CN111115577B - Catalytic hydrogen production system and system for reducing nitrogen oxides by hydrogen combustion - Google Patents
Catalytic hydrogen production system and system for reducing nitrogen oxides by hydrogen combustion Download PDFInfo
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- CN111115577B CN111115577B CN202010101200.1A CN202010101200A CN111115577B CN 111115577 B CN111115577 B CN 111115577B CN 202010101200 A CN202010101200 A CN 202010101200A CN 111115577 B CN111115577 B CN 111115577B
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- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
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- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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Abstract
The invention belongs to the technical field of hydrogen production, and particularly relates to a catalytic hydrogen production system and a nitrogen oxide reduction system by hydrogen combustion. The catalytic hydrogen production system comprises a heat preservation and insulation layer, a raw material vaporization superheater, a raw material reaction temperature lifting regulator and a catalytic reactor, wherein the raw material vaporization superheater, the raw material reaction temperature lifting regulator and the catalytic reactor are arranged in the heat preservation and insulation layer and are connected in sequence; the raw material vaporization superheater is used for vaporizing the liquid hydrogen production raw material into hydrogen production raw material mixed gas; the raw material reaction temperature lifting regulator is used for lifting the temperature of the hydrogen production raw material mixed gas; the catalytic reactor is used for preparing hydrogen from hydrogen production raw material mixed gas under the temperature and pressure conditions required by the process through the catalysis of the catalyst; the high-temperature hydrogen generated by the catalytic reactor enters the raw material vaporization superheater and exchanges heat with the liquid hydrogen production raw material. The invention greatly reduces the reaction temperature in the hydrogen production process, saves energy, greatly improves the reaction rate, increases the hydrogen production amount and well controls the residual amount of the hydrogen production raw material which is not involved in the reaction.
Description
Technical Field
The invention belongs to the technical field of hydrogen production, and particularly relates to a catalytic hydrogen production system and a nitrogen oxide reduction system by hydrogen combustion.
Background
At present, the scientific and technical level of China is rapidly advanced, the social economy is also rapidly developed, the requirements of people on living environments are higher and higher, so that people must pay great attention to environmental protection, particularly, the environment protection is better than the environment protection, the requirements are changed from the traditional concept, the functions of various combustion equipment are further improved, more combustion equipment capable of ensuring that various combustion equipment can fully and cleanly burn is designed, the heat efficiency is high, and the combustion equipment provided with a flue gas ultra-clean exhaust effect is very ideal.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a catalytic hydrogen production system and a system for reducing nitrogen oxides by hydrogen combustion.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
A catalytic hydrogen production system comprising: the raw material vaporization superheater, the raw material reaction temperature lifting regulator and the catalytic reactor are arranged in the heat insulation layer and are connected in sequence; the raw material vaporization superheater is used for vaporizing the liquid hydrogen production raw material into hydrogen production raw material mixed gas; the raw material reaction temperature lifting regulator is used for lifting the temperature of the hydrogen production raw material mixed gas and reaching the catalytic reaction temperature of the hydrogen production raw material mixed gas; the catalytic reactor is used for preparing hydrogen from hydrogen production raw material mixed gas under the temperature and pressure conditions required by the process through the catalytic action of the catalyst;
the high-temperature hydrogen generated by the catalytic reactor enters the raw material vaporization superheater and exchanges heat with the liquid hydrogen production raw material, so that the liquid hydrogen production raw material is vaporized at high temperature.
The raw material vaporization superheater comprises a raw material vaporization superheater shell and a plurality of raw material channels arranged in the raw material vaporization superheater shell, wherein the raw material channels are of a tube bundle structure or a plate structure and are communicated with the raw material reaction temperature lifting regulator;
the shell of the raw material vaporization superheater is provided with a high-temperature hydrogen gas inlet and a high-temperature hydrogen gas outlet, and the high-temperature hydrogen gas inlet is communicated with the catalytic reactor.
The raw material reaction temperature lifting regulator comprises a raw material reaction temperature self-control regulating heater, a raw material reaction temperature lifting regulator heat conduction material and a raw material reaction temperature lifting regulator heat receiving pipe, wherein one or more raw material reaction temperature lifting regulator heat receiving pipes are arranged in the raw material reaction temperature self-control regulating heater, and the raw material reaction temperature self-control regulating heater and the raw material reaction temperature lifting regulator heat receiving pipe are filled with the raw material reaction temperature lifting regulator heat conduction material; the heat receiving pipe of the raw material reaction temperature lifting adjuster is a straight pipe or a curve pipe, and two ends of the heat receiving pipe are respectively communicated with the raw material vaporization superheater and the catalytic reactor.
The catalytic reactor comprises a catalytic reactor constant temperature regulation heater, a catalytic reactor heat conduction material and a catalyst Cheng Zhuangguan, wherein one or more catalyst containing tubes are arranged in the catalytic reactor constant temperature regulation heater, and the catalytic reactor heat conduction material is filled between the catalytic reactor constant temperature regulation heater and the catalyst containing tubes; the catalyst Cheng Zhuangguan is a straight pipe or a curve pipe, one end of the catalyst Cheng Zhuangguan is connected with the heated pipe of the raw material reaction temperature lifting regulator through a communication pipeline, and the other end of the catalyst Cheng Zhuangguan is connected with the raw material vaporization superheater.
The heat conducting material of the raw material reaction temperature lifting regulator and the heat conducting material of the catalytic reactor are made of heat conducting powder or heat conducting fine particles made of red copper, brass, magnesium oxide, aluminum or heat conducting graphite.
The catalytic hydrogen production system also comprises a raw material auxiliary heating vaporization device and a raw material quantitative control conveyor, wherein the raw material auxiliary heating vaporization device is connected between the raw material vaporization superheater and the raw material quantitative control conveyor; the raw material quantitative control conveyor is used for quantitatively conveying hydrogen production raw materials; the raw material auxiliary heating vaporization device is used for heating and vaporizing the liquid hydrogen production raw material when the catalytic hydrogen production system is started for the first time in a cold mode, and the catalytic hydrogen production system is closed after normal operation.
The catalytic hydrogen production system also comprises a gas-liquid separator, a hydrogen condenser and a hydrogen purifying processor which are sequentially connected, wherein the gas-liquid separator is communicated with high-temperature hydrogen in the raw material vaporization superheater; the bottom of the raw material vaporization superheater and the bottom of the gas-liquid separator are connected through a condensate discharge valve, and the bottom of the gas-liquid separator is provided with a raw material liquid discharge port which is used for discharging unreacted liquid hydrogen production raw material.
A system for reducing nitrogen oxides by hydrogen combustion, comprising a combustion device, a hydrogen burner and a catalytic hydrogen production system as claimed in any one of claims 1 to 7, wherein the combustion device comprises a main combustion chamber and a flue arranged at the upper part of the main combustion chamber; the catalytic hydrogen production system sprays the ignited hydrogen to the upper part of the combustion chamber and/or the exhaust flue through the hydrogen burner, and the burnt hydrogen reduces nitrogen oxides contained in the flue gas at the upper part of the combustion chamber and/or in the exhaust flue.
The hydrogen burner comprises a jacket, an ignition assembly, a central gas inlet pipeline, a hydrogen injection burner, a burner head and a flame stabilizing combustion disk, wherein the side wall of the jacket is of a hollow structure, and a cooling medium is filled in the side wall of the jacket; a central gas inlet pipeline and a plurality of hydrogen gas inlet pipelines surrounding the central gas inlet pipeline are arranged in the outer sleeve; the flame stabilizing combustion disc is arranged at the end part of the outer sleeve, and is provided with a combustion head, a plurality of hydrogen injection combustion nozzles and a plurality of rotational flow ventilation holes, wherein the hydrogen injection combustion nozzles and the rotational flow ventilation holes are distributed around the combustion head; the combustion head is connected with the central gas inlet pipeline and is used for igniting hydrogen; each hydrogen injection burner is connected with each hydrogen inlet pipeline respectively;
The ignition component is arranged on one side of the combustion head and is used for igniting fuel gas sprayed out of the combustion head.
The outer circumference of the flame stabilizing combustion disc is provided with a plurality of swirl guide grooves, and the end face of the flame stabilizing combustion disc is provided with at least one group of swirl vent holes uniformly distributed along the circumferential direction; the cyclone vent holes are obliquely arranged, and wind led out by the cyclone vent holes and the cyclone guide grooves spirally ascend and are fully mixed with nitrogen oxides in the hydrogen and the flue gas.
The side wall of the exhaust flue is of a water-cooled wall type structure, and a water-cooled pipe is arranged in the exhaust flue.
The invention has the advantages and beneficial effects that:
1. The invention utilizes the hydrogen production raw material and the catalytic hydrogen production system, and under the guarantee of the elements such as temperature, pressure, feeding quantity and the like, the invention is matched with the application of the hydrogen production catalyst, so that the reaction temperature is greatly reduced, the energy is saved, the activation energy in the reaction is also reduced, the reaction rate is greatly improved, the hydrogen production quantity is increased, the residual quantity of the hydrogen production raw material which is not involved in the reaction is well controlled, and the residual raw material can be reused.
2. The invention can utilize the combination of the waste heat of the combustion equipment and normal heat energy, accurately set the temperature, and react methanol and methanol water under the catalysis of the catalyst to prepare hydrogen gas, so that the heat energy can be increased and the hydrogen gas can be used as a reducing agent for reducing nitrogen oxides when the hydrogen gas is used for combustion of the combustion equipment, the urea or various ammonia materials used for the traditional flue gas denitration are changed, a large amount of funds are saved when the urea or various ammonia materials are used for the denitration technology, and the hydrogen gas is used for combustion to reduce the nitrogen oxides, so that the combustion heat energy can be increased for the combustion equipment, the denitration can be realized, and two purposes are achieved.
3. The invention can collect and utilize the high-temperature steam discharged by the thermal power plant after the work is done (after the steam turbine is pushed to do work), can be directly used as one of reaction raw materials, saves a great amount of funds for resource consumption, and can also utilize the heat energy of the steam as raw materials for temperature raising and heat exchange, thereby saving the conventional energy.
Drawings
FIG. 1 is a schematic diagram of a catalytic hydrogen production system in accordance with the present invention;
FIG. 2 is a schematic diagram of a system for reducing nitrogen oxides by burning hydrogen in accordance with the present invention;
FIG. 3 is a schematic view of a hydrogen burner according to the present invention;
Fig. 4 is a right side view of fig. 3.
In the figure: 1. a methanol water or water vapor raw material inlet, a methanol deionized water mixed liquid raw material inlet, a refined methanol raw material inlet, a raw material quantitative control conveyor, a system control raw material residual overflow return valve, a raw material auxiliary heating vaporization device, 7, a raw material vaporization superheater, 8, a catalytic reactor constant temperature regulation heater, 9, a catalytic reactor heat conduction material, 10, a catalyst containing tube, 11, a catalytic reactor, 12, a raw material reaction temperature lifting regulator heat conduction material, 13, a raw material reaction temperature self-control regulating heater, 14, a raw material reaction temperature lifting regulator heat receiving tube, 15, a raw material reaction temperature lifting regulator, 16, a communication pipeline, 17, a heat preservation heat insulation layer, 18, a hydrogen gas combustion tempering prevention security device, 19, a combustion equipment upper hydrogen gas conveying pipeline, 20, a main combustion chamber upper hydrogen gas combustion control valve, a hydrogen gas control valve of a discharge flue, 22, a hydrogen gas burner in the discharge flue, 23, a hydrogen gas conveying pipeline of a combustion zone, 24, a hydrogen gas purifying processor, 25, a hydrogen gas burner at the upper part of a main combustion chamber, 26, a smoke discharging direction after the main combustion chamber of the combustion device performs combustion reaction, 27, a nitrogen oxide combustion reduction area II, 28, a nitrogen oxide combustion reduction area I, 29, a hydrogen gas condenser, 30, a hydrogen gas conveying pipeline control valve of the combustion zone, 31, a hydrogen gas burner of the combustion zone, 32, a combustion zone, 33, a main combustion chamber, 34, a gas-liquid separator, 35, a raw material liquid discharging port, 36, a condensate discharging valve, 37, a high-voltage power transmission wire, 38, a central gas inlet pipeline, 39, a flame temperature detection signal feedback wire, 40, a middle-ring hydrogen gas inlet pipeline, 41 and an outer-ring hydrogen gas inlet pipeline, 42. the cooling medium, 43, the outer sleeve, 44, the outer ring hydrogen jet burner, 45, the middle ring hydrogen jet burner, 46, the flame temperature detection sensing needle, 47, the burner, 48, the high-voltage discharge ignition needle, 49, the flame stabilizing combustion disk, 50, the swirl guiding groove, 51, the outer ring swirl vent, 52 are middle ring swirl vent, 53 are the flame of the burner combustion.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
Example 1
As shown in fig. 1, the catalytic hydrogen production system provided by the present invention includes: the heat preservation and insulation layer 17 is arranged in the heat preservation and insulation layer 17 and is sequentially connected with the raw material vaporization superheater 7, the raw material reaction temperature lifting regulator 15 and the catalytic reactor 11; the raw material vaporization superheater 7 is used for vaporizing the liquid hydrogen production raw material into hydrogen production raw material mixed gas; the raw material reaction temperature lifting adjuster 15 is used for lifting the temperature of the hydrogen production raw material mixed gas and reaching the catalytic reaction temperature of the hydrogen production raw material mixed gas; the catalytic reactor 11 is used for preparing hydrogen from hydrogen production raw material mixed gas under the condition of temperature and pressure required by the process through the catalysis of a catalyst; the high-temperature hydrogen generated by the catalytic reactor 11 enters the raw material vaporization superheater 7 and exchanges heat with the liquid hydrogen production raw material, so that the liquid hydrogen production raw material is vaporized at high temperature.
The raw material vaporization superheater 7 comprises a raw material vaporization superheater shell and a plurality of raw material channels arranged in the raw material vaporization superheater shell, wherein the raw material channels are of a tube bundle structure or a plate structure and are communicated with the raw material reaction temperature lifting regulator 15; the shell of the raw material vaporization superheater is provided with a high-temperature hydrogen gas inlet and a high-temperature hydrogen gas outlet, and the high-temperature hydrogen gas inlet is communicated with the catalytic reactor 11.
The raw material reaction temperature lifting regulator 15 comprises a raw material reaction temperature self-control regulating heater 13, a raw material reaction temperature lifting regulator heat conducting material 12 and a raw material reaction temperature lifting regulator heat receiving pipe 14, wherein one or more raw material reaction temperature lifting regulator heat receiving pipes 14 which are uniformly arranged are arranged in the raw material reaction temperature self-control regulating heater 13, and the raw material reaction temperature lifting regulator heat conducting material 12 is filled between the raw material reaction temperature self-control regulating heater 13 and the raw material reaction temperature lifting regulator heat receiving pipe 14; the material reaction temperature elevation adjuster heat receiving pipe 14 is a straight pipe or a curved pipe, and both ends are respectively communicated with the material passage of the material vaporization superheater 7 and the catalytic reactor 11.
In the embodiment of the invention, the outer layer of the raw material reaction temperature lifting adjuster 15 is a raw material reaction temperature self-control adjusting heater 13, and the raw material reaction temperature self-control adjusting heater 13 comprises an electric heating ring heater, an electric heating plate heater, a crawler-type ceramic high-temperature heater or an electromagnetic high-Wen Diaokong heater and the like. The raw material reaction temperature rise adjuster thermally conductive material 12 is a thermally conductive powder, for example: red copper powder, brass powder, magnesia powder, aluminum powder or heat conducting graphite powder, etc.; or the raw material reaction temperature rise adjuster heat conductive material 12 is a heat conductive fine particle, for example: fine red copper particles, fine brass particles, fine magnesium oxide particles, fine aluminum particles or fine thermally conductive graphite particles; at low temperature, the heat conducting oil can be adopted as the heat conducting material 12 of the raw material reaction temperature lifting regulator; or the raw material reaction temperature rise adjuster heat conduction material 12 adopts high temperature heat conduction oil, high temperature dry steam (water vapor), high temperature air, or the like. The material reaction temperature rise adjuster heat-receiving pipe 14 is a high temperature resistant stainless steel pipe, the shape of which is made into a spiral pipe type or a continuous S-shaped pipe type structure.
The catalytic reactor 11 comprises a catalytic reactor constant temperature regulating heater 8, a catalytic reactor heat conducting material 9 and a catalyst containing tube 10, wherein one or more catalyst containing tubes 10 which are uniformly arranged are arranged in the catalytic reactor constant temperature regulating heater 8, and the catalytic reactor heat conducting material 9 is filled between the catalytic reactor constant temperature regulating heater 8 and the catalyst containing tubes 10; the catalyst containing tube 10 is a straight tube or a curved tube, and one end is connected with the raw material reaction temperature rise adjuster heat receiving tube 14 through a communication pipeline 16, and the other end is connected with the high-temperature hydrogen gas inlet of the raw material vaporization superheater 7.
In the embodiment of the invention, the outer layer of the catalytic reactor 11 is a catalytic reactor constant temperature regulation heater 8, and the catalytic reactor constant temperature regulation heater 8 comprises an electric heating coil heater, an electric heating plate heater, a crawler-type ceramic high temperature heater or an electromagnetic high Wen Diaokong heater and the like. The catalytic reactor heat conducting material 9 is a heat conducting powder, for example: red copper powder, brass powder, magnesia powder, aluminum powder or heat conducting graphite powder, etc.; or the catalytic reactor heat conducting material 9 is a heat conducting fine particle, for example: fine red copper particles, fine brass particles, fine magnesium oxide particles, fine aluminum particles or fine thermally conductive graphite particles. And heat conducting oil is used at medium and low temperatures.
In an embodiment of the present invention, the catalyst holding tube 10 is a stainless steel straight tube or a continuous S-shaped bent tube. After the hydrogen production catalyst is filled in the tube, the tube heads at the two ends are 10-50 mm higher than the sealing plates at the two ends, holes (smaller than the air inlet or outlet holes with the particle size of the catalyst) are drilled on the tube heads, two end covers (preventing the catalyst from flowing out) are simultaneously arranged or welded on the tube heads, and the air inlet or outlet holes (smaller than the particle size of the catalyst) are drilled on the two end covers.
In the embodiment of the invention, the heat insulation layer 17 comprises a metal shell and a high-temperature resistant heat insulation material arranged in the metal shell, wherein the metal shell is made of stainless steel plates or painted iron plates; the high-temperature resistant heat-insulating material adopts rock wool fiber felt, aluminum silicate fiber felt or light heat-insulating particles and the like.
In the embodiment of the invention, the catalytic hydrogen production system further comprises a raw material auxiliary heating vaporization device 6 and a raw material quantitative control conveyor 4, wherein the raw material auxiliary heating vaporization device 6 is connected between the raw material vaporization superheater 7 and the raw material quantitative control conveyor 4; the raw material quantitative control conveyor 4 is used for quantitatively conveying hydrogen production raw materials and is provided with a methanol water or water vapor raw material inlet 1, a methanol deionized water mixed solution raw material inlet 2 and a refined methanol raw material inlet 3; the top of the raw material quantitative control conveyor 4 is provided with a system control raw material allowance overflow return valve 5. The raw material auxiliary heating vaporization device 6 is used for heating and vaporizing the liquid hydrogen production raw material when the catalytic hydrogen production system is started for the first time in a cold mode, and the catalytic hydrogen production system is closed after normal operation.
In the embodiment of the invention, the raw material auxiliary heating vaporization device 6 is a commercially available product, and a miniature steam generator provided by Shangjiu Kong Shangyi thermal energy equipment Co., ltd is adopted. The raw material quantitative control conveyor 4 adopts a quantitative conveying pump.
In the embodiment of the invention, the catalytic hydrogen production system further comprises a gas-liquid separator 34, a hydrogen gas condenser 29 and a hydrogen gas purifying processor 24 which are connected in sequence, wherein the gas-liquid separator 34 is communicated with high-temperature hydrogen in the raw material vaporization superheater 7; the bottom of the raw material vaporization superheater 7 and the bottom of the gas-liquid separator 34 are connected through a condensate discharge valve 36, and the bottom of the gas-liquid separator 34 is provided with a raw material liquid discharge port 35, and the raw material liquid discharge port 35 is used for discharging unreacted liquid hydrogen production raw material.
In the embodiment of the invention, the three hydrogen production raw materials and three hydrogen production catalysts are included, and the three hydrogen production catalysts are respectively used in three temperature sections, namely, the low temperature sections: 150-200 ℃, and a medium temperature section: 200-300 ℃ and a high temperature section: 300-500 ℃. In the embodiment of the invention, three hydrogen production catalysts are commercial products, and the high-temperature hydrogen production catalyst is a nickel-based multielement combined metal catalyst; the medium-temperature hydrogen production catalyst is a copper-based multielement combined metal catalyst; the low-temperature hydrogen production catalyst is a noble metal rare earth combined multielement catalyst.
The three groups of hydrogen production raw materials are respectively selected according to the geographical environment and different use modes required by different hydrogen production, the three groups of hydrogen production raw materials are respectively refined methanol (purity 99%), refined methanol and deionized water are prepared into mixed liquid according to a ratio of 1:1, the refined methanol and water vapor are respectively conveyed by the three groups of pipes according to the same mass (weight) of the 1:1 ratio, and the three groups of hydrogen production raw materials are respectively fed and mixed into a catalytic hydrogen production system to be used as raw materials for preparing hydrogen gas (one group of raw materials are selected for hydrogen production according to actual needs).
When the temperature of the three groups of hydrogen production raw materials rises to the reaction temperature, the set operating pressure of the system can be reached, the operating pressure is generally determined according to the hydrogen production amount per unit hour of the catalytic hydrogen production system, the operating pressure determined by the embodiment is 0.3 MPa-3 MPa, the feeding flow rate (liquid airspeed) of the three groups of raw materials is determined according to the hydrogen production amount which can be completed after passing through the hydrogen production catalyst bed layer per hour of the catalytic hydrogen production system, and the feeding flow rate is 0.1-3 h < -1 >, and is the counting range of the liquid airspeed specified by the catalytic hydrogen production system.
The three groups of hydrogen production raw materials can prepare hydrogen gas under the conditions of reaction temperature, operating pressure, liquid airspeed, catalyst catalysis and the like, and the chemical reaction formula is as follows:
The general formula: CH 30H+H20＝C02+3H2 -49.5KJ/mol
Dividing into: 1. CH 30H＝C0+2H2 -90.7KJ/mol
2、C0+H20＝C02+H2 +41.19KJ/mol
The application system selects three hydrogen production catalysts according to different hydrogen production environments and various additional favorable conditions, wherein the three hydrogen production catalysts are respectively: the catalyst for low-temperature hydrogen production has the use temperature of 150-200 ℃. The catalyst for medium temperature hydrogen production has the use temperature range of 200-300 ℃. The catalyst for high temperature hydrogen production has the application temperature ranging from 300 ℃ to 500 ℃.
The working process of the invention is as follows:
One group of hydrogen production raw materials is selected according to actual needs, a certain group of hydrogen production raw materials are conveyed into a raw material quantitative control conveyor 4 through a pipeline, the entering quantity of the hydrogen production raw materials is precisely controlled by the raw material quantitative control conveyor 4, meanwhile, redundant raw materials are conveyed back to a place where the raw materials are stored through a system control allowance overflow return valve 5, the quantified raw materials enter a raw material auxiliary heating vaporization device 6 (the device is only used when the catalytic hydrogen production system just starts to work, and the like, the system normally operates, after high-temperature hydrogen gas is produced, the raw material auxiliary heating function is immediately closed, the system overpressure security interlocking function normally works), and the raw materials at the moment are conveyed into a raw material vaporization superheater 7 after being vaporized at high temperature. Then, the vaporized and overheated hydrogen production raw material is conveyed to a raw material reaction temperature lifting regulator 15, heated to a required reaction temperature, conveyed into a catalyst containing tube 10 in the catalytic reactor 11 through a communication pipeline 16 between the catalytic reactor 11 and the raw material reaction temperature lifting regulator 15, subjected to methanol decomposition reaction and carbon monoxide and water vapor conversion reaction to generate high-temperature mixed gas (mixed gas rich in hydrogen) such as hydrogen, carbon dioxide and the like, and the reacted high-temperature mixed gas leaves the catalytic reactor 11 and enters the raw material vaporization superheater 7. The high-temperature mixed gas after the reaction is cooled greatly in the space by cooling and heat exchange (heat exchange, vaporization and overheating of the hydrogen production raw material) for a certain time, and then enters the gas-liquid separator 34 for gas-liquid separation treatment. In addition, when the system is designed, a small part of high-temperature mixed gas after reaction can be considered, condensate generated after the system stops working can enter the gas-liquid separator 34 through the condensate discharge valve 36, and the condensate and the raw material liquid which is cooled and separated by the gas-liquid separator 34 and is not involved in the reaction are discharged through the raw material liquid discharge port 35 and returned to the place where the raw material is stored. The separated hydrogen gas enters the hydrogen gas condenser 29 for condensation and cooling, and then enters the hydrogen gas purifying processor 24 for purifying treatment, so that the prepared hydrogen gas has certain use purity and requirements, and then is conveyed through a pipeline, and the prepared hydrogen gas is practically applied.
The application range of the hydrogen gas is as follows: the first catalyst is used for hydrogenating protective gas, hydrogen fuel cells, high-energy gas fuel and grease; and secondly, the combustion is used for reducing nitrogen oxides, because various fuels used by large and medium-sized combustion equipment are mostly used for supporting combustion in the combustion process of a combustion chamber, nitrogen in the air is oxidized into nitrogen oxide gas at high temperature, the nitrogen oxide is harmful gas, and nitrogen oxides can be reduced into nitrogen and water through the combustion of hydrogen gas for removing nitrogen hydride.
In summary, the hydrogen gas prepared by the catalytic hydrogen production system is applied to the fields of chemical gas protection, hydrogen fuel cells, special high-energy gas fuel, powder metallurgy, industrial metal heat treatment, bioengineering, electronic industry, glass industry, reduction treatment of nitrogen oxides generated by grease hydrogenation and high-temperature combustion, and the like.
Example two
As shown in fig. 2, the system for reducing nitrogen oxides by hydrogen combustion provided by the invention comprises combustion equipment, a hydrogen combustor and the catalytic hydrogen production system provided by any embodiment, wherein the catalytic hydrogen production system sprays ignited hydrogen to the upper part (also called the tail part) of the combustion chamber and/or the exhaust flue of the combustion equipment through the hydrogen combustor, and the burnt hydrogen reduces the nitrogen oxides in the flue gas at the upper part of the combustion chamber and/or in the exhaust flue.
After the hydrogen gas produced by the catalytic hydrogen production system is purified by the hydrogen gas purifying processor 24, pure hydrogen gas is conveyed into the hydrogen gas combustion tempering-preventing security device 18, so that the hydrogen gas can be safely applied to conventional combustion and reduction of nitrogen oxides in flue gas.
As shown in fig. 2, the combustion apparatus includes a main combustion chamber 33 and a flue disposed at an upper portion of the main combustion chamber 33, wherein a combustion area 32 is disposed at a lower portion of the main combustion chamber 33, a nitrogen oxide combustion reduction area i 28 is disposed at an upper portion of the main combustion chamber 33, an inner cavity of the flue is a nitrogen oxide combustion reduction area ii 27, a side wall of the flue is in a water-cooled wall structure, a water-cooled tube is disposed in the flue, and the water-cooled wall of the flue and the water-cooled tube are both communicated with the water-cooled tube of the combustion apparatus, so that water in the water-cooled wall of the flue and the water-cooled tube inside can fully absorb heat energy generated by hydrogen combustion reduction of nitrogen oxides.
The hydrogen gas produced by the catalytic hydrogen production system is distributed into two pipeline transmissions, namely a hydrogen gas transmission pipeline 19 at the upper part of the combustion equipment and a hydrogen gas transmission pipeline 23 at the combustion zone. The upper hydrogen gas delivery pipe 19 of the combustion apparatus injects hydrogen gas into the upper portion of the main combustion chamber 33 and the inside of the exhaust flue through the upper hydrogen burner 25 of the main combustion chamber and the inside of the exhaust flue 22, respectively. The upper hydrogen gas conveying pipeline 19 of the combustion device is provided with a main combustion chamber upper hydrogen gas combustion control valve 20 and a discharge flue hydrogen gas control valve 21, wherein the main combustion chamber upper hydrogen gas combustion control valve 20 is used for controlling hydrogen gas entering the upper part of the main combustion chamber 33, and the discharge flue hydrogen gas control valve 21 is used for controlling hydrogen gas entering the discharge flue. The combustion-zone hydrogen gas supply pipe 23 injects hydrogen gas into the combustion zone 32 through a plurality of combustion-zone hydrogen burners 31, and a combustion-zone hydrogen gas supply pipe control valve 30 is provided on the combustion-zone hydrogen gas supply pipe 23.
Injecting hydrogen gas into combustion zone 32 for conventional fuel combustion; a hydrogen gas is injected into the upper portion of the main combustion chamber 33 and the exhaust flue for combustion reduction of nitrogen oxides. Because various fuels used by large and medium-sized combustion equipment are mostly used for supporting combustion in the combustion process of the combustion chamber, nitrogen in the air is oxidized into nitrogen oxide gas at high temperature, and the nitrogen oxide is harmful gas. To remove nitrogen hydrides, nitrogen oxides can be reduced to nitrogen water and carbon dioxide by mixing the hydrogen gas and carbon monoxide gas with the nitrogen oxides and then burning.
The chemical reaction formula for reducing nitrogen oxides by hydrogen combustion is as follows:
The chemical reaction formula for burning and reducing nitrogen oxide by carbon monoxide gas is as follows:
As shown in fig. 3-4, the hydrogen burner comprises a jacket 43, an ignition assembly, a central gas inlet pipe 38, a hydrogen inlet pipe, a hydrogen injection burner, a burner head 47 and a flame stabilizing combustion disk 49, wherein the side wall of the jacket 43 is of a hollow structure, and a cooling medium 42 is filled in the side wall; the outer sleeve 43 is provided with a central gas inlet pipe 38 and a plurality of hydrogen gas inlet pipes surrounding the central gas inlet pipe 38; the flame stabilizing combustion disk 49 is arranged at the end part of the outer sleeve 43, and the flame stabilizing combustion disk 49 is provided with a combustion head 47, a plurality of hydrogen gas injection combustion nozzles and a plurality of rotational flow ventilation holes around the combustion head 47; the burner head 47 is connected to the central gas inlet duct 38 for igniting the hydrogen; each hydrogen injection burner is connected with each hydrogen inlet pipeline respectively; the ignition assembly is disposed at one side of the combustion head 47 for igniting the fuel gas sprayed from the combustion head 47.
The ignition assembly comprises a high-voltage power transmission wire 37, a flame temperature detection signal feedback wire 39, a flame temperature detection sensing needle 46 and a high-voltage discharge ignition needle 48, wherein the flame temperature detection sensing needle 46 and the high-voltage discharge ignition needle 48 are arranged on a flame stabilizing combustion disk 49, the high-voltage power transmission wire 37 is connected with the high-voltage discharge ignition needle 48, and the flame temperature detection signal feedback wire 39 is connected with the flame temperature detection sensing needle 46. The detection signal feedback task of the flame temperature detection sensing needle 46 is that the flame temperature detection signal feedback wire 39 is fed back to the control terminal of the application system, so that the operation safety of the application system and the combustion equipment is ensured.
In the embodiment of the invention, the hydrogen jet burner comprises a plurality of middle-ring hydrogen jet burner tips 45 distributed along the circumferential direction and a plurality of outer-ring hydrogen jet burner tips 44 distributed along the circumferential direction; the hydrogen gas inlet pipe includes a plurality of middle-ring hydrogen gas inlet pipes 40 and a plurality of outer-ring hydrogen gas inlet pipes 41, wherein the plurality of middle-ring hydrogen gas inlet pipes 40 are respectively connected with each middle-ring hydrogen gas injection burner 45; a plurality of outer-ring hydrogen gas intake pipes 41 are connected to each outer-ring hydrogen gas injection burner 44.
As shown in fig. 4, the outer circumference of the flame stabilizing combustion disk 49 is provided with a plurality of swirl guide grooves 50, and the end surface of the flame stabilizing combustion disk 49 is provided with at least one group of swirl vent holes uniformly distributed along the circumferential direction; the swirl vent holes are obliquely arranged, and the wind led out by the swirl vent holes and the swirl guide grooves 50 rises spirally and is fully mixed with the nitrogen oxides in the hydrogen and the flue gas. The middle hydrogen gas injection burner 45 and the outer ring hydrogen gas injection burner 44 supply hydrogen gas from the middle hydrogen gas intake pipe 40 and the outer ring hydrogen gas intake pipe 41, respectively, for injection combustion.
In the embodiment of the invention, the flame stabilizing combustion disk 49 is provided with a middle ring swirl vent hole 52 and an outer ring swirl vent hole 51, wherein the middle ring swirl vent hole 52 is arranged between the middle ring hydrogen gas injection burner 45 and the outer ring hydrogen gas injection burner 44, and the outer ring swirl vent hole 51 is arranged outside the outer ring hydrogen gas injection burner 44.
In the embodiment of the present invention, the outer jacket 43 is made of a high temperature resistant material, which includes high temperature resistant stainless steel or high temperature impact resistant series ceramics, etc., and the cooling medium includes cooling water or high pressure high speed cooling air, etc. The flame stabilizing combustion disk 49 is made of high temperature resistant stainless steel or high temperature impact resistant ceramic series, a swirl guide groove 50 forming a certain angle and depth with the axis is arranged on the outer diameter of the flame stabilizing combustion disk 49, a hydrogen gas injection combustion nozzle passing hole and a swirl vent forming a certain angle with the axis are drilled on the end face of the flame stabilizing combustion disk, and a high voltage discharge ignition needle 48, a flame temperature detection sensing needle 46, a combustion head 47 and the like are arranged on the end face of the flame stabilizing combustion disk 49. The flame stabilizing combustion disk 49 provides strong air intake swirl by providing a swirl guide groove 50 and a swirl vent, thereby improving the stability of hydrogen combustion. In order to eliminate the influence of high-temperature hot corrosion and high-temperature heat conduction on the normal operation of the hydrogen gas special-purpose burner, the special-purpose burner is cooled by the cooling medium 42 in the outer sleeve 43.
In the embodiment of the invention, the hydrogen gas combustion tempering prevention security device 18 is a commercial product purchased from Zhejiang Zhengxuan valve Limited company, and the model is DN15. The hydrogen gas combustion backfire-preventing security device 18 consists of a plurality of hydrogen backfire flame arresters connected in parallel, a multi-channel electric control hydrogen valve island (a combined electromagnetic valve) and the like. In order to prevent the hydrogen from backfire during the combustion process, the hydrogen flame arrestor must be installed in the hydrogen gas combustion backfire prevention device 18 because the hydrogen gas flow rate is smaller than the hydrogen gas combustion speed. In addition, the multi-channel electric control hydrogen valve island is convenient for controlling the safe use of the hydrogen burner on the multi-channel pipeline, and the valve islands respectively control the closing of the hydrogen pipelines and cannot provide hydrogen under the assumption that the flame temperature sensing needle on the flame stabilizing disc of the hydrogen burner does not detect the temperature generated by the combustion of the gas combustion head.
The invention utilizes hydrogen production raw materials (methanol and water or methanol and water vapor) to prepare the hydrogen in a catalytic hydrogen production system, and under the guarantee of the factors such as temperature, pressure, feeding quantity and the like, the invention is matched with the application of the hydrogen production catalyst, so that the reaction temperature is greatly reduced, the energy is saved, the activation energy in the reaction is also reduced, the reaction rate is greatly improved, the hydrogen production quantity is increased, the residual quantity of the hydrogen production raw materials which are not involved in the reaction is well controlled, and the residual raw materials can be reused.
The catalytic hydrogen production system using methanol water as raw material adopts integral heat preservation and insulation treatment (except devices which are respectively formed by cooling, condensing and burning to reduce nitrogen oxides), and other catalytic hydrogen production systems adopt integral heat preservation and insulation packaging measures so as to reduce energy consumption, improve waste heat recovery utilization rate, facilitate control of integral reaction temperature of the catalytic hydrogen production system, prolong service life of hydrogen production catalyst and increase hydrogen production of the system.
The system for reducing nitrogen oxides by hydrogen combustion provided by the invention can be integrated into any equipment using various fuels for combustion, and has the functions of being capable of being independently used as a conventional gas fuel for combustion, being further capable of being used as a reducing agent for reducing nitrogen oxides of harmful gases, reducing the content of nitrogen oxides of the harmful gases in smoke into nitrogen and water, discharging the nitrogen and water, avoiding the harm of pollutants to human beings, and ensuring that the human beings live in good green environments.
The foregoing is merely an embodiment of the present invention and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, expansion, etc. made within the spirit and principle of the present invention are included in the protection scope of the present invention.
Claims (9)
1. The system for reducing nitrogen oxides by hydrogen combustion is characterized by comprising combustion equipment, a hydrogen combustor and a catalytic hydrogen production system, wherein the combustion equipment comprises a main combustion chamber (33) and a discharge flue arranged at the upper part of the main combustion chamber (33); the catalytic hydrogen production system sprays ignited hydrogen to the upper part of the combustion chamber (33) and/or the inside of the exhaust flue through a hydrogen burner, and the burnt hydrogen reduces nitrogen oxides contained in the flue gas at the upper part of the combustion chamber (33) and/or in the exhaust flue;
The hydrogen burner comprises a jacket (43), an ignition assembly, a central gas inlet pipeline (38), a hydrogen inlet pipeline, a hydrogen jet burner, a burner head (47) and a flame stabilizing combustion disc (49), wherein the side wall of the jacket (43) is of a hollow structure, and cooling medium is filled in the side wall; a central gas inlet pipeline (38) and a plurality of hydrogen gas inlet pipelines surrounding the central gas inlet pipeline (38) are arranged in the outer sleeve (43); the flame stabilizing combustion disc (49) is arranged at the end part of the outer sleeve (43), and the flame stabilizing combustion disc (49) is provided with a combustion head (47), a plurality of hydrogen gas injection combustion nozzles and a plurality of cyclone ventilation holes, wherein the hydrogen gas injection combustion nozzles and the cyclone ventilation holes are distributed around the combustion head (47); the combustion head (47) is connected with the central gas inlet pipeline (38) and is used for igniting hydrogen; each hydrogen injection burner is connected with each hydrogen inlet pipeline respectively;
the ignition component is arranged on one side of the combustion head (47) and is used for igniting fuel gas sprayed out of the combustion head (47);
The outer circumference of the flame stabilizing combustion disc (49) is provided with a plurality of rotational flow guide grooves (50), and the end face of the flame stabilizing combustion disc (49) is provided with at least one group of rotational flow vent holes uniformly distributed along the circumferential direction; the cyclone vent holes are obliquely arranged, and wind led out by the cyclone vent holes and the cyclone guide grooves (50) ascend spirally and are fully mixed with nitrogen oxides in the hydrogen and the flue gas.
2. The system for reducing nitrogen oxides by hydrogen combustion according to claim 1, wherein the side wall of the exhaust flue is of a water cooled wall type structure, and a water cooled tube is arranged in the exhaust flue.
3. The hydrogen combustion nitrogen oxide reduction system according to claim 1, wherein the catalytic hydrogen production system comprises a heat preservation and insulation layer (17) and a raw material vaporization superheater (7), a raw material reaction temperature lifting regulator (15) and a catalytic reactor (11) which are arranged in the heat preservation and insulation layer (17) and are sequentially connected; the raw material vaporization superheater (7) is used for vaporizing the liquid hydrogen production raw material into hydrogen production raw material mixed gas; the raw material reaction temperature lifting regulator (15) is used for lifting the temperature of the hydrogen production raw material mixed gas and reaching the catalytic reaction temperature of the hydrogen production raw material mixed gas; the catalytic reactor (11) is used for preparing hydrogen from hydrogen production raw material mixed gas under the temperature and pressure conditions required by the process through the catalysis of a catalyst;
The high-temperature hydrogen generated by the catalytic reactor (11) enters the raw material vaporization superheater (7) and exchanges heat with the liquid hydrogen production raw material to enable the liquid hydrogen production raw material to be vaporized at high temperature.
4. A hydrogen combustion nitrogen oxide reduction system according to claim 3, wherein the raw material vaporization superheater (7) comprises a raw material vaporization superheater housing and a plurality of raw material channels arranged in the raw material vaporization superheater housing, the raw material channels being of a tube bundle structure or a plate structure and being in communication with the raw material reaction temperature elevation regulator (15);
The shell of the raw material vaporization superheater is provided with a high-temperature hydrogen gas inlet and a high-temperature hydrogen gas outlet, and the high-temperature hydrogen gas inlet is communicated with the catalytic reactor (11).
5. A hydrogen combustion nitrogen oxide reduction system according to claim 3, wherein the raw material reaction temperature elevation adjuster (15) comprises a raw material reaction temperature self-control adjustment heater (13), a raw material reaction temperature elevation adjuster heat conduction material (12) and a raw material reaction temperature elevation adjuster heat receiving pipe (14), wherein one or more raw material reaction temperature elevation adjuster heat receiving pipes (14) are arranged in the raw material reaction temperature self-control adjustment heater (13), and the raw material reaction temperature elevation adjuster heat conduction material (12) is filled between the raw material reaction temperature self-control adjustment heater (13) and the raw material reaction temperature elevation adjuster heat receiving pipe (14); the heating pipe (14) of the raw material reaction temperature lifting adjuster is a straight pipe or a curve pipe, and two ends of the heating pipe are respectively communicated with the raw material vaporization superheater (7) and the catalytic reactor (11).
6. The system for reducing nitrogen oxides by hydrogen combustion according to claim 5, wherein the catalytic reactor (11) comprises a catalytic reactor constant temperature regulating heater (8), a catalytic reactor heat conducting material (9) and a catalyst Cheng Zhuangguan (10), wherein one or more catalysts Cheng Zhuangguan (10) are arranged in the catalytic reactor constant temperature regulating heater (8), and the catalytic reactor heat conducting material (9) is filled between the catalytic reactor constant temperature regulating heater (8) and the catalyst Cheng Zhuangguan (10); the catalyst Cheng Zhuangguan (10) is a straight pipe or a curve pipe, one end of the catalyst Cheng Zhuangguan is connected with the raw material reaction temperature lifting regulator heated pipe (14) through a communication pipeline (16), and the other end of the catalyst Cheng Zhuangguan is connected with the raw material vaporization superheater (7).
7. The system for reducing nitrogen oxides by hydrogen combustion according to claim 6, wherein the raw material reaction temperature elevation adjuster heat conducting material (12) and the catalytic reactor heat conducting material (9) are heat conducting powder or heat conducting fine particles made of red copper, brass, magnesium oxide, aluminum or heat conducting graphite.
8. A hydrogen combustion nitrogen oxide reduction system according to claim 3, characterized in that the catalytic hydrogen production system further comprises a raw material auxiliary heating vaporization device (6) and a raw material quantitative control conveyor (4), wherein the raw material auxiliary heating vaporization device (6) is connected between the raw material vaporization superheater (7) and the raw material quantitative control conveyor (4); the raw material quantitative control conveyor (4) is used for quantitatively conveying hydrogen production raw materials; the raw material auxiliary heating vaporization device (6) is used for heating and vaporizing the liquid hydrogen production raw material when the catalytic hydrogen production system is started for the first time in a cold mode, and the catalytic hydrogen production system is closed after normal operation.
9. The hydrogen combustion nitrogen oxide reduction system according to any one of claims 3-8, further comprising a gas-liquid separator (34), a hydrogen gas condenser (29) and a hydrogen gas purification processor (24) connected in sequence, wherein the gas-liquid separator (34) is in communication with high temperature hydrogen in the raw material vaporization superheater (7); the bottom of the raw material vaporization superheater (7) and the bottom of the gas-liquid separator (34) are connected through a condensate discharge valve (36), a raw material liquid discharge outlet (35) is arranged at the bottom of the gas-liquid separator (34), and the raw material liquid discharge outlet (35) is used for discharging unreacted liquid hydrogen production raw material.
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| CN113432125B (en) * | 2021-07-15 | 2023-03-28 | 山西新源煤化燃料有限公司 | White oil hydrogen-mixed combustion device |
| CN116477571B (en) * | 2023-04-06 | 2024-07-16 | 四川亚联氢能科技股份有限公司 | Integrated hydrogen production reactor |
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| CN211770294U (en) * | 2020-02-19 | 2020-10-27 | 李根钧 | Catalytic hydrogen production system and system for reducing nitrogen oxide by burning hydrogen |
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| CN101362973A (en) * | 2008-08-28 | 2009-02-11 | 西南化工研究设计院 | Technique for preparing mixed fuel of hydrogen and dimethyl ether from methanol |
| CN110566961A (en) * | 2019-10-29 | 2019-12-13 | 深圳市佳运通电子有限公司 | Central flame-stabilizing combustion head for low-nitrogen combustor |
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