many industrial multicylinder engines, the injection temperature of the prepared mixture of individual cylinders can vary depending on the difference in distance from the inlet and the heat loss in the suction header. This temperature difference of 3 to 5 ° C is very important and the cylinder's operation will vary. Methane, the main component of the filling fuel, is not well mixed with air and can be injected with various compositions of individual cylinders. Special procedures are used to adjust the mode to prevent the influence of these two factors on the composition of the syngas produced.

Valve control in the ICE ensures instantaneous opening and closing of the inlet and outlet valves. In this case, this moment is chosen for safety reasons and as a result the oxygen of the oxidant (air) should not enter the final syngas.

The reversible motor generator is tightly coupled to the engine, where the expression "strictly coupled" is coupled to the clutch without slipping, meaning the same engine speed and the rate of electricity generation.

The constant engine speed is determined by the main frequency 50 Hz and may be 1500, 100, 630, etc., depending on the synchronous generator selected and the ICE used. The higher the engine speed, the higher the unit output capacity, but there are limitations to the speed-torque characteristics and chemical reaction speed. In all modes of operation, the selected device "diesel-electric generator" runs at a constant engine speed.

Control of the partial oxidation process of hydrocarbon gas is quite demanding, especially when the entire cycle is performed for 10 "3 seconds, when performed in a cylinder of a chemical compression reactor (modified ICE) at high speed engine operation. The critical moment according to is the moment of ignition of the mixture in the cylinder, which is obtained by the process provided in the present invention and is called controlled spontaneous ignition mode.

α and t ⁰ The value depends on the composition of hydrocarbon gas applied to one device and in each case is determined by calculation and experiment. The t ⁰ total range is from 70 ° C. to 250 ° C. The present invention further provides a method of producing syngas applicable to a catalytic process.

The application of the claimed method produces syngas using a special apparatus based on a commercial compression-ignition internal combustion engine that operates on the principle of a chemical compression reactor. The latter works as a compression engine, for example, to ignite a mixture of air and hydrocarbonaceous raw materials due to compression in external vaporization.

In particular, the use of methane, ethane and other hydrocarbons as a hydrocarbonaceous feedstock produced upon the release of a broad class of light hydrocarbons from the relevant petroleum gas will improve the ecological situation in the oil extraction and treatment area.

The specific capacity of the claimed invention is about 2.5 to 3 times higher than the known method, and the volume ratio H ₂ / CO is 1.4: 2. This is particularly important because syngas production efficiency is known to largely determine the production efficiency of methanol and synthesis engine fuels.

The use of the partial oxidation process of methane or other hydrocarbon gases in the cylinders of internal combustion engines is very attractive, which in fact acts as a compressor to compress and heat the filling fuel of the chemical reactor in which the process takes place, as well as the expansion and mechanical operation of the received product. This is because a complex chemical treatment takes place in one unit which acts as a cooler that is performed simultaneously.

High values that could be reached in the compression chemical reactor (CCR) is a very short period of time - allows to obtain a synthesis gas composition with a substantially thermodynamic equilibrium with the (10 ^"3 10" ⁴ seconds).

The start of the CCR operation, the control of operation and the control of the syngas composition are controlled in the set mode by the adjustment of the preheating temperature in the heat exchanger 2 and the excess (lack) coefficient of the oxidant, or at the starting point to the outlet temperature of the air heater 11. Is performed.

The CCR process of real time effect at the starting point and work control in set mode is performed by influencing the moment of spontaneous ignition of the vapor-gas mixture, depending on the composition of the hydrocarbon gas. For this purpose, the consumption of methanol, gasoline or other product production with a spontaneous ignition temperature lower than the primary gas makes it possible to precisely set the moment of filling fuel ignition, especially in transients, which is characterized by the composition of the syngas and the treatment of carbon black and Determine the amount of electrical output.

The start of operation of a unit with a reversible motor generator provides the opportunity to support a constant speed by line frequency without additional equipment during delivery at very low speeds, and to provide a compressor supply from its own energy source.

As a solution to the problem of CCR operation in the spontaneous ignition mode of the claimed invention group, for example, a chemical compression reactor can be used based on Minsk Motor's D-245 engine, where a wide range of modes, including long-term mode during multiple starts, can be used. The mode was activated.

The start and operation of the mode of operation in the unit is methane with an increased content of natural liquefied gas (NGL), the associated petroleum gas (a broad class of light hydrocarbons), with varying α values, at various mixture preheating temperatures, and at various starting points. This was done through additive feed and process control.

Thus, according to the claimed group, the mode of operation of a multicylinder modified four-cycle or double-piston two-cycle compression ignition internal combustion engine operating in the mode of chemical compression reactor is explosive depending on the composition of the hydrocarbon gas, for example. Partial oxidation of hydrocarbon gas by engine heating and the effect of residual amount of syngas in the cylinder, determined by re-regulation of valve control from intensive carbon black formation in areas where the hydrocarbonaceous mixture burns slowly with air before commencement of combustion In order to realize the process and start the CCR, additional heating and volume ignition in the TDC region during compression movements is due to spontaneous ignition due to the additional introduction of the required amount of liquid or gaseous material into the filling fuel with a lower spontaneous ignition temperature to the main volume. 0.3 to methane in the range of engine cylinders A surplus coefficient of 0.58 includes the supply of preheated charged fuel in an external device comprising a mixture of hydrocarbon gas and air or oxygen-enriched air. This eliminates the need for a supplemental urea supply, and the resulting syngas expands in the engine piston return stripping, which causes the composition to quench (“freezing”) and machine Achieved by routine work performance.

 After starting the CCR operation at the low heating temperature of the filling fuel due to the additional supply of gas or liquid material with a lower spontaneous ignition temperature to the main volume, the walls of the cylinder and the piston start to warm up intensively and reduce the filling fuel heating temperature. Let's do it. This is due to hot syngas, which prevents heat loss, but mainly has a low spontaneous ignition temperature remaining in the cylinder. The amount of this syngas is determined by presetting the inlet and outlet valves to accurately determine the voluntary ignition of the filling fuel in the established situation of the CCR operation.

The CCR provides a constant speed depending on the frequency of the mains and is tightly coupled to an electrical generator connected to the alternating current mains.

In order to confirm the operation of the individual cylinders connected in accordance with the difference in the strength of the compression, with the expansion of the mixture injection temperature and the heterogeneity of the composition, an additional supply of the elements necessary for the adjustment of the mixture ignition instant directly for each cylinder in the injection valve region. Chance exists.

Thus, the method is executed as follows.

1. Preheat the air in the air blower.

2. Also heat the air (oxidant) in the heat exchanger to the required temperature, for example T ° C. = 180 to 240.

3. Mix the heated air (oxidizer) and the hydrocarbonaceous raw material until α = 0.3 -0.58 and feed the mixture to the inlet of the engine (diesel).

4. Add steam and also heat up to T ° C. = 180-240.

5. Constantly feed the injected mixture (filling fuel) into the engine cylinder (within the displacement cylinder volume).

6. TDC due to additional elements (liquid or gas) which are preheated to the filling fuel during the compression movement of the engine piston, further heating the filling fuel and having a lower spontaneous ignition temperature with respect to the main volume and a temperature of 1800-2100 ° C. Perform volume spontaneous ignition in the area.

7. Start CCR operation and perform partial oxidation of hydrocarbon gas.

8. Cool the expanding product while the engine piston moves to the BDC.

9. Separate the process product containing syngas from the engine cylinder while the engine piston moves to the TDC.

10. Cool the synthesis gas to T ° C = 100 -240.

11. Purify syngas through a carbon black filter.

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

13. Compress the syngas and convert it to methanol or dimethyl ether.

Table 1 shows an example in which the method for producing a syngas according to the present invention is realized.

  Table 1

name "Natural" syngas Syngas before compression Syngas before High Pressure Cylinder in Syngas Compressor Syngas at Inlet with Methanol Synthesis Unit Exhaust syngas Composition,% vol N2 49.05 52.62 54.63 54.98 76.5 H2 24.05 25.81 26.79 26.77 11.2 O2 0.26 0.28 0.29 0.00 0.0 H20 10.41 3.91 0.25 0.10 0.1 CO 13.30 14.27 14.81 14.52 7.2 CO2 2.40 2.57 2.67 3.07 4.3 CH4 0.51 0.54 0.56 0.57 0.8 NH3 0.02 0.00 0.00 0.00 0.0 100.00 100.00 100.00 100.00 100.00 Molecular Weight 21.050 21.271 21.469 25.69 Temperature ℃ 370.00 45 35 140-150 200 Specific yield, kg / kg natural gas 8.095 7.625 7.387 7.366 6.336 Minimum Combustion Heat KJ / nm ³ 4459 2231 Consumption, kg / h 11383 10718 10384 10354 8907

The main feature of the above is that it provides reliable ignition and operation of the unit through the application of the most diverse hydrocarbonaceous gases (natural gas, mine coal methane, and related petroleum gases) with simultaneous generation of electric forces. The claimed invention provides a method for producing a synthesis gas that can be applied for further catalytic treatment.

The application of the claimed method permits the production of syngas, which employs special equipment based on chemical compression ignition internal combustion engines operating according to the principles of chemical compression reactors. The latter acts as a compression engine, ie ignition of a mixture of air and liquid hydrocarbonaceous raw materials, based on compression on external vaporization.

In the release of a broad residue of light hydrocarbons from the relevant petroleum gas, in particular applying methane, ethane and other hydrocarbons as the resulting liquid hydrocarbonaceous feedstock will improve the ecological situation in the petroleum extraction and treatment area.

The specific yield of the claimed invention is 2.5 to 3 times that of the known method, and the volume ratio H2 / C0 is 1.4: 2. This is particularly important because the synthesis gas production efficiency largely determines the production efficiency of methanol and synthesis engine fuels.

It is highly attempted to apply a partial oxidation process of methane or other hydrocarbon gas in the cylinder of an internal combustion engine, which is also a compressor where a complex chemical process actually compresses and heats the packed fuel in a chemical reactor in which the process takes place. This is because the expansion of the product received takes place and the mechanical work can be carried out in a single unit operating as a cooler which is carried out simultaneously.

The high values achievable in chemical compression reactors (CCR) allow to accept substantially thermodynamically equivalent syngas compositions for very short time periods (10-3 to 10-4) seconds, with the amount of carbon black being minimal do.

There may be several alternatives to CCR operations that are primarily dependent on the ignition of the vapor and gas mixture. The basic difficulty is to ignite the vapor and gas mixture with a low excess coefficient of oxidant that synthesis gas of acceptable composition can reach. Generally this is a slow burning zone, where high energy sources of ignition are necessary to sustain the chain reaction of combustion.

Claims (3)

Preparation of a mixture of hydrocarbonaceous raw materials, steam and air or oxygen enriched air-filled fuel having an excess coefficient of air (oxidant) from 0.3 to 0.58 to methane, further heating of the formed fuel, Constant supply of fuel to the engine cylinder, Additional heating of the filling fuel during compression movement with the cylinder piston, Top dead center (TDC) due to spontaneous ignition additionally introduced into the packed fuel of liquid or gaseous materials having a lower spontaneous ignition temperature relative to the main volume of the fuel, causing the start of operation of the chemical compression reactor and partial oxidation of the hydrocarbonaceous mixture. Volume ignition of the filling fuel in the zone, -Filling the fuel in the volume of the internal combustion cylinder, Then during the return strip, the expansion and cooling of the process product formed during the movement of the engine piston to the bottom dead center, Recovery of process products containing syngas, Then cooling the syngas, Purification of process products containing syngas from carbon black, Final cooling of the process product containing syngas and conversion to methanol or dimethyl ether, During the process of partial oxidation to the chemical compression reactor (CCR) unit, the entire operation is maintained by the residual gas in the cylinder, the amount of residual gas in the cylinder is re-adjusted valve adjustment, additional heating and charging due to engine preparation A method for producing syngas in a device consisting of a multicylinder four-cycle or double-piston two-cycle compression-ignition internal combustion engine operating in the manner of a chemical compression reactor, controlled by external control of the fuel heating temperature. The method of claim 1, The engine described above Air supply and hydrocarbonaceous raw material supply system, A heating system comprising air-heater, heat exchanger and mixer, comprising preheating of air and hydrocarbonaceous raw materials, Syngas cooling system consisting of a reversible motor-generator which produces heat exchangers and coolers, provides power to a multi-stage syngas compressor and is tightly coupled to the engine, Also hot carbon black collection filter for syngas purification cooler, Providing a drop catcher, Control of the operation of the engine when starting the engine in the manner of a chemical compression reactor, and control of the syngas composition produced, regulates the excess coefficient of oxidant and the preheat temperature in the heat exchanger or the start-up discharge temperature of the air heater in the fitted manner. Has the difference that Operating in the manner of a chemical compression reactor with a system of inlet and outlet valves, wherein the apparatus consists of a multicylinder four-cycle or two-piston two-cycle compression-ignition internal combustion engine. The method according to claim 1 or 2, An additional supply to verify the operation of the individual cylinders may be provided (directly in the region of the injection valve) for the control of the ignition moment of the mixture in each cylinder, The essential components are natural gas or petroleum gas, methanol or water-methanol mixtures, and further methanol or dimethyl ether, generated during the petroleum fractionation process.

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