CN219136372U - Urea hydrolysis ammonia production system suitable for high temperature condition - Google Patents
Urea hydrolysis ammonia production system suitable for high temperature condition Download PDFInfo
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- CN219136372U CN219136372U CN202223264769.3U CN202223264769U CN219136372U CN 219136372 U CN219136372 U CN 219136372U CN 202223264769 U CN202223264769 U CN 202223264769U CN 219136372 U CN219136372 U CN 219136372U
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Abstract
The utility model discloses a urea hydrolysis ammonia production system suitable for high temperature conditions, which relates to the technical field of atmospheric pollution control and comprises a urea solution heater, a urea hydrolysis microchannel reactor and a hydrolysis residual liquid reaction separator which are connected in sequence; the urea solution heater is used for heating urea and conveying the heated urea to the urea hydrolysis microchannel reactor; the urea hydrolysis microchannel reactor comprises a heating device and a plurality of reaction microchannels, wherein the heating device is used for heating the reaction microchannels, and the urea hydrolysis microchannel reactor is used for conveying urea from the reaction microchannels to a hydrolysis residual liquid reaction separator; the hydrolysis raffinate reaction separator is used for separating gas and liquid. By adopting the scheme, a large amount of urea solution is distributed into the micro-channel tube for hydrolysis reaction, so that the intermolecular diffusion distance in the urea solution is short, the mass transfer efficiency is improved, the reaction rate is improved, and the back mixing in the urea hydrolysis process is greatly reduced.
Description
Technical Field
The utility model relates to the technical field of air pollution control, in particular to a urea hydrolysis ammonia production system suitable for high-temperature conditions.
Background
In the ultralow emission requirement of the flue gas of the coal-fired boiler, ammonia is generally adopted as a reducing agent for removing nitrogen oxides in the flue gas. The raw materials of ammonia in the thermal power plant mainly comprise liquid ammonia and urea. Because liquid ammonia belongs to toxic dangerous chemicals, the transportation and storage of the liquid ammonia have great potential safety hazards, and when the storage capacity exceeds 10t, the liquid ammonia is a serious dangerous source. The national energy agency, national energy letter safety (2018) No. 12), encourages power plants to retrofit liquid ammonia plants to urea ammonia plants. The urea ammonia production process mainly comprises two kinds: urea pyrolysis and urea hydrolysis. As the operation cost, the energy consumption and the failure rate of the urea pyrolysis technology are higher than those of the urea hydrolysis ammonia production technology, the urea hydrolysis ammonia production technology gradually becomes the main flow technology in the flue gas denitration ammonia production engineering.
At present, a kettle type reactor is generally adopted for preparing ammonia by urea hydrolysis, 40-60% urea solution is subjected to hydrolysis reaction under the conditions of 140-160 ℃ and 0.4-0.6 MPa, and the product gas is as follows: ammonia, carbon dioxide and water vapor. As urea is continuously reacted in the kettle reactor, the reaction materials have larger back mixing phenomenon, and even the full mixed flow is achieved. Back mixing affects the temperature distribution and concentration distribution in the system, and also affects the reaction process; urea hydrolysis is a positive stage reaction, and back mixing also reduces the concentration of reactants in the reactor, necessarily reducing the apparent reaction rate.
In addition, in recent years, although the urea hydrolysis reaction rate is increased by adding an ammonium dihydrogen phosphate solution as a catalyst, the effect of increasing the reaction rate is not remarkable under the operating condition that the designed ammonia production capacity is achieved at more than 150 ℃.
Disclosure of Invention
The utility model aims to solve the defects of the prior art and provides a urea hydrolysis ammonia production system suitable for high temperature conditions.
The utility model is realized by the following technical scheme:
a urea hydrolysis ammonia production system suitable for high temperature conditions comprises a urea solution heater, a urea hydrolysis microchannel reactor and a hydrolysis residual liquid reaction separator which are connected in sequence;
the urea solution heater is used for heating urea and conveying the heated urea to the urea hydrolysis microchannel reactor;
the urea hydrolysis microchannel reactor comprises a heating device and a plurality of reaction microchannels, wherein the heating device is used for heating the reaction microchannels, and the urea hydrolysis microchannel reactor is used for conveying urea from the reaction microchannels to a hydrolysis residual liquid reaction separator;
the hydrolysis raffinate reaction separator is used for separating gas and liquid.
Compared with the prior art, as urea adopts continuous reaction in the kettle type reactor, the reaction materials have larger back mixing phenomenon, and even reach full mixed flow. Back mixing affects the temperature distribution and concentration distribution in the system, and also affects the reaction process; the urea hydrolysis reaction is positive-stage reaction, the back mixing can reduce the concentration of reactants in the reactor, and the apparent reaction rate is inevitably reduced, etc., in the scheme, the urea hydrolysis reaction device comprises a urea solution heater, a urea hydrolysis microchannel reactor and a hydrolysis residual liquid reaction separator, wherein the urea solution is conveyed into a plurality of reaction microchannels in the urea hydrolysis microchannel reactor after being heated to the required reaction temperature in the urea solution heater, and the reaction microchannels are continuously heated by a heating device, so that hydrolysis reaction can occur in the reaction microchannels to generate ammonia, carbon dioxide and water vapor, and after passing through the urea hydrolysis microchannel reactor, hydrolysis residual liquid, hydrolysis products, namely ammonia, carbon dioxide and water vapor are all collected into the hydrolysis residual liquid reaction separator, and product gas and hydrolysis residual liquid are separated in the hydrolysis residual liquid reaction separator; in the scheme, a large amount of urea solution is distributed into the reaction micro-channels for hydrolysis reaction, so that the intermolecular diffusion distance in the urea solution is short, the mass transfer efficiency is improved, and the reaction rate is improved; the heat transfer surface area of each reaction microchannel is increased, so that the heat transfer efficiency is improved, and the reaction rate is also improved; secondly, urea solution molecules continuously flow in the channels in the microchannel reactor, and the influence of back mixing on the reaction rate can be effectively eliminated; in addition, a convection tube type heat exchanger is adopted in the urea solution heating system, high-temperature steam in the heat exchanger passes through a shell side, and urea solution passes through a tube side; the urea solution heating system can be steam heating medium, or hot air or flue gas can be used as heating medium.
Further optimizing, the urea solution heater, the urea hydrolysis microchannel reactor and the hydrolysis residual liquid reaction separator are all made of titanium alloy; for the reaction temperature to exceed 160 ℃, thereby greatly improving the reaction rate.
Further preferably, the heating device is an electric heating pipe, electric heating pipes are distributed on the peripheral side of each reaction micro-channel, and the reaction micro-channels are straight-through pipelines; for increasing the reaction rate.
Further optimized, the urea hydrolysis microchannel reactor also comprises a liquid distribution device, wherein the inlet ends of a plurality of reaction microchannels are connected with the liquid distribution device; for uniformly distributing the liquid into the several reaction microchannels.
Further optimizing, the number of the urea hydrolysis micro-channel reactors is several, and the urea solution heater is connected to each urea hydrolysis micro-channel reactor through a plurality of branch pipes; and the urea hydrolysis device is used for selecting a plurality of urea hydrolysis microchannel reactors to decompose urea according to actual working conditions.
Further optimized, the hydrolysis residual liquid reaction separator is internally provided with a distributor, the inlet of the distributor is communicated with the reaction product inlet of the hydrolysis residual liquid reaction separator, the outlet of the distributor is provided with a plurality of spray heads, and the top of the hydrolysis residual liquid reaction separator is also communicated with a product gas pipeline; is used for realizing gas-liquid separation.
Further optimizing, wherein overflow discharge ports are arranged on the side walls of the hydrolysis residual liquid reaction separators below the spray heads; the hydrolysis residual liquid reaction zone is arranged below the overflow discharge port, and the gas-liquid separation zone is arranged above the overflow discharge port of the hydrolysis residual liquid reaction separator.
Further optimizing, a demister is further arranged in the hydrolysis residual liquid reaction separator, and the demister is positioned between a plurality of spray heads and a product gas pipeline; for removing mist in the product gas.
Further optimizing, the circumference of the hydrolysis raffinate reaction separator is also provided with a heating coil; for allowing the urea solution in the hydrolysis raffinate to continue to react until maximum conversion is reached.
Further optimizing, wherein a pressure regulating valve is arranged on the product gas pipeline; the pressure regulating valve is an automatic valve, and is automatically regulated according to the pressure required by the system, and meanwhile, the operating pressure of the hydrolysis residual liquid reaction separator is controlled.
Compared with the prior art, the utility model has the following advantages and beneficial effects:
1. the urea hydrolysis ammonia production system is provided with a urea solution heater, a urea hydrolysis micro-channel reactor and a hydrolysis residual liquid reaction separator, so that heating, reaction and separation required in the urea hydrolysis process are accurately operated and controlled.
2. The utility model provides a urea hydrolysis ammonia production system suitable for high temperature conditions, and a designed micro-channel reactor for urea hydrolysis can convert most of urea into ammonia and carbon dioxide; the reaction micro-channel can improve the mass transfer and heat transfer efficiency in the urea hydrolysis reaction process, greatly reduce back mixing in the urea hydrolysis process, accurately control the reaction conditions and improve the reaction rate of urea hydrolysis.
3. The urea hydrolysis ammonia production system suitable for the high temperature condition can freely combine the number of micro-channel reactors for urea hydrolysis according to the raw material amount of urea solution; the electric heating pipes are uniformly arranged around the micro-channels, so that quick and efficient heat transfer can be realized.
4. The hydrolysis residual liquid reaction separator designed by the utility model can further improve the conversion rate of urea hydrolysis, fully convert urea, quickly separate product gas from residual liquid, reduce entrainment in the product gas, and prevent the product gas from being corroded by entrainment liquid drops and condensation.
5. The urea hydrolysis ammonia production system suitable for high temperature conditions provided by the utility model is made of titanium alloy, so that the urea hydrolysis reaction can be ensured not to corrode the urea hydrolysis system at the temperature exceeding 160 ℃, the limitation of the original 316L material on the urea hydrolysis reaction temperature due to corrosion is broken through, and the reaction temperature is increased, so that the urea hydrolysis reaction rate is greatly increased.
6. The urea hydrolysis ammonia production system suitable for high temperature conditions provided by the utility model has the advantages that the reaction rate is improved by adopting the micro-channel reactor and the titanium alloy material, and the reaction volume required by the urea hydrolysis reactor is reduced under the working condition that the ammonia yield is unchanged, so that the system is easier to assemble and install.
Drawings
The accompanying drawings, which are included to provide a further understanding of embodiments of the utility model and are incorporated in and constitute a part of this application, illustrate embodiments of the utility model. In the drawings:
FIG. 1 is a schematic diagram of a connection mechanism of a urea hydrolysis ammonia production system suitable for high temperature conditions.
In the drawings, the reference numerals and corresponding part names:
the device comprises a 1-urea solution heater, a 2-urea hydrolysis microchannel reactor, a 21-branch pipe, a 22-liquid distribution device, a 23-reaction microchannel, a 24-electric heating pipe, a 25-branch pipe, a 3-hydrolysis raffinate reaction separator, a 31-main pipe, a 32-reaction product inlet, a 33-distributor, a 34-spray head, a 35-demister, a 36-product gas outlet, a 37-overflow discharge port, a 38-liquid discharge port, a 39-heating coil pipe, a 310-purge port, a 311-gas phase pressure relief pipe, a 312-safety valve, a 4-product gas pipeline and a 41-regulating valve.
Detailed Description
For the purpose of making apparent the objects, technical solutions and advantages of the present utility model, the present utility model will be further described in detail with reference to the following examples and the accompanying drawings, wherein the exemplary embodiments of the present utility model and the descriptions thereof are for illustrating the present utility model only and are not to be construed as limiting the present utility model.
Examples
The embodiment provides a urea hydrolysis ammonia production system suitable for high temperature conditions, which comprises a urea solution heater 1, a urea hydrolysis microchannel reactor 2 and a hydrolysis residual liquid reaction separator 3 which are connected in sequence as shown in figure 1;
the urea solution heater 1 is used for heating urea and delivering the heated urea to the urea hydrolysis microchannel reactor 2;
the urea hydrolysis microchannel reactor 2 comprises a heating device and a plurality of reaction microchannels 23, the heating device is used for heating the reaction microchannels 23, and the urea hydrolysis microchannel reactor 2 is used for conveying urea from the reaction microchannels 23 to the hydrolysis raffinate reaction separator 3;
the hydrolysis raffinate reaction separator 3 is used for separating gas and liquid.
Compared with the prior art, as urea adopts continuous reaction in the kettle type reactor, the reaction materials have larger back mixing phenomenon, and even reach full mixed flow. Back mixing affects the temperature distribution and concentration distribution in the system, and also affects the reaction process; the urea hydrolysis reaction is positive-stage reaction, the back mixing can reduce the concentration of reactants in the reactor, and the apparent reaction rate can be reduced, etc., in the scheme, the urea hydrolysis reaction device comprises a urea solution heater 1, a urea hydrolysis microchannel reactor 2 and a hydrolysis residual liquid reaction separator 3, wherein urea solution is conveyed into a plurality of reaction microchannels 23 in the urea hydrolysis microchannel reactor 2 after being heated to the required reaction temperature in the urea solution heater 1, and the hydrolysis reaction can occur in the plurality of reaction microchannels 23 due to the continuous heating of the reaction microchannels 23 by a heating device, so that ammonia, carbon dioxide and water vapor are generated, and hydrolysis residual liquid, hydrolysis products, namely ammonia, carbon dioxide and water vapor are all collected into the hydrolysis residual liquid reaction separator 3 after passing through the urea hydrolysis microchannel reactor 2, and product gas and hydrolysis residual liquid are separated in the hydrolysis residual liquid reaction separator 3; in the scheme, a large amount of urea solution is distributed into the reaction micro-channel 23 for hydrolysis reaction, so that the intermolecular diffusion distance in the urea solution is short, the mass transfer efficiency is improved, and the reaction rate is improved; the heat transfer surface area of each reaction microchannel 23 is increased, so that the heat transfer efficiency is improved, and the reaction rate is also improved; secondly, urea solution molecules continuously flow in a channel in the micro-channel reactor, and the influence of back mixing on the reaction rate can be effectively eliminated; in addition, a convection tube type heat exchanger is adopted in the urea solution heating system, high-temperature steam in the heat exchanger passes through a shell side, and urea solution passes through a tube side; the urea solution heating system can be steam heating medium, or hot air or flue gas can be used as heating medium.
Because the urea hydrolysis reactor is made of 316L materials, the intermediate product of the urea hydrolysis process, namely ammonium carbamate, can cause serious corrosion to the urea hydrolysis reactor after the temperature exceeds 160 ℃, the highest temperature of urea hydrolysis is limited to 160 ℃, the urea hydrolysis reaction rate is slower, the response time of the hydrolyzer to the load change of a boiler is longer, and the volume of the reactor required by the urea hydrolyzer is overlarge; according to the chemical reaction kinetics principle, the higher the temperature is, the faster the reaction rate is;
in order to solve the above problems, the present embodiment provides a specific embodiment for improving the reaction rate, which is set as follows: the urea solution heater 1, the urea hydrolysis microchannel reactor 2 and the hydrolysis residual liquid reaction separator 3 are all made of titanium alloy; it will be appreciated that the urea solution heater 1, the urea hydrolysis microchannel reactor 2 and the hydrolysis raffinate reaction separator 3 are all made of corrosion resistant titanium alloy, so that the urea solution can be rapidly heated to a desired reaction temperature, which exceeds 160 ℃, and the reaction rate is greatly increased by increasing the reaction temperature.
As a specific embodiment for increasing the reaction rate, there is provided: the heating device is an electric heating pipe 24, the electric heating pipe 24 is distributed on the periphery of each reaction micro-channel 23, and the reaction micro-channels 23 are straight-through pipelines; the electric heating pipe 24 is used for maintaining the temperature required by the reaction and providing the heat required by the hydrolysis reaction, the electric heating pipe 24 is arranged around the outer wall of each channel, so that the peripheral side of each reaction micro-channel 23 is contacted with the heating pipe, the surface area for heat transfer is increased, the heat transfer efficiency is improved, and the reaction rate is improved.
As a specific embodiment of uniform distribution, it is provided that: the urea hydrolysis microchannel reactor 2 also comprises a liquid distribution device 22, and the inlet ends of a plurality of reaction microchannels 23 are connected with the liquid distribution device 22; the urea hydrolysis microchannel reactor 2 is similar to a T-shaped structure in that the liquid is uniformly distributed into several reaction microchannels 23 by a liquid distribution device 22.
As a redundancy scheme, the number of the urea hydrolysis micro-channel reactors 2 is several, and the urea solution heater 1 is connected to each urea hydrolysis micro-channel reactor 2 through a plurality of branch pipes 21; according to the actual working conditions, a plurality of urea hydrolysis microchannel reactors 2 can be selected for urea decomposition, and after passing through each liquid distribution device 22 through a plurality of branch pipes 21, the urea solution heater 1 respectively and uniformly enters a plurality of main reactors for producing ammonia through urea hydrolysis, and hydrolysis reaction occurs to generate ammonia, carbon dioxide and water vapor.
As a specific embodiment for realizing the gas-liquid separation, it is provided that: a distributor 33 is arranged in the hydrolysis residual liquid reaction separator 3, the inlet of the distributor 33 is communicated with the reaction product inlet of the hydrolysis residual liquid reaction separator 3, the outlet of the distributor 33 is provided with a plurality of spray heads 34, and the top of the hydrolysis residual liquid reaction separator 3 is also communicated with a product gas pipeline 4; it should be understood that in this embodiment, the hydrolysis raffinate reaction separator 3 is provided with a reaction product inlet, a distributor 33, a spray head 34, a demister 35, an overflow drain, a purge port 310, a liquid discharge port and a heating coil 39, the hydrolysis raffinate reaction separator 3 is of a vertical cylinder structure, the gas-liquid mixture after the reaction of each urea hydrolysis microchannel reactor 2 is converged into the main pipe 31, so that the gas-liquid mixture enters the distributor 33 in the hydrolysis raffinate reaction separator 3 through the reaction product inlet, the distributor 33 uniformly sprays the gas-liquid mixture into the hydrolysis raffinate reaction separator 3 through the spray head 34, so that the hydrolysis raffinate is deposited at the bottom of the hydrolysis raffinate reaction separator 3, and the product gas enters the product gas pipeline 4 at the top of the hydrolysis raffinate reaction separator 3, thereby realizing separation of the product gas and the hydrolysis raffinate of the microchannels.
As some possible embodiments, in this example, overflow drain ports 37 are provided on the side wall of hydrolysis raffinate reaction separator 3 below several spray heads 34; the hydrolysis residual liquid reaction zone is arranged below the overflow discharge port 37, the gas-liquid separation zone is arranged above the overflow discharge port 37 of the hydrolysis residual liquid reaction separator 3, and the product gas enters the product gas pipeline 4 through the demister 35 and the product gas outlet 36 in the hydrolysis residual liquid reaction separator 3 by gas-liquid separation, so as to be discharged into the ammonia supply pipeline.
As some possible embodiments, in this example, a demister 35 is further disposed in the hydrolysis raffinate reaction separator 3, and the demister 35 is located between the plurality of spray nozzles 34 and the product gas line 4; for removing mist in the product gas.
As some possible embodiments, in this example, the hydrolysis raffinate reaction separator 3 is also provided with a heating coil 39 on the peripheral side; wherein the heat provided by the heating coil 39 is used for maintaining the operation temperature required by the hydrolysis raffinate reaction separator 3, and is used for enabling the unreacted urea solution in the hydrolysis raffinate to continuously react in the hydrolysis raffinate reaction separator to generate ammonia, carbon dioxide and water vapor, so that the separation of product gas and liquid is realized, and meanwhile, the urea solution in the hydrolysis raffinate is continuously reacted until the maximum conversion rate is reached; the heating coil 39 may be an electric heating coil 39 or a steam heating coil 39.
As some possible embodiments, in this embodiment, the product gas line 4 is provided with a pressure regulating valve 41; the pressure regulating valve 41 is an automatic valve, and is automatically regulated according to the pressure required by the system, and the operating pressure of the hydrolysis residual reaction separator 3 is controlled.
The urea hydrolysis ammonia production system for high-temperature reaction in the embodiment further comprises the following specific use method, and the method comprises the following steps:
step 1: heating 40-60% urea solution to 180-200 ℃ in a urea solution heater 1;
step 2: uniformly distributing the urea solution reaching the reaction temperature in the step 1 into each urea hydrolysis microchannel reactor 2 through a branch pipe 21, and then distributing the urea solution into each reaction microchannel 23 through a liquid distribution device 22, wherein the urea solution continuously flows in the reaction microchannels 23 and continuously reacts, and the urea hydrolysis temperature is ensured to be 180-200 ℃;
step 3: and (2) merging the gas-liquid phase mixtures after the reaction in the step (2) into a gas-liquid phase main pipe 31, then entering a hydrolysis residual liquid reaction separator (3) through a spray nozzle (34), wherein the operation temperature of the reaction separator is 180-200 ℃, the pressure can reach 0.8-2.0 MPa, continuing to react urea solution in the hydrolysis residual liquid to the maximum conversion rate, and separating product gas from the hydrolysis residual liquid and then entering an ammonia supply pipeline.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the utility model, and is not meant to limit the scope of the utility model, but to limit the utility model to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the utility model are intended to be included within the scope of the utility model.
Claims (10)
1. The urea hydrolysis ammonia production system suitable for the high temperature condition is characterized by comprising a urea solution heater (1), a urea hydrolysis microchannel reactor (2) and a hydrolysis residual liquid reaction separator (3) which are connected in sequence;
the urea solution heater (1) is used for heating urea and conveying the heated urea to the urea hydrolysis microchannel reactor (2);
the urea hydrolysis microchannel reactor (2) comprises a heating device and a plurality of reaction microchannels (23), wherein the heating device is used for heating the reaction microchannels (23), and the urea hydrolysis microchannel reactor (2) is used for conveying urea from the reaction microchannels (23) to a hydrolysis residual liquid reaction separator (3);
the hydrolysis raffinate reaction separator (3) is used for separating gas and liquid.
2. The urea hydrolysis ammonia production system suitable for high temperature conditions according to claim 1, wherein the urea solution heater (1), the urea hydrolysis microchannel reactor (2) and the hydrolysis raffinate reaction separator (3) are all made of titanium alloy.
3. Urea hydrolysis ammonia production system according to claim 1, characterized in that the heating means are electric heating pipes (24), each reaction microchannel (23) being provided with electric heating pipes (24) on its peripheral side, the reaction microchannel (23) being a straight-through pipe.
4. A urea hydrolysis ammonia production system adapted for high temperature conditions according to claim 1, characterized in that the urea hydrolysis microchannel reactor (2) further comprises a liquid distribution device (22), the inlet ends of several reaction microchannels (23) being connected to the liquid distribution device (22).
5. Urea hydrolysis ammonia production system according to claim 1, characterized in that the number of urea hydrolysis microchannel reactors (2) is several, the urea solution heater (1) being connected to each urea hydrolysis microchannel reactor (2) by means of several branches (21).
6. The urea hydrolysis ammonia production system suitable for high temperature conditions according to any one of claims 1-5, wherein a distributor (33) is arranged in the hydrolysis raffinate reaction separator (3), an inlet of the distributor (33) is communicated with a reaction product inlet (32) of the hydrolysis raffinate reaction separator (3), an outlet of the distributor (33) is provided with a plurality of spray heads (34), and a product gas pipeline (4) is also communicated with the top of the hydrolysis raffinate reaction separator (3).
7. A urea hydrolysis ammonia production system adapted for high temperature conditions according to claim 6, characterized in that overflow drains (37) are provided on the side wall of the hydrolysis raffinate reaction separator (3) below several of the spray heads (34).
8. The urea hydrolysis ammonia production system suitable for high temperature conditions according to claim 6, wherein a demister (35) is further arranged in the hydrolysis raffinate reaction separator (3), and the demister (35) is positioned between a plurality of spray heads (34) and the product gas pipeline (4).
9. The urea hydrolysis ammonia production system suitable for high temperature conditions as recited in claim 6, wherein a heating coil (39) is further provided on the peripheral side of the hydrolysis raffinate reaction separator (3).
10. A urea hydrolysis ammonia production system adapted for high temperature conditions according to claim 6, characterized in that the product gas line (4) is provided with a pressure regulating valve (41).
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