Method of realization of the chemical transformations by compression of the gas-containing mixtures

FIELD: chemical industry; methods of realization of the chemical transformations by compression of the gas-containing mixtures.

SUBSTANCE: the invention is pertaining to the chemical technology and may be used in chemical industry for realization of the different chemical transformations, for example, for the air nitrogen fixation or for production of the synthesis gas. The method of realization of the chemical transformations by compression of the gas-containing mixtures includes the two-stage superadiabatic compression of the reaction mixture in two successive strokes by the piston in the cylinder of the superadiabatic compression reactor divided into the main and additional chambers the transversal septum made with a possibility of the mixture bypassing. The second stage of the superadiabatic compression on each stroke is realized simultaneously with the bypassing of the reaction mixture into the additional chamber of the cylinder. At that the compression power is kept equal on the first and the second compression strokes by selection of the value of the relative volume of the additional chamber of the cylinder β = V2/(V1 + V2), where V1 is the volume of the main chamber, V2 is the volume of the additional chamber, which for the pressure of up to 300 atm should be of no less than 0.01, and the injection of the reaction mixture into the reactor is performed before the first stroke of the two-stage compression at the piston motion to the lower dead point. The simultaneous bypassing and compression of the mixture at the second stage of the superadiabatic compression on each stroke is performed at constant pressure. Before or in the beginning of the second compression stroke the component consisting out of the polyatomic molecules is introduced. At realization of the exothermal chemical transformations the heat-accumulating component with the developed surface is mounted in the additional chamber of the cylinder. The invention ensures the reliable and high-effective running of the chemical reactions.

EFFECT: the invention ensures the reliable and high-effective running of the chemical reactions.

4 cl, 1 dwg

 

The invention relates to chemical technology and can be used in the chemical industry for a variety of chemical transformations, for example, to bind nitrogen from the air by its oxidation to produce synthesis gas from rich uglepodgotovitelnyj mixtures, in particular, when the partial oxidation of methane.

One of the main problems of chemical production is the development of highly efficient and economical process and apparatus for their implementation. In the framework of the problems in the most successful technological solution is the method of carrying out chemical reactions using chemical reactor compression (HRS)based on internal combustion engine (ice). HRS is a thermal machine cycle operation, in which the adiabatic compression of the reaction mixture by the piston to the temperature required for rapid course of chemical reactions. Then in the expansion stage of the reaction products are cooled and are hardened. Thus, HRS combines the heater, the actual reactor and the quenching device (Kolmanovskii Y.A. and other Pulse compression of gases in chemistry and technology. M.: Nauka, 1982, s).

But there is a fundamental limitation for wide application such reacto is s, associated with the inefficiency of the adiabatic compression of polyatomic gases with low adiabatic: γ˜1.2. This means that for many practically important reactions, in particular for the implementation of the partial oxidation of methane at a characteristic temperature Tmax˜1500 required To compress the gas up too high pressure Pmax˜1000 bar.

A method of obtaining synthesis gas (Patent RU 2096313 C1, CL 01 In 3/36, publ. 20.11.97), in which the partial oxidation of a mixture of hydrocarbons with air is carried out in the cylinders HRS based on the internal combustion engine of the compression type, with cylinders HRS serves preheated to 200-450°With a mixture of hydrocarbons with air when the air excess factor α=0.5-0.8, a compression mixture is conducted to the ignition and obtaining a temperature of 1,300-2,300°for a period of 10-2-10-3with, the cycle is repeated with a frequency exceeding 350 min-1. The rotation of the crankshaft HRS is provided by an external actuator, such as an electric motor.

This known method is only suitable for moderately enriched uglepodgotovitelnyj mixtures requires significant design complexity HRS due to the installation of the external heating of the mixture and not a high specific efficiency due to the decrease of the density supplied to the cylinders HRS with the art.

There is a method of destruction of toxic compounds (Patent RU 2072477 C1, class F 23 G 5/00, F 23 G 7/00, publ. 27.01.1997), which destroy the object, the fuel and air with the air excess factor α from 0.5 to 1.5 served in HRS, where it is subjected to pulse compression-expansion at maximum temperature pulse 1500-3000 K, the maximum pressure pulse 9-20 MPa and characteristic times 10-3-10-2C. Exhaust from the first reactor gases are again subjected to pulse compression-expansion at maximum temperature pulse 1500-2300 To the maximum pressure pulse 9-20 MPa and characteristic times 10-3-10-2C.

This method is to provide two successive cycles of compression requires significant design complexity HRS through the use of an additional cylinder. The method does not have high specific efficiency as in the second cylinder of the reactor served chilled mixture after its expansion in the first cylinder of the reactor.

The closest in technical essence and the achieved result of the present invention (the prototype) is a method of performing chemical transformations compression of the fuel-air mixture (FA) when the internal combustion engine (Patent RU 2162530 C1, class F 02 B 75/02, F 02 B 23/00, publ. 27.01.2001), in which the compression of the fuel assemblies in the engine (chemical reactor sverkhadiabaticheskoe compression - HRS carried out in two successive stages in nasoenteric mode - with the increase of entropy (sverkhadiabaticheskoe compression) - why use a cylinder divided by a transverse partition, configured to bypass the fuel assemblies. This method can be implemented as a 4-stroke internal combustion engine (one step of the two-stage compression), and 6-stroke - with two cycles of compression, divided idle speed.

When using the 4-stroke internal combustion engine in the first stage of compression by the movement of the piston from bottom dead center (BDC) to the closed partition produce heating of the fuel Assembly by compression to a temperature T1=(1.5-2)T0where T0- the initial temperature of the FA, then the hole in the wall open, carry bypass the heated fuel assemblies in the space of the cylinder behind the partition and conduct the second stage of compression FA movement of the piston to the top dead center (TDC) until a temperature TWith=(4.2-7.8)T0with subsequent ignition and combustion of the fuel assemblies.

When using a 6-stroke internal combustion engine successive stages of two-stage nasoenteric compression can be combined with cycles of compression motor, then the first stage compression ratio of FA to a temperature T1conduct an open hole in the wall by movement of the piston to TDC, then the hole in the wall closed and implement idling piston to BDC at the end of which a hole in the wall open, and the cylinder zapolnyaetsya with temperature T 1and carry out the second stage of compression of the fuel Assembly to a temperature TWiththe movement of the piston to TDC. To achieve higher temperatures, such as poor combustion of fuel assemblies, the two-stage sverkhadiabaticheskoe compression FA carried out at each cycle of the 6-stroke internal combustion engine, for which the first stage compression FA on the first beat of up to T1begin at the closed partition, which is then open and perform bypass the mixture into the space behind the partition, followed by a second stage of compression (the first time) the movement of the piston to TDC before reaching TWithafter which the partition is closed and implement idling speed of the piston to the bottom dead point at the end of which the partition is open for cylinder filling, the heated mixture with a temperature TWithclose the partition and repeat the two-stage sverkhadiabaticheskoe compression FA at the second clock cycle engine operation similar to the first beat, but with T0=TWith.

The disadvantage of the described method (prototype) is a limited opportunity to use ice as HRS, so as to ensure operation of the internal combustion engine according to this method, you only need to use exothermic fuel assemblies of a particular composition, because it is not possible to achieve at pressures up to 300 atmospheres of high temperatures (of the order of 2500-3000 K)necessary for the implementation of endothermic the x reactions, while HRSS must be suitable for performing chemical transformations in the gas mixtures of different composition, including for carrying out endothermic chemical reactions occurring with absorption of heat (for example, the binding of air nitrogen him oxidation), as well as for reactions performed using mixtures containing no free oxygen (for example, the reaction of the pyrolysis of hydrocarbons, hydropyrolysis hydrocarbons and so on).

Object of the present invention is to provide such a method of carrying out chemical transformations compressed gas mixture in HRS, which would provide reliable and highly efficient flow as exothermic chemical reactions and endothermic, would allow for reaction mixtures containing no free oxygen, and would increase the efficiency of the process. In addition, the inventive method should be able to use as HRS engine, slightly modified (according to the method prototype) compared to conventional internal combustion engines, manufactured by the industry.

The solution of this problem is achieved by the proposed method of carrying out chemical transformations compressed gas mixture comprising the two-stage sverkhadiabaticheskoe compression of the reaction mixture in two consecutive cycles of the piston cylindre chemical reactor sverkhadiabaticheskoe compression, divided into basic and additional camera transverse partition made with the possibility of bypass mixture, in which, according to the invention, the second stage sverkhadiabaticheskoe compression on each step carried out simultaneously with the bypass of the reaction mixture in the secondary chamber of the cylinder, the pressure of the compression provide the same on the first and second cycles of compression by selecting the magnitude of the relative amount of additional cameras cylinder β=V2/(V1+V2), where V1- the volume of the main chamber, V2- the amount of additional camera, for which a maximum pressure of 300 ATM should not be below 0.01, and the inlet of the reaction mixture in the reactor is carried out before the first beat of the two-stage compression during movement of the piston to the bottom dead point.

To improve the efficiency of the process of simultaneous bypass and compressing the mixture in the second stage sverkhadiabaticheskoe compression on each step is carried out at constant pressure.

To improve the efficiency of the compression component of polyatomic molecules is introduced into the reactor before or at the beginning of the second compression stroke is when the piston toward the bottom dead center position (idling) or to the upper dead point (the second cycle).

To achieve maximum efficiency of the reactor when carrying out exothermic chemical reactions in D. the additional reactor chamber set the heat storage element with a developed surface.

The proposed method was developed on the basis of a detailed theoretical and experimental studies of the process of heating and chemical reactions between reactants of different gas mixtures during their two-stage sverkhadiabaticheskoe compression in two consecutive cycles to model ballistic installation with a free piston, made in the form of a cylinder with two chambers - the main (volume V1a secondary volume V2)separated by a transverse partition wall is configured to bypass the mixture. The piston performs a reciprocating motion in the main chamber of the cylinder. Examined the relationship of such process parameters as the composition of the reaction mixture, the compression of the mixture, its temperature and pressure.

The principal result of the test is the fact that endothermic reactions by sverkhadiabaticheskoe compression gas mixtures. In the proposed method, two-stage sverkhadiabaticheskoe compression reaction mixture is carried out in two successive cycles of operation HRS. Two-stage sverkhadiabaticheskoe compression in the first stage reactor allows to heat the gas mixture to a temperature of 1000-1200 K at a maximum pressure of 300 ATM. The repetition of the two-stage sverkhadiabaticheskoe compressed the I in the second stage HRS raises the temperature of the reaction mixture up to 2500-3000 K. The maximum pressure at the second clock cycle is not increased and remains the same as in the first step, which is achieved by selection of the magnitude of the relative amount of additional cameras cylinder βthat is determined by the required reaction pressure and a maximum pressure of 300 ATM should not be below 0.01.

The proposed method provides an effective reaction bind nitrogen from the air with high yield nitric oxide (at a temperature of 2800-3000 K To 6%):

N2+O2→2NO

Investigate the possibility of obtaining the proposed method of synthesis gas by the incomplete oxidation of methane in mode C without any external preheating of the reaction mixture. In accordance with the reaction equation for the oxidation of methane to synthesis gas oxygen source methane concentration should be about 30%:

CH4+0.5O2+1.9N2→CO+2H2+1.9N2

Theoretical analysis shows that this process is feasible and the method prototype in compression λs˜20 and with the use of coercive means of igniting the mixture. In the proposed method by conducting the second stage sverkhadiabaticheskoe compression simultaneously with the bypass of the reaction mixture in the secondary chamber of the cylinder is achieved at higher temperatures, the and thereby surround the ignition of the mixture even at a low compression ratio λ s=13.9, which allows to obtain a synthesis gas with greater efficiency. When the methane content in the reaction mixture is not more than 10-15%, that is, when increasing ekzotermicheskie reaction, obtaining a synthesis gas according to the proposed method in a single quantum two-stage sverkhadiabaticheskoe compression.

In experiments with sverkhadiabaticheskoe compressing mixtures of the proposed method was demonstrated the possibility of partial oxidation of hydrocarbons such as methane, propane, isooctane.

See our chart (see drawing) illustrate the implementation of the claimed method in the above model setup. The relative amount of additional camera β=V2/(V1+V2)=0.07. The maximum pressure of 100 ATM. The compression ratio λs=13.9. The number of revolutions of the crankshaft of the reactor N=3000 rpm/min

The drawing shows:

(a) diagram of the pressure change, where curves 1 reflect changes in the pressure in the main chamber of the cylinder with two-stage sverkhadiabaticheskoe the compression is carried out in two consecutive cycles, curves 2 - change in pressure in the secondary camera (in two consecutive cycles). (For comparison, curve 4 shows the variation of pressure with single-stage compression in conventional internal combustion engines).

b) diagram of temperature change on katarikawe 1 reflect changes in the temperature in the main chamber of the cylinder with two-stage sverkhadiabaticheskoe compression, carried out in two consecutive cycles, curves 2 - change of temperature in the secondary camera (in two consecutive cycles). (For comparison, curve 4, which shows the temperature change when the one-stage compression in conventional internal combustion engines).

Curve 3 is the diagram of the bypass opening - refers to both charts. The horizontal axis represents the dimensionless time τ=tp/ttwhere tp- real time tt- clock time (determined by the number of revolutions of the crankshaft N).

The inlet of the reaction mixture (air) in the reactor is carried out before the first compression stroke when the piston to BDC (τ=0). After filling the reactor bypass hole close and begin the first stage of two-stage sverkhadiabaticheskoe compression on the first beat of the movement of the piston to TDC before reaching the pressure in the main chamber 100 ATM (see chart a), curve 1), after which the hole in the wall opening (see curve 3) and carry out simultaneous bypass the reaction mixture in the secondary chamber and the compression in the second stage sverkhadiabaticheskoe compression continued movement of the piston to TDC.

In the experiment, reflected in the drawing, the flow area of the openings in the partition in the process of simultaneous flow and compression of the mixture in the second stage sverkhadiabaticheskoe compression on each of the act) is automatically changed so in order to maintain a constant gas pressure in the main chamber, which ensures maximum performance compression and increases the efficiency of the process. The highest effect was achieved while maintaining a constant maximum pressure.

After the piston reaches TDC (τ=0.5) is more than 90% of the entire mass of the gas is in the additional chamber of the cylinder with a temperature of 1200 K (see chart b), curve 2). The bypass valve closes and the piston moves towards BDC, creating a vacuum in the main chamber of the cylinder. In time τ=0.9 valve open (see curve 3), and hot gas without doing the work flows in the main camera. At the moment the piston reaches BDC (τ=1) hole in the wall closed. The first stage reactor and idling completed, but now the cylinder is hot gas.

The second compression stroke of hot gas was similar to the first two stages, with the final compression temperature in the secondary chamber reached approximately 2500 K (see chart b), curve 2). The maximum gas pressure in the second stage was the same as in the first and did not exceed 100 ATM that was specified by the value parameter β=0.07, which is selected so that the final pressure of compression in the second stage would correspond to the maximum pressure in the first compression stroke (in the experiment, presented in black the hedgehog, P2=P1=100 ATM). By the end of the compression in the second stage - after the piston reaches TDC at the time τ=1.5 to about 98% of the entire mass of the gas is in the additional chamber of the cylinder and the process is complete. When the movement of the piston to BDC is the free expansion of the reaction products, cooling, hardening and subsequent conclusion. In the presented charts experiment NO output was 1%. With increasing temperatures up to 3000 K, and pressure, respectively, up to 300 ATM output reached 6%.

Thus, the above example of the proposed method shows that when air is compressed in two bars in HRS achieved a high temperature of 2500 K at a final pressure of 100 ATM. (In normal HRS temperature compression in 2 times below even when the squeezing pressure of 250 atmospheres. In order to achieve a temperature of 2500 K in the usual HRS, it is necessary to compress the air to a pressure of more than 2000 ATM). In the method prototype the maximum temperature 2300 K is achieved at a significantly higher pressure is not lower than 300 ATM.

The compression efficiency of the reaction mixture containing polyatomic molecules (of three or more atoms), lower due to the reduction of the adiabatic exponent of the mixture. As polyhydric components of the reaction mixture can be used, for example, hydrocarbons or substituted hydrocarbons. The compression efficiency can be significantly increased if the OS is out of the inlet (injection) component of polyatomic molecules before the second compression stroke - during idling when the movement of the piston to BDC or during the second compression stroke when the piston to TDC. In this case, in the first compression stroke will be effective compression gas consisting only of diatomic molecules (e.g., air or hydrogen), which are characterized by high the adiabatic exponent: γ˜1.4.

An additional possibility to increase the efficiency of the proposed method appears if the reaction of the chemical transformation occurs with evolution of heat. In this case, an additional chamber of the cylinder HRS install thermal storage element with a developed surface (the set of thin metal plates, porous ceramics), which will absorb part of the heat of reaction, starting near the maximum temperature. Then the stock heat will be transferred to a fresh portion of the cold reaction mixture entering the chemical reactor before the two-stage surfaceanalysis compression, that is implemented technological method of heat recovery, resulting in an additional increase of the maximum temperature compression 30-60%, and consequently, increases the efficiency of the process.

The use of the claimed invention will allow the way HRSS, which will provide reliable and highly efficient reactions chemical transformations in who the ear mixes, held, including with the absorption of heat (endothermic reactions), and will also allow for reaction mixtures containing no free oxygen. The proposed method provides increased efficiency of the process for chemical reactions to produce heat, when installed in HRS thermal storage element with a developed surface. As HRSS you can use ice, manufactured, subject to minor modifications.

1. The method of carrying out chemical transformations compressed gas mixture comprising the two-stage sverkhadiabaticheskoe compression of the reaction mixture in two consecutive cycles of the piston in the cylinder of a chemical reactor sverkhadiabaticheskoe compression, divided into main and secondary camera with a longitudinal partition, configured to bypass the mixture, characterized in that the second stage sverkhadiabaticheskoe compression on each step carried out simultaneously with the bypass of the reaction mixture in the secondary chamber of the cylinder, the pressure of the compression provide the same on the first and second cycles of compression by selecting the magnitude of the relative amount of additional cameras cylinder β=V2/(V1+V2), where V1- the volume of the main chamber, V2- the volume of the secondary camera, which for pressures up to 300 atmospheres Dol is to not be below 0.01, and the inlet of the reaction mixture in the reactor is carried out before the first beat of the two-stage compression during movement of the piston to the bottom dead point.

2. The method according to claim 1, characterized in that the simultaneous bypass and compressing the mixture in the second stage sverkhadiabaticheskoe compression on each step is carried out at constant pressure.

3. The method according to claim 1, characterized in that the reactor before or at the beginning of the second compression stroke introduce a component of polyatomic molecules.

4. The method according to claim 1, characterized in that the additional reactor chamber set the heat storage element with a developed surface.



 

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7 cl, 2 dwg

FIELD: power engineering; methods of production of hydrogenous gas in the turbine-generator installations.

SUBSTANCE: the invention is pertaining to the field of power engineering, in particular, to the method of production of hydrogenous gas in a turbine-generator installation. The method of production of hydrogenous gas is realized in a turbine-generator installation containing: the I-st, the II-d and the III-d stages; a framework, on which there is an installed fuel tank for two-component mixture H2О +CnH2n+2 with a stirrer and a drive unit; a turbine burner system; an induction heater of the I-st stage; a pulse source of ignition for a start-up and a system of gas pipelines. At that the two-component mixtureH2О +CnH2n+2 is fed to the fuel tank, start the drive and exercise its stirring action and pumping under pressure in the I stage of the turbine-generator installation, where with the help of an induction heater conduct heating up to 500°C. Then the two-component mixture transformed into a gaseous state is feed in the turbine burner system and from the pulse source of ignition realize the I-st stage start-up. After that a part of the gas is fed into the II-d stage, keeping the heating up to 1000°C; and the other part of the gas is fed into the turbine burner system for provision of the gas heating at the I-st, the II-d and the III-d stages. At that after the II-d stage the gas for its final heating up to the temperature of 1300°C is fed into the III-d stage with production of a hydrogenous gas, which is fed into turbine burner system. The invention ensures a decrease of the power input of the process in a combination with utilization of a low-cost hydrocarbon mixture.

EFFECT: the invention ensures a decrease of the power input of the process in a combination with utilization of a low-cost hydrocarbon mixture.

3 dwg

FIELD: chemical industry; methods and the devices for production of carbamide from ammonia and carbon dioxide.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the methods and the devices for production of carbamide from ammonia and carbon dioxide. The method of production of carbamide includes the interaction of ammonia and carbon dioxide in the zone of synthesis at the heightened temperatures and pressures with formation of the melt of the carbamide containing carbamide, water, ammonium carbamate, ammonia and carbon dioxide. The carbamide melt distillation conduct at the heat feeding on the two stages of pressure preferentially at 15-25°C and 2-5 kgf/cm2. The carbamide melt distillation on the first step of the pressure conduct sequentially in two zones. In the first zone the distillation is conducted adiabatically or at the heat feeding, and in the second zone - at the heat feeding in the stream of carbon dioxide. The condensation-absorption process at refrigeration of the gases of the distillation is conducted with utilization of the aqueous absorbers. The formed aqueous solutions of the carbon- ammonium salts are recycled from the stage of the condensation-absorption of the gases of the distillation of the second step to the stage of the condensation-absorption of the gases of distillation of the first step, and also from the stage of the condensation-absorption of the gases of distillation of the first step into the zone of the synthesis. The evaporation of the aqueous solution of carbamide is exercised in some steps at the heat exchange between the gases of the distillation of the first step and the aqueous solution of carbamide at the stage of the preliminary evaporation. The installation for production of carbamide consists of: the reactor of the carbamide synthesis; the device with the heat feeding from the external source for distillation of the carbamide melt produced in the reactor of the carbamide synthesis at the first step of the pressure and consisting of the column of distillation melt of the first step and the film-type heat exchanger; the device with the heat feeding for the distillation of the carbamide melt on the second step of pressure; apparatuses for evaporation at heating of the aqueous solution of the carbamide produced on the second step of distillation. The devices for condensation-absorption at refrigeration of the gases of the distillation of the both steps switch on the heat exchanger-recuperator for heat interchange between the gases of the distillation of the first step and the aqueous solution of carbamide. The installation also contains a means for feeding of ammonia and carbon dioxide into the reactor of synthesis of carbamide, feeding of the carbamide melt from the reactor of synthesis into the column of distillation of the first step, from the column of distillation of the first step into the film-type heat exchanger and from the film-type heat exchanger into the device for distillation of the second step, the aqueous solution of carbamide from the device for distilling of the second step into the heat exchanger-recuperator and from the heat exchanger-recuperator - into the apparatus for the subsequent evaporation; the gases of distillation from the device for distilling of the first step - in the heat exchanger-recuperator and from the heat exchanger-recuperator - into the device for condensation-absorption of the gases of distillation of the first step; the gases of distillation from the apparatus for distillation of the second step - into the device for condensation-absorption of the gases of distillation of the second step; the solution of the carbon-ammonium salts from the device for condensation-absorption of the gases of distillation of the second step - into the device for condensation-absorption of the gases of distillation of the first step and from the device for condensation-absorption of the gases of distillation of the first step - into the reactor of synthesis, a means for feeding of carbon dioxide into the film-type heat exchanger. The technical result of the invention is the increased degree of the heat recuperation of the production cycle and reduction of he quantity of the heat exchangers using the heating steam from the external sources.

EFFECT: the invention ensures the increased degree of the heat recuperation of the production cycle and reduction of he quantity of the heat exchangers using the heating steam from the external sources.

8 cl, 3 ex, 3 dwg

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