Method for production of synthesis gas and a device for its implementation

 

(57) Abstract:

The invention relates to the processing of hydrocarbon raw materials, and specifically to obtain synthesis gas from gaseous hydrocarbons. Method for production of synthesis gas comprises mixing the hydrocarbon with air in the ratio corresponding to the ratio of the excess oxidizing agent is less than 1, the forced combustion of the air-hydrocarbon mixture and the partial oxidation of hydrocarbons with oxygen in the reaction zone, cooling and subsequent withdrawal of the product of the process containing synthesis gas, and the introduction of a new portion of hydrocarbons and air, thus heating of the hydrocarbon and air is carried out at elevated pressure and temperature, 50-100oC below the temperature of ignition mixtures thereof, the process of partial oxidation of hydrocarbons is carried out in flowing the combustion chamber, with forced ignition is carried out at a ratio of excess oxidant =0,6-0,7, and after warming up the flow of the combustion chamber, the ratio of oxygen to hydrocarbon raw material is brought to a level corresponding to the value = 0,30-0,56. The process of cooling of the products of partial achilees gas includes camera partial oxidation of hydrocarbons with oxygen, mixer, system expansion and cooling of the products of partial oxidation and output of the synthesis gas. It also has a system of preheating hydrocarbon and air flow regulator hydrocarbons. The camera partial oxidation of hydrocarbons contains a means of ignition and made in the form of a flow of the combustion chamber, inlet through which antipredatory lattice docked mixer, and the mixer is connected to the inlet pipe of hydrocarbons and the inlet air pipe, both said inlet pipe is covered with a gap recuperator pipe, one end of which is connected to the output of flow of the combustion chamber, and the other, open end communicates with the cavity of the heat exchanger, which is formed by a shell bounding the cavity around recuperating pipe. In addition, in the cavity of the heat exchanger are tubular heater hydrocarbons and tubular air heater. Thus to one end of the tubular heater hydrocarbons connected to the flow regulator of hydrocarbons, and the other end through the mentioned inlet pipe is connected with a mixer. One end of the tubular heater of the hcpa shall ployment provided with a fitting conclusion of his oral synthesis gas. The invention improves the efficiency of the process. 2 C. and 10 C.p. f-crystals, 1 Il.

The invention relates to the field of hydrocarbon processing, and specifically to the oxidative conversion of hydrocarbon gases in the synthesis gas.

There are various ways to produce synthesis gas from hydrocarbons, including partial oxidation of methane with oxygen

CH4+0.5 O2=CO+2H2< / BR>
It is known, patented USSR 1831468, MKI 5 C 01 B 3/38 "Method for production of synthesis gas from a hydrocarbon feedstock, which comprises a mixture of hydrocarbons and the oxidant is oxygen or oxygen-containing gas or vapor, and conversion of the mixture in the presence of a solid catalyst at the temperature in the reaction zone is not less than 93oBelow the point of ignition of the mixture, and the speed of introduction of the mixture into the reaction zone exceeds the speed of the process of breakthrough flame. The known method requires the use of a highly selective catalyst. The main disadvantage of invention under the patent of the USSR 1831468 is the high cost of the catalyst, the possibility of destruction of the catalyst due to local overheating, the possibility of formation of soot.

Known the m layer of the catalyst, for U.S. patent 5.980.782, MKI C 01 B 3/24, 1999, in which gaseous components are pre-heated and Inuktitut in the reaction zone for a period less than the time of ignition, i.e. less than 9 MS with a speed of from 8 to 333 m/s produced synthesis gas is cooled and sent for further processing.

The main disadvantage of the invention in U.S. patent 5.980.782 is the need for a catalyst.

The known method for production of synthesis gas by RF patent 2096313, MKI 6 01 3/36, which eliminates the use of catalysts. The known method is carried out in the following order:

- pre-mixed hydrocarbon feedstock with air to =0,5-0,8;

- heat the resulting mixture to a temperature of 200-450oC;

- served hot mixture into the volume of the cylinder of the internal combustion engine of the compression type with the movement of the piston to the bottom dead point;

- compression of the mixture in the cylinder by movement of the piston to the top dead point to its ignition and obtaining a temperature of 1,300-2,300oWith a period of 10-2- 10-3carry out the partial oxidation of hydrocarbons;

- next, cool the resulting products of the oxidation process, expanding them when d is ocess, containing synthesis gas.

The described cycle is repeated with a frequency exceeding 350 min-1. The main drawback of the method according to the patent of the Russian Federation 2096313 is the lack of continuity of the process of obtaining synthesis gas because of its periodicity, which reduces the efficiency of the process.

Known apparatus for producing synthesis gas by RF patent 2096313, MKI 6 01 3/36, which carry out the above method for production of synthesis gas. The device is based on the internal combustion engine of the compression type, the cylinder of which is a closed reaction volume, which houses the piston. The intake and exhaust valves located in the area of the top dead point of the cylinder while the intake valve is associated with a mixer oxidant and hydrocarbon raw materials and their device heating, and an exhaust valve associated with the receiver oxidation products. The piston cylinder through a crank mechanism associated with the drive.

The described device for the generation of synthesis gas works in cycles with a frequency of movement of the piston in the cylinder is not less than 350 min-1. Less frequency cycle leads to relatively lower speed compression, which does not provide an ignition RAB is the inability to ensure continuity of the process of formation of synthesis gas, that reduces the efficiency of the process of its receipt.

There is also known a method for production of synthesis gas by RF patent 2120913, MKI 6 01 3/36, adopted as the closest analogue of the proposed method. Method for production of synthesis gas includes the partial oxidation of hydrocarbons with oxygen of the air in the cylinder of the internal combustion engine when a ratio of the amount of oxygen to the amount of hydrocarbons = 0.4 to 0.5. However, at the moment the piston position at top dead center, a part of the mixture of hydrocarbons with air in the ratio of oxygen to the amount of hydrocarbons =0,8-1,2 in the amount of 5-10% of the volume of the original mixture in isolation from it is subjected to fire and deep oxidation. Next mix the products of deep oxidation with the original mixture in the working volume of the cylinder and ignite it. Expand and cool the products of the process when the movement of the piston to the bottom dead point, remove the products from the process containing synthesis gas from the reaction zone during movement of the piston to the top dead point. Then the cycle is repeated. Due to the fact that in the known method a portion of hydrocarbons with air at a =0.8 to 1.2 in the amount of 5-10% of the volume of the original mixture at Palaeogene from the main volume of the mixture, and then this part of the injected high-energy jet in the main volume of the mixture in the working volume of the cylinder the initial mixture is subjected to intensive mixing and ignition, improved performance of this method for production of synthesis gas. The main disadvantage of the known method of producing synthesis gas by RF patent 2120913 is the lack of continuity of the process of conversion because of its periodicity, which reduces performance.

A known device for producing synthesis gas by RF patent 2120913, MKI 6 01 3/36, which is accepted as the closest analogue (prototype) of the claimed device. Using the known installation carry out the above method for production of synthesis gas. The installation includes based on the internal combustion engine chemical reactor compression, including the cylinder and the camera pre-ignition. The cylinder is placed a piston and an inlet valve through which the cylinder and into the chamber prior to ignition serves a mixture of hydrocarbons with air. On the cylinder, an exhaust valve, which is to display the products of the process. The camera pre-ignition has a separate valve through coset 5% of the cylinder volume when the piston position at top dead center.

In the process for production of synthesis gas at the position of the piston near top dead point of the hydrocarbon-air mixture of the composition in the chamber prior to ignition is subjected to ignition from sparks. Next, high-energy jet of highly turbulizing gas was injected at a rate of about 10-3m/s in the working volume of the cylinder during the 10-3-10-2C. In the working volume of the cylinder the initial mixture is subjected to mixing with the products of deep oxidation and ignition, the process of partial oxidation. When the movement of the piston in the cylinder to the bottom dead point is the extension products of the process, the cooling and hardening. Subsequent movement of the piston to the top dead point of the products of the process is withdrawn from the cylinder through the exhaust valve. Flow into the cylinder and into the chamber prior to the ignition of the fresh mixture is produced when the movement of the piston to the bottom dead center and the opening of the intake valves. So cyclically setup works and is a method for production of synthesis gas.

The main disadvantage of the plant for producing synthesis gas by RF patent 2120913 is the inability to achieve a continuous process of conversion uglevodorodnaya installation is not strong enough and durable enough, because her work is related to the cyclic movement of the main parts, such as piston, crank and valves.

Before the inventive method for production of synthesis gas tasked to implement a continuously flowing process, without cycles, thereby to improve its performance.

The task before the method for production of synthesis gas is solved by a method comprising mixing the hydrocarbon with air in the ratio corresponding to the ratio of the excess oxidizing agent is less than 1, forced combustion of the air-hydrocarbon mixture and the partial oxidation of hydrocarbons with oxygen in the reaction zone, the expansion and cooling with subsequent withdrawal of the product of the process containing synthesis gas, and the introduction of a new portion of hydrocarbons and air, that you are carrying out heating of the hydrocarbon and air at elevated pressure and a temperature of 50-100oC below the temperature of ignition mixtures thereof, the process of partial oxidation of hydrocarbons is carried out in flowing the combustion chamber, with forced ignition is carried out at a ratio of excess oxidant or =0.6-0.7 and after warming up protonotary heated hydrocarbon and air is conducted into the heat exchanger by the heat of the cooled products of partial oxidation.

Mutual mixing of the hydrocarbon and air is carried out after completion of preheating in the heat exchanger.

The expansion and cooling of the products of the process of partial oxidation with the purpose of quenching is performed on the output from running the combustion chamber in the closed volume of the heat exchanger, with the simultaneous transfer of heat from the hydrocarbon feedstock and the air coming through the tubular heater to the input of the mixer.

The process of partial oxidation of methane is taken as the hydrocarbon, oxygen is carried out in flowing the combustion chamber at a temperature equal to 1200-1300oWith, and when the ratio of oxygen to methane, the appropriate value =0,34-0,36.

The process of partial oxidation by oxygen of associated petroleum gas containing 10-15% vol. ethane and propane and adopted as hydrocarbons, carried out at a temperature in flowing the combustion chamber equal to 1200-1300oWith, and when level =0,34-0,36.

The process of cooling of the products of partial oxidation, leaving the reaction zone is conducted at a speed of not less than 3000oWith/s

The technical result, namely the process of obtaining the both produce synthesis gas.

Before a device for producing synthesis gas is tasked to ensure the continuous nature of the process for production of synthesis gas by eliminating its cycles, thereby increasing its productivity, while improving the reliability and durability of the device by excluding from its design cyclically moving parts.

The problem is solved due to the fact that the device for producing synthesis gas, the camera including partial oxidation of hydrocarbons with oxygen, mixer, system expansion and cooling of the products of partial oxidation and output of the synthesis gas, is supplied with pre-heated hydrocarbon and air flow regulator hydrocarbons, the camera partial oxidation of hydrocarbons contains a means of ignition and made in the form of a flow of the combustion chamber, inlet through which antipredatory lattice docked mixer, and the mixer is connected to the inlet pipe of hydrocarbons and air inlet pipe covered with a gap recuperator pipe, one end of which is connected with the exit flow of the combustion chamber, and the other, open alyausa recuperating pipe, forming an enclosed space for the expansion and cooling of the products of the process of partial oxidation, in addition to the heat exchanger installed tubular heater hydrocarbons and tubular air heater, with one end of the tubular heater hydrocarbons connected to the flow regulator of hydrocarbons, and the other end through the mentioned inlet pipe is connected with a mixer, one end of the tubular air heater is connected to the air source and the other end through the supply pipe is connected with a mixer, however, the heat exchanger is equipped with a fitting for the conclusion of his oral synthesis gas.

In flowing the combustion posted by biasing the process of partial oxidation of hydrocarbons with oxygen in the air, made in the form of heat inserts made of heat-resistant material forming a multi-channel duct for the products of oxidation.

In flowing the combustion posted by biasing the process of partial oxidation of hydrocarbons with oxygen in the air, made in the form of heat inserts made of heat-resistant materials such as ceramics, forming a multi-channel duct for the products of oxidation.

CTE is ardenia, equipped with a hose of air, and the shell of the heat exchanger is made of double-layer hollow and its cavity with one side connected with an air gap cooling flow of the combustion chamber and on the other hand is connected with the tubular air heater located in the heat exchanger.

Wall recuperating the tube is hollow and closed cavity with one end of the pipe is connected with the cavity of the air gap cooling flow of the combustion chamber, and the other end is connected with the intake air pipe connected to the mixer.

Apparatus for producing synthesis gas allows to obtain a technical result, namely provides continuous nature of the process of partial oxidation of hydrocarbons with oxygen in the air, due to the exclusion of his work cycles, and expelled from the device design details that would be mutually cyclically movable, which significantly increases the reliability and durability of the device.

The drawing shows a General view of the device for the generation of synthesis gas in longitudinal section.

Apparatus for producing synthesis gas includes flowing the combustion chamber 1, the entrance of which is through and what about the raw materials and the supply pipe 5 air the inlet pipe 4 and the inlet pipe 5 both together covered with a gap recuperator pipe 6, one end 7 of which is connected with the exit flow of the combustion chamber 1, and the other, open end 8 recuperating pipe 6 communicates with the cavity of the heat exchanger 9. The heat exchanger 9 is formed with the shell 10, which covers recuperating pipe 6 with the formation of a closed space for expansion and cooling of the products of the process of partial oxidation of hydrocarbons. In the heat exchanger 9 are tubular heater 11 of hydrocarbons and tubular heater 12 of the air, with one end 13 of the tubular heater 11 hydrocarbons connected to the controller 14 of the flow of hydrocarbons, and the other end 15 of the tubular heater 11 through the supply pipe 4 is connected with the mixer 3. One end 16 of the tubular heater 12 air connected to the air source and the other end 17 through the inlet pipe 5 is connected with the mixer 3. The heat exchanger 9 is provided with a socket 18 for the conclusion of his oral synthesis gas. The socket 18 is connected with the cavity of the collector 19 surrounding the outside of the heat exchanger 9.

In flowing the combustion chamber 1 is placed stabilizer 20 process p is reproch materials, for example, ceramic, forming a multi-channel duct 21 for oxidation products. The wall 22 of the flowing combustion chamber 1 is covered with a gap hermetic shell 23, forming an air layer 24 cooling. The shell 23 is provided with a socket 25 for entry of air in the air layer 24, and the shell 10 of the heat exchanger 9 is made of double-layer, hollow and its cavity 26 with one side connected with an air gap 24 of the cooling flow in the combustion chamber 1, and on the other hand, the cavity 26 is connected with the end 16 of the tubular heater 12 of the air, while the tubular heater 12 of the air with his end 17 through the inlet pipe 5 is connected with a mixer 3.

The wall 27 recuperating pipe 6 is made hollow and its closed cavity 28 with one end 7 of the pipe 6 is connected with the cavity of the air gap 24, and the other end 8 of the pipe 6, the cavity 28 is connected with the supply pipe 5 air connected to the mixer 3.

Flowing the combustion chamber 1 is equipped with a spark 29 ignition.

In the process of the synthesis gas production device for producing synthesis gas operates as follows.

Hydrocarbons through the flow regulator 14, a tubular heater 11 hydrocarbon is th layer 24 of the cooling flow cells 1 burning, her air with one hand through a closed cavity wall 28 27 recuperating pipe 6 enters the inlet pipe 5 and into the mixer 3 and the other side of the air gap 24 air through the cavity 26 of the double-layer hollow shell 10 of the heat exchanger 9 flows into the tubular heater 12, and a tubular heater 12 air through the inlet pipe 5 is also supplied to the mixer 3. In the mixer 3 hydrocarbon and air are mutually mixed and through antipredatory grill 2 go on flowing the combustion chamber 1. Here, in a flow chamber 1, the combustion at the initial stage of air-hydrocarbon mixture is forcibly ignited by the spark 29 and into the chamber 1, the combustion process starts oxidation of hydrocarbons with oxygen. The products of partial oxidation out of the flow cells 1 combustion in recuperating pipe 6, in which, contacting with one hand with the inlet pipes 4 and 5, transfer heat received by him in the mixer 3 hydrocarbon feedstock and air, and on the other hand heat the air flowing through the cavity 28 of the hollow wall 27 recuperating pipe 6. Then through the open end 8 of the pipe 6 products of the oxidation process extend into the cavity taproom and 12 and flowing through him hydrocarbon feedstock and air, pass the final hardening. The products of the process containing synthesis gas from the cavity of the heat exchanger 9 is brought out through the fittings 18 and the manifold 19 for further processing.

The initial forced combustion of the air-hydrocarbon mixture is performed in a flow chamber 1 burning candles 29 ignition when the ratio of oxygen to the amount of hydrocarbons =0,6-0,7 necessary for sustainable initiation of the ignition process when cold flowing the combustion chamber 1, and, after warming up the flow of the combustion chamber 1 to a temperature close to 1200oWith, is brought to a level =0,30-0,56 optimal for the process of partial oxidation of hydrocarbons in a mixture with oxygen. In the processing of specific hydrocarbon value may vary within a specified range. For example, the process of partial oxidation of methane is taken as hydrocarbons, oxygen is carried out at a temperature in flowing the combustion chamber 1, is equal to 1200-1300oWith, and when the ratio of oxygen-methane =0,34-0,36. The processing of associated petroleum gas containing 10-15% vol. ethane and propane, is carried out in the same conditions, i.e. at temperatures equal to 1200-1300

The continuity of the process of partial oxidation of hydrocarbons with oxygen in the air and high efficiency are achieved including due to the return of a large part of the heat released in the oxidation reaction, by transferring heat from the products of oxidation of hydrocarbon raw materials and the air entering the flow chamber 1 burning through recuperating pipe 6 and the heat exchanger 9, containing tubular heaters 11 and 12.

The technical result obtained by using a method of producing synthesis gas, is that the process of partial oxidation of hydrocarbons with oxygen flows continuously, without cycles, which improves the performance of the method.

Apparatus for producing synthesis gas enables the specified method in the continuous mode and with high efficiency. In addition, the device has a high reliability and durability.

1. Spouse coefficient of excess oxidant is less than 1, forced combustion of the air-hydrocarbon mixture and the partial oxidation of hydrocarbons with oxygen in the reaction zone, the expansion and cooling with subsequent withdrawal of the product of the process containing synthesis gas, and the introduction of a new portion of hydrocarbons and air, characterized in that carry heated hydrocarbon and air at elevated pressure and temperature, 50-100oC below the temperature of ignition mixtures thereof, the process of partial oxidation of hydrocarbons is carried out in flowing the combustion chamber, with forced ignition is carried out at a ratio of excess oxidant =0,6-0,7, and after warming up the flow of the combustion chamber, the ratio of oxygen to hydrocarbon feedstock is brought to level =0,30-0,56.

2. The method according to p. 1, characterized in that the preheating hydrocarbon and air is conducted into the heat exchanger by the heat of the cooled products of partial oxidation.

3. The method according to p. 1, characterized in that the mixing of the hydrocarbon and air is carried out after completion of preheating in the heat exchanger.

4. The method according to p. 1, characterized in that the expansion and OHL burning in the closed volume of the heat exchanger with the simultaneous transfer of heat from the hydrocarbon feedstock and air, received by tubular heaters to the input of the mixer.

5. The method according to p. 1, characterized in that the process of partial oxidation of methane is taken as the hydrocarbon, oxygen is carried out in flowing the combustion chamber at a temperature equal to 1200-1300oWith, and when the ratio of oxygen to methane, the appropriate value =0,34-0,36.

6. The method according to p. 1, characterized in that the process of partial oxidation by oxygen of associated petroleum gas containing 10-15% vol. ethane and propane and adopted as hydrocarbons, carried out at a temperature in flowing the combustion chamber equal to 1200-1300oWith, and when level =0,34-0,36.

7. The method according to p. 1, characterized in that the cooling process of the products of partial oxidation, leaving the reaction zone is conducted at a speed of not less than 3000oWith/s

8. Apparatus for producing synthesis gas, the camera including partial oxidation of hydrocarbons with oxygen, mixer, system expansion and cooling of the products of partial oxidation and output synthesis gas, characterized in that it is equipped with a system of preheating hydrocarbon and air which contains a means of ignition and made in the form of a flow of the combustion chamber, to the entrance through which antipredatory lattice docked mixer, and the mixer is connected to the inlet pipe of hydrocarbons and air inlet pipe covered with a gap recuperator pipe, one end of which is connected with the exit flow of the combustion chamber, and the other, open, end recuperating pipe communicates with the cavity of the heat exchanger, which is made in the form of a shell covering recuperating pipe, thus forming a closed space for expansion and cooling of the products of the process of partial oxidation, in addition, the heat exchanger is installed tubular heater hydrocarbons and tubular air heater, thus to one end of the tubular heater hydrocarbons connected to the flow regulator of hydrocarbons, and the other end through the mentioned inlet pipe is connected with a mixer, one end of the tubular air heater is connected to the air source and the other end through the supply pipe is connected with a mixer, however, the heat exchanger is equipped with a fitting for the conclusion of his oral synthesis gas.

9. The device under item 8, characterized in that the flow of the combustion chamber placed stabilizer process Partia is cnyh materials, forming a multi-channel duct for the products of oxidation.

10. The device under item 8 or 9, characterized in that the stabilizer of the process of partial oxidation of hydrocarbons with oxygen in the air is made of ceramic.

11. The device under item 8, wherein the wall flow of the combustion chamber is covered with a gap hermetic shell, forming the layer of air cooling, equipped with a hose of air, and the shell of the heat exchanger is made of double-layer hollow and its cavity with one side connected with an air gap cooling flow of the combustion chamber and on the other hand is connected with the tubular air heater located in the heat exchanger.

12. The device under item 8, characterized in that the wall recuperating the tube is hollow and closed cavity with one end of the pipe is connected with the cavity of the air gap cooling flow of the combustion chamber, and the other end is connected with the intake air pipe connected to the mixer.

 

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SUBSTANCE: proposed singlet oxygen generator has case, chlorine injector, throttling valve, and solution injector. Inserted in each hole of injector are at least two forming threads disposed at hole ends with gap formed in-between. Solution jet escaping the hole is then formed in its downward motion over surfaces of threads and between them. When chlorine flows between solution jets, chlorination reaction of alkali solution of hydrogen peroxide takes place; in the process singlet oxygen is produced and chlorine is recovered. Threads may pass from one hole at certain angle to one another, or they may cross one another, or come in contact with threads of other hole in solution injector. At least two threads provided in solution injector hole make it possible not only to guide the thread but also to control its flow and to form desired geometry of jet characteristic by varying relative position of threads in jet. Such design enables development of various types of singlet oxygen generators characterized in enlarged reaction surface and operating effectiveness with added advantage of enhanced operating reliability due to steady flow of jet between threads.

EFFECT: enlarged functional capabilities.

5 cl, 6 dwg

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