CN209957391U - Preparation system for preparing hydrogen chloride and ammonia gas by utilizing ammonium chloride - Google Patents
Preparation system for preparing hydrogen chloride and ammonia gas by utilizing ammonium chloride Download PDFInfo
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- CN209957391U CN209957391U CN201821968123.4U CN201821968123U CN209957391U CN 209957391 U CN209957391 U CN 209957391U CN 201821968123 U CN201821968123 U CN 201821968123U CN 209957391 U CN209957391 U CN 209957391U
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Abstract
The application discloses a preparation system for preparing hydrogen chloride and ammonia gas by utilizing ammonium chloride, which comprises at least one decomposition reactor and a regeneration reactor, or comprises a reactor which can be used as both the decomposition reactor and the regeneration reactor. Continuously adding ammonium chloride particles into a decomposition reactor through a solid particle feeding device on the reactor, and reacting with molten ammonium bisulfate to generate hydrogen chloride gas and intermediate materials; discharging the intermediate material into a regeneration reactor, and heating and decomposing the intermediate material in the regeneration reactor to form ammonium bisulfate and ammonia gas; the ammonium bisulfate returns to the decomposition reactor for recycling. The utility model provides a continuous decomposition ammonium chloride industrially feasible embodiment, through the continuous slow joining of ammonium chloride solid particle, reduced the volatility of ammonium chloride, improved the utilization ratio of ammonium chloride.
Description
Technical Field
The application relates to the field of inorganic salt and soda chemical industry, in particular to a technology for preparing hydrogen chloride and ammonia gas by using ammonium chloride.
Background
In recent years, the demand of soda ash is rapidly increased, and the ammonium chloride byproduct is limited in the application of fertilizers, so that a proper utilization mode is urgently needed. If ammonium chloride is decomposed into NH with higher economic value3And HCl, NH3Can be recycled in the soda industry, and the HCl can also be applied in various fields such as organic chlorine chemical industry and the like.
NH4Cl can be decomposed into NH by heating3And HCl, but with a large amount of NH4Cl sublimes and NH is formed3Is difficult to separate from HCl and very easy to regenerate very small NH4Cl particles, so that the decomposition of ammonium chloride to prepare hydrogen chloride and ammonia gas has not been realized in large-scale industrial application in the world.
To obtain NH4Decomposition product NH of Cl3And HCl, one possible method being in the reactant NH4Adding reusable acidic (or alkaline) circulation medium into Cl, and reacting with NH generated by heating3(or HCl) is first reacted to an intermediate product, thereby reacting HCl (or NH)3) Released first and then NH is released by further pyrolysis of the intermediate3(or HCl). Some patents and literature have proposed some chemical routes or conceptual processes based on the above routes. For example, patent US1718420 proposes NH4HSO4For circulating the medium, HCl and NH are obtained step by step3The chemical route of (1); patent US2787524 uses NaHSO4/NH4HSO4And is a circulating medium to obtain HCl and NH step by step3US4293532 further proposes the temperature and the stoichiometric ratio of the reactants for each reaction based on the above route. None of the published documents, however, proposes a complete preparation system and corresponding operating method which are easy to implement industrially.
SUMMERY OF THE UTILITY MODEL
In view of the above, the present invention provides a system for preparing hydrogen chloride and ammonia gas by using ammonium chloride, which solves the above problems in the prior art.
In one aspect of the present invention, there is provided a preparation system for preparing hydrogen chloride and ammonia gas using ammonium chloride, the preparation system comprising at least one reactor, wherein in the reactor, ammonium chloride and molten state ammonium bisulfate undergo decomposition reaction to output hydrogen chloride gas and obtain intermediate material; the intermediate material is subjected to a regeneration reaction to output ammonia gas and obtain ammonium bisulfate; the decomposition reaction and the regeneration reaction occur in different working stages of the same reactor, or in multiple reactors which may be in communication. One feature of the preparation system of the present invention is that the ammonium chloride is continuously added to the reactor in the form of solid particles, and therefore, the reactor contains at least one solid particle feeding device capable of continuously feeding the ammonium chloride for adding the ammonium chloride particles to the reactor.
The solid particle feeding device comprises a quantitative conveying device, a feeding pipe positioned on the decomposition reactor, and a pipeline communicated with the conveying device and the feeding pipe; one end of the feeding pipe is positioned on the wall of the reactor, and the other end of the feeding pipe is positioned in the reactor and below the liquid level of the liquid material.
In one form of the preparation system of the present invention, the decomposition reaction and the regeneration reaction occur in a plurality of reactors which are communicable. At this time, the at least one reactor includes: the decomposition reactor is used for generating decomposition reaction and is provided with a solid particle feeding device, a liquid feeding port, a liquid discharging port and an exhaust port; at least one regeneration reactor connected with the decomposition reactor for regeneration reaction, and having a liquid inlet, a liquid outlet and an exhaust port; the system also comprises at least one desorption device connected with the decomposition reactor, and hydrogen chloride gas dissolved in the reaction materials is separated out from the desorption device. The desorption device comprises a liquid feeding port, a carrier gas inlet, a liquid discharging port and an exhaust port; and a liquid feeding port of the desorption device is connected with a liquid discharging port of the decomposition reactor, and a liquid discharging port of the desorption device is connected with a liquid feeding port of the regeneration reactor. A connecting pipeline for returning the liquid material from the regeneration reactor to the decomposition reactor is also arranged between the regeneration reactor and the decomposition reactor.
The decomposition reactor and the regeneration reactor are both provided with a heating device and a temperature control device.
One of the cases where the decomposition reaction and the regeneration reaction occur in a plurality of the reactors that can be connected is that: the number of the decomposition reactors and the regeneration reactors is 1.
The second situation is as follows: the number of the decomposition reactors is more than one, and the number of the regeneration reactors is 1.
The third situation is that: the number of the decomposition reactors is 1, and the number of the regeneration reactors is plural.
The fourth case is: the number of the decomposition reactors and the regeneration reactors is multiple.
When the decomposition reaction and the regeneration reaction occur in a plurality of reactors which can be communicated, the preparation system also comprises at least one molten salt pump which is positioned at the joint of the liquid discharge port of the decomposition reactor and the liquid feed port of the regeneration reactor and/or at the joint of the liquid feed port of the decomposition reactor and the liquid discharge port of the regeneration reactor. The preparation system also comprises: and the heat preservation device is positioned at the joint between the reactors.
When the number of the decomposition reactors is multiple, the connection mode of the multiple decomposition reactors is in series connection, namely, a liquid discharge port of the former decomposition reactor is connected with a liquid feed port of the latter decomposition reactor; the liquid discharge port of the last decomposition reactor is connected with the feed port of the desorption device; at this time, at least the first decomposition reactor has a solid particle feeding means and a heating means; all decomposition reactors have a temperature control device.
Preferably, the reaction temperature of the latter decomposition reactor is not higher than that of the former decomposition reactor;
preferably, the plurality of series connected decomposition reactors each have a solid particle feeding device.
Preferably, the number of the plurality of serially connected decomposition reactors is 2 to 3.
When the number of the regeneration reactors is multiple, the plurality of regeneration reactors are connected in series, namely, a liquid discharge port of a previous regeneration reactor is connected with a liquid feed port of a next regeneration reactor; and the liquid discharge port of the last regeneration reactor is at least connected with the liquid feed port of the first decomposition reactor.
When the number of the at least one regeneration reactor is multiple, the connection mode of the plurality of regeneration reactors can also be parallel connection, namely, the liquid discharge port of each regeneration reactor is connected with the liquid feed port of the decomposition reactor, and the liquid feed port of each regeneration reactor is connected with the liquid discharge port of the decomposition reactor.
Preferably, the decomposition reactor comprises a stirred tank reactor and/or a rotary drum reactor; the regeneration reactor comprises a tubular reactor, a stirred tank reactor and/or a rotary drum reactor.
The utility model discloses a another form of preparation system is: the decomposition reaction and the regeneration reaction occur in different working stages of the same reactor. In this case, the reactor is a stirred reactor or a drum reactor.
The utility model discloses an on the other hand provides a based on above-mentioned preparation system to ammonium chloride is the method of raw materials preparation hydrogen chloride gas and ammonia: adding ammonium bisulfate from the regeneration reactor into the decomposition reactor through a liquid feeding port; ammonium chloride particles are continuously added into the decomposition reactor through a solid particle feeding device, the ammonium chloride in the decomposition reactor reacts with molten ammonium bisulfate, the generated hydrogen chloride gas is continuously discharged through an exhaust port, and the generated intermediate material is discharged through a liquid discharge port; enabling the intermediate material to flow into a feed inlet of the desorption device by using a high potential difference or a molten salt pump, and introducing inert carrier gas into the desorption device so as to enable the dissolved hydrogen chloride gas to enter the carrier gas; discharging the desorbed intermediate material from a liquid discharge port of the desorption device, and feeding the intermediate material into a regeneration reactor; the desorbed intermediate material is heated and decomposed in a regeneration reactor to form ammonium bisulfate and ammonia gas; the generated ammonia gas is continuously discharged through an exhaust port, the generated ammonium bisulfate is discharged through a liquid discharge port, and the generated ammonium bisulfate returns to the decomposition reactor by using a molten salt pump or a high potential difference.
The reaction temperature range of the decomposition reaction is 150-280 ℃, and the reaction temperature range of the regeneration reaction is 280-380 ℃.
The inert carrier gas is hot air and the temperature is 240-280 ℃.
Based on the utility model discloses a preparation system uses ammonium chloride to be the method of raw materials preparation hydrogen chloride and ammonia, works as decomposition reaction and regeneration reaction take place in a plurality of that can communicate during the reactor, a preferred mode of operation is continuous operation: the ammonium chloride particles are added into the decomposition reactor through a solid particle feeding device at a constant speed, and the molten ammonium bisulfate from the regeneration reactor flows into the decomposition reactor through a liquid feeding port; reacting ammonium chloride with ammonium bisulfate in the decomposition reactor, discharging generated hydrogen chloride gas through an exhaust port, and continuously discharging generated intermediate materials through a liquid discharge port; enabling the intermediate material to flow into a feed inlet of the desorption device by using a high potential difference or a molten salt pump, and introducing inert carrier gas into the desorption device so as to enable the dissolved hydrogen chloride gas to enter the carrier gas; continuously discharging the desorbed intermediate material from a liquid discharge port of the desorption device, and feeding the intermediate material into a regeneration reactor; the desorbed intermediate material is heated and decomposed in a regeneration reactor to form ammonium bisulfate and ammonia gas; the generated ammonia gas is continuously discharged through an exhaust port, the generated ammonium bisulfate is continuously discharged through a liquid discharge port, and the generated ammonium bisulfate returns to the decomposition reactor by using a molten salt pump or a high potential difference.
Preferably, in the decomposition reactor, the flow rate ratio of the ammonium bisulfate to the ammonium chloride is 1.5:1 to 3:1, and the flow rate is measured by the amount of the substance.
Based on the utility model discloses a preparation system to ammonium chloride is the method of raw materials preparation hydrogen chloride and ammonia, works as decomposition reaction with regeneration takes place in the same during the different working phase of reactor, the operation mode as follows: heating ammonium bisulfate to a molten state in the reactor; continuously adding ammonium chloride particles into a reactor at a certain speed through a solid particle feeding device, and generating the hydrogen chloride gas and intermediate materials in the reactor by using ammonium chloride and the ammonium bisulfate at the decomposition reaction temperature; continuously discharging hydrogen chloride gas through an exhaust port; after the ammonium chloride completely reacts, raising the temperature of the reactor to the regeneration reaction temperature, and heating and decomposing the intermediate material in the reactor to form ammonium bisulfate and ammonia gas; ammonia gas is discharged through an exhaust port; after the intermediate material is completely reacted, the temperature of the reactor is reduced to the decomposition reaction temperature so as to enter the next operation batch.
Preferably, in the reactor, the ratio of the added ammonium chloride to the amount of the ammonium bisulfate in the system in one operation batch is 2: 3-2: 5.
Preferably, when the decomposition reaction and the regeneration reaction occur in different working stages of the same reactor, the temperature range of the decomposition reaction is 150-280 ℃, and the temperature range of the regeneration reaction is 280-380 ℃.
Based on the utility model discloses a preparation system to the method of ammonium chloride preparation hydrogen chloride gas and ammonia, it is preferred, the mesh number of ammonium chloride granule is not less than 20 meshes, the mesh number is based on taylor standard sieve system.
The utility model discloses an utilize system of ammonium chloride preparation hydrogen chloride and ammonia, compare with prior art, the utility model provides a detailed system design, device and preparation method have given the concrete implementation scheme that the ammonium chloride industry is feasible is decomposed in succession, and through the continuous slow joining of ammonium chloride solid particle, the volatility of ammonium chloride has been reduced moreover, has improved the conversion rate and the utilization ratio of ammonium chloride.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent from the following description of the embodiments of the present invention with reference to the accompanying drawings.
Fig. 1 is a schematic view of a manufacturing system according to a first embodiment of the present invention.
Fig. 2 is a schematic view of a preparation system according to a second embodiment of the present invention.
Fig. 3 is a schematic view of a preparation system according to a third embodiment of the present invention.
Fig. 4 is a schematic view of a preparation system according to a fourth embodiment of the present invention.
Fig. 5 is a schematic view of a preparation system according to a fifth embodiment of the present invention.
Fig. 6 is a schematic view of a manufacturing system according to a sixth embodiment of the present invention.
Detailed Description
The invention will be described in more detail below with reference to the accompanying drawings. Like elements in the various figures are denoted by like reference numerals. For purposes of clarity, the various features in the drawings are not necessarily drawn to scale. In addition, certain well known components may not be shown.
Numerous specific details of the invention are set forth in the following description in order to provide a more thorough understanding of the invention. However, as will be understood by those skilled in the art, the present invention may be practiced without these specific details.
The principles and embodiments of the present invention are described below with reference to the accompanying drawings and specific examples. NH used in the present invention unless otherwise specified4Cl、NH4HSO4The solid starting materials in (A) are all commercial technical-grade chemical starting materials, NH4The particle size of Cl was 50 mesh (Taylor standard sieve system), NH4HSO4The melt is prepared by heating NH4HSO4And (3) obtaining a solid.
The utility model utilizes the concept of chemical circulation and introduces the circulating medium ammonium bisulfate (NH)4HSO4) To effect decomposition of ammonium chloride and NH3And separation of HCl. The utility model relates to a chemical reaction as follows:
NH4and (3) Cl decomposition reaction:
NH4Cl+NH4HSO4→(NH4)2SO4+HCl↑ΔH＝68.3kJ/mol
NH4HSO4and (3) regeneration reaction:
(NH4)2SO4→NH4HSO4+NH3↑ΔH＝108.0kJ/mol
fig. 1 is a schematic view of a preparation system according to a first embodiment of the present invention, the preparation system of the first embodiment includes: decomposition reactor 110, regeneration reactor 120, desorption apparatus 130, molten salt pump 140, and connecting line 150.
In this embodiment, decomposition reactor 110 is a stirred tank reactor comprising: a liquid inlet 111, an outlet 112, a liquid outlet 113, and a solid particle feeder 114. Wherein the solid particle feeding device 114 comprises: a feeding pipe 101 and a quantitative conveying device. The feeding pipe 101 extends from the wall of the decomposition reactor 110 to a position below the liquid level of the liquid material inside, and the quantitative conveying device is communicated with the feeding pipe 101 through a pipeline. The regeneration reactor 120 is a tank reactor comprising: a liquid inlet 121, an air outlet 122, and a liquid outlet 123. The desorption apparatus 130 is a bubble column including: a liquid inlet 131, a carrier gas inlet 132, an exhaust 133, and a liquid outlet 134.
In this embodiment, the number of the decomposition reactors 110 and the regeneration reactors 120 is 1. The liquid outlet 113 of the decomposition reactor is connected to the liquid inlet 131 of the desorption apparatus via a connecting line 150. The liquid outlet 134 of the desorption device is communicated with the liquid inlet 121 of the regeneration reactor through a connecting pipeline 150. The liquid outlet 123 of the regeneration reactor is communicated with the liquid inlet 111 of the decomposition reactor through a connecting pipeline 150.
The utility model discloses the working process of preparation system of first embodiment does: in continuous operation, ammonium chloride particles are continuously fed into decomposition reactor 110 through solid particle feed device 114 at a flow rate to react with molten ammonium bisulfate. HCl gas generated by the decomposition reaction overflows from the molten liquid and is discharged through the exhaust port 112, and then is sent to a subsequent process outside the system. The reacted intermediate material (the mixed solution of ammonium bisulfate and ammonium sulfate) is discharged into the desorption device 130 through the liquid discharge port 113, the connecting pipeline 150 and the liquid feed port 131 of the decomposition reactor. Hot air (inlet temperature 240-280 ℃) is used as carrier gas and is conveyed to the interior of the desorption device 130 through the carrier gas port 132, hydrogen chloride gas dissolved in the intermediate material is removed, and the hydrogen chloride gas is discharged through the exhaust port 133. Removal of hydrogen chloride gasThe intermediate material of the body then enters the regeneration reactor 120 through the liquid outlet 134, the connecting line 150 and the liquid inlet 121 of the regeneration reactor. Specifically, the intermediate material may be transferred by a high head (the decomposition reactor 120 is positioned higher than the desorption device 130, and the desorption device 130 is positioned higher than the regeneration reactor 120) or by providing the molten salt pump 140 on the connection line 150. In the regeneration reactor 120, the intermediate material from the decomposition reactor 110 is heated to regenerate ammonium bisulfate and release NH3Gas, NH3The gas overflows from the molten liquid and is discharged through the gas outlet 122, and the molten liquid of the ammonium bisulfate returns to the decomposition reactor from the liquid discharge port 123 of the regeneration reactor and the liquid feed port 111 of the decomposition reactor. The specific conveying method is the same as the above method for conveying the intermediate material after the decomposition reaction, and is not described in detail.
Since the decomposition reaction is a two-phase reaction (ammonium chloride is added into the reactor as solid particles), a mixing device is required to distribute the solid particles and to uniformly react with heat, and therefore, the decomposition reactor 110 in this embodiment is a stirring reactor. Of course, the skilled person, based on his common knowledge and experience, will choose other types of reactors with mixing devices, which are intended to be included in the scope of the present invention. To ensure a high conversion of ammonium chloride, the ammonium bisulfate is in stoichiometric excess. In some preferred embodiments, the ratio of the flow rate of ammonium bisulfate to the flow rate of ammonium chloride (based on the amount of the substance, the same applies hereinafter) is in a range from 1.5:1 to 3: 1. Since the regeneration reaction is a homogeneous reaction and the reaction rate is relatively slow, a mixing device is not required in principle, and a tank reactor can also be used.
In addition, the decomposition reaction and the regeneration reaction are endothermic reactions, and heat exchange can be carried out by arranging a jacket on the outer wall of the kettle and arranging a coil pipe in the kettle. The heating medium can adopt heat conducting oil. Heating can also be achieved by infrared or electromagnetic heating. Wherein the reaction temperature in the decomposition reactor ranges from 150 ℃ to 280 ℃. The reaction temperature of the regeneration reactor ranges from 280 ℃ to 380 ℃.
As a specific example, the decomposition reactor 110 has a volume of 4m31.5m in diameter and 2 high.25m, a packing factor of 0.7 and a volume of the regeneration reactor 120 of 2.5m3The diameter was 1.25m, the height was 2m, and the packing factor was 0.7.
As a specific example, the ratio of the flow rates of the ammonium bisulfate and the ammonium chloride added was fixed to be 2:1, that is, the flow rate of the ammonium chloride was 8.23kmol/h and the flow rate of the ammonium bisulfate was 16.46 kmol/h. The decomposition reactor 110 was set at 150 deg.C, 180 deg.C, 200 deg.C, 220 deg.C, 240 deg.C, 260 deg.C, and 280 deg.C, respectively, and the regeneration reactor 120 was set at 350 deg.C. The contents of the generated hydrogen chloride and ammonia gas were measured to calculate the conversion rate, and the measurement results are shown in table 1, in which the regeneration conversion rate is the decomposition conversion rate of ammonia gas with respect to the generated ammonium sulfate.
TABLE 1 results of the reactions at different decomposition temperatures
As a specific example, the ratio of the flow rates of ammonium bisulfate and ammonium chloride was fixed to 2:1, i.e., the flow rate of ammonium chloride was 8.23kmol/h and the flow rate of ammonium bisulfate was 16.46 kmol/h. The decomposition reactor 110 was set at 240 ℃ and the regeneration reactor 120 was set at 280 ℃, 300 ℃, 325 ℃, 350 ℃ and 380 ℃ respectively. The contents of the generated hydrogen chloride and ammonia gas were measured to calculate the conversion rate, and the measurement results are shown in table 2, in which the regeneration conversion rate is the decomposition conversion rate of ammonia gas with respect to the generated ammonium sulfate.
TABLE 2 reaction results at different regeneration temperatures
As a specific example, the process conditions of 240 ℃ temperature setting of the decomposition reactor 110 and 325 ℃ temperature setting of the regeneration reactor 120 were selected, and the material balance and heat balance data obtained by Aspen simulation are shown in Table 3. It should be noted that, due to the high temperature of the regeneration reactor 120, unreacted NH in the decomposition reactor 1104Cl is completely volatilized (actually converted to NH) after entering the regeneration reactor 1203And HCl, these NH3And HCl actually forms NH after being cooled in other processes outside the system4Cl crystallization) to cause waste of raw material and clogging of equipment piping, which explains passing through the technical scheme of the present invention, improve NH4Conversion of Cl is very necessary.
TABLE 3 Material balance and Heat balance data
As a comparison of the present invention, the batch operation was adopted, and 8.23kmol of ammonium chloride particles were added to 16.46kmol of ammonium bisulfate at a time (the ratio of the flow rate of ammonium bisulfate to that of ammonium chloride was 2: 1). The decomposition reactor 110 was set at 240 ℃ and the regeneration reactor at 300 ℃. The contents of the generated hydrogen chloride and ammonia gas were measured, and the conversion was calculated, and the measurement results are shown in Table 4. It can be seen that the decomposition conversion of ammonium chloride when the ammonium chloride particles are added in one portion is significantly lower than when they are added continuously. Wherein the regeneration conversion rate is a decomposition conversion rate of ammonia gas with respect to the generated ammonium sulfate.
Table 4 results of one-shot addition of ammonium chloride particles
| Categories | HCl/kmol/h | NH3/kmol/h | Decomposition conversion rate/%) | Regeneration conversion rate/%) |
| Results | 6.5 | 6.0 | 79.0 | 92.3 |
Fig. 2 is a schematic view of a preparation system according to a second embodiment of the present invention, the preparation system of the second embodiment includes: decomposition reactors 110(1) and 110(2), regeneration reactor 120, desorption apparatus 130, molten salt pump 140, and connecting line 150.
In this embodiment, decomposition reactor 110 is a stirred tank reactor comprising: a liquid inlet 111, an outlet 112, a liquid outlet 113, and a solid particle feeder 114. Wherein the solid particle feeding device 114 comprises: the feeding pipe 101 extends from the wall of the decomposition reactor 110 to a position below the liquid level of the liquid material inside, and the quantitative conveying device is communicated with the feeding pipe 101 through a pipeline. The regeneration reactor 120 is a tank reactor comprising: a liquid inlet 121, an air outlet 122, and a liquid outlet 123. The desorption apparatus 130 is a bubble column including: a liquid inlet 131, a carrier gas inlet 132, an exhaust 133, and a liquid outlet 134.
In this example, the number of decomposition reactors was plural, and the number of regeneration reactors was 1. The plurality of decomposition reactors are connected in series, that is, the liquid outlet 113 of the former decomposition reactor is communicated with the liquid inlet 111 of the latter decomposition reactor through the connecting pipeline 150. The liquid outlet 113 of the last decomposition reactor is connected to the inlet 131 of the desorption device via a connecting line 150. The liquid outlet 134 of the desorption device is communicated with the liquid inlet 121 of the regeneration reactor through a connecting pipeline 150. The liquid outlet 123 of the regeneration reactor is communicated with the liquid inlet 111 of the decomposition reactor through a connecting pipeline 150.
The preparation device of the second embodiment of the present invention is substantially the same as the working principle and process of the first embodiment, except for the difference. In order to control the reaction depth, a plurality of decomposition reactors are connected in series, and of course, the regeneration reactor may also be connected in series or in parallel, which is not described herein.
As a specific example, each decomposition reactor 110 has a volume of 1.25m31m in diameter and 1.5m in height, and a packing factor of 0.7. The volume of the regeneration reactor 120 was 2.5m3The diameter was 1.25m, the height was 2m, and the packing factor was 0.7. The ratio of the total flow of ammonium bisulfate to the total flow of ammonium chloride was fixed at 2:1, i.e., the total flow of ammonium chloride was 8.23 kmol/h. Wherein NH in the decomposition reactor 110(1)4Cl flow 4.92kmol/h, NH in decomposition reactor 110(2)4The Cl flow was 3.31kmol/h and the ammonium bisulfate flow was 16.46 kmol/h. The temperatures of both the decomposition reactors were 240 ℃ and the regeneration reactor was set at 300 ℃, the contents of generated hydrogen chloride and ammonia gas were measured, the conversion was calculated, and the measurement results are shown in table 5, in which: the flow rate of the hydrogen chloride is the sum of the hydrogen chloride flow rates of the two reactors. The regeneration conversion rate is a decomposition conversion rate of ammonia gas with respect to the produced ammonium sulfate.
TABLE 5 results of decomposition reactors with two identical reaction vessels connected in series
| Categories | HCl/kmol/h | NH3/kmol/h | Decomposition conversion rate/%) | Regeneration conversion rate/%) |
| Results | 7.9 | 7.4 | 96.0 | 93.7 |
Fig. 3 is a schematic view of a preparation system according to a third embodiment of the present invention. The system comprises only one reactor in which both decomposition and regeneration reactions are carried out, but with different periods and conditions of operation. The third embodiment reactor 210 comprises: a liquid inlet 211, an outlet 212, a liquid outlet 113, and a solid particle feeder 214. Wherein the solid particle feeding device 214 comprises: the feeding pipe 201 extends from the wall of the decomposition reactor 210 to a position below the liquid level of the liquid material inside, and the quantitative conveying device is communicated with the feeding pipe 201 through a pipeline.
The utility model discloses the working process of preparation system of third embodiment does: with batch operation, the ammonium bisulfate is heated to a molten state in reactor 210. At a first preset temperature, ammonium chloride particles are continuously added into the reactor 210 at a certain flow rate by a solid particle feeding device 214, ammonium chloride and ammonium bisulfate generate hydrogen chloride gas and intermediate materials in the reactor 210, and the hydrogen chloride gas is discharged through an exhaust port 212 of the reactor. After the first predetermined time interval, the intermediate material is thermally decomposed at a second predetermined temperature in the reactor 210 to form ammonium bisulfate and ammonia gas, and the ammonia gas is discharged through the exhaust port 212 of the reactor.
The operation can follow the operation of a common batch reaction kettle, ammonium chloride and ammonium bisulfate are added according to the optimal proportion, the temperature is raised to the optimal decomposition temperature (first preset temperature), the hydrogen chloride gas is sent to the subsequent process outside the system, the temperature is raised to the optimal regeneration temperature (second preset temperature) after the first preset time, the ammonia gas is sent to the subsequent process outside the system, the temperature is lowered to the optimal decomposition temperature after the second preset time, and the operation is repeated.
As a specific example, reactor 210 is stirredA kettle reactor with a volume of 4m3The diameter was 1.5m, the height was 2.25m, the packing factor was 0.7, and the ratio of the amounts of the added ammonium bisulfate and ammonium chloride was fixed at 2: 1. In a batch operation, ammonium chloride was added at a rate of 220kg/h, 16.46kmol of ammonium bisulfate was previously melted in the reactor, the decomposition temperature was set to 240 ℃, the regeneration temperature was set to 300 ℃, the contents of generated hydrogen chloride and ammonia gas were measured, the conversion rate was calculated, and the measurement results are shown in Table 6, wherein: the regeneration conversion rate is a decomposition conversion rate of ammonia gas with respect to the produced ammonium sulfate.
TABLE 6 results of operating with one reactor
| Categories | HCl/kmol/h | NH3/kmol/h | Decomposition conversion rate/%) | Regeneration conversion rate/%) |
| Results | 6.3 | 5.7 | 76.5 | 90.5 |
Fig. 4 is a schematic view of a preparation system according to a fourth embodiment of the present invention. The production system of the fourth embodiment includes: decomposition reactors 110(1) and 110(2), regeneration reactors 120(1) and 120(2), desorption apparatus 130, molten salt pump 140, and connecting line 150.
In this embodiment, the decomposition reactors 110(1) and 110(2) are stirred tank reactors, each comprising: a liquid inlet 111, an outlet 112, a liquid outlet 113, and a solid particle feeder 114. Wherein the solid particle feeding device 114 comprises: the feeding pipe 101 extends from the wall of the decomposition reactor to a position below the liquid level of the liquid material inside the decomposition reactor, and the quantitative conveying device is communicated with the feeding pipe 101 through a pipeline. The regeneration reactors 120(1) and 120(2) are tubular reactors, each comprising: a liquid inlet 121, an air outlet 122, a liquid outlet 123, and a heat conducting oil outlet/inlet 124. The desorption apparatus 130 is a bubble column including: a liquid inlet 131, a carrier gas inlet 132, an exhaust 133, and a liquid outlet 134.
In this example, the number of the decomposition reactors and the regeneration reactors is plural. The plurality of decomposition reactors are connected in series, that is, the liquid outlet 113 of the former decomposition reactor is communicated with the liquid inlet 111 of the latter decomposition reactor through the connecting pipeline 150. The liquid outlet 113 of the last decomposition reactor is connected to the inlet 131 of the desorption device via a connecting line 150. The plurality of regeneration reactors are connected in series, that is, the liquid outlet 123 of the previous regeneration reactor is communicated with the liquid inlet 121 of the next regeneration reactor through a connecting pipe 125, the liquid inlet 121 of the first regeneration reactor is communicated with the outlet 134 of the desorption device through a connecting pipe 150, and the liquid outlet 123 of the last regeneration reactor is communicated with the liquid inlet 111 of the first decomposition reactor through a connecting pipe 150.
The utility model discloses the preparation system of fourth embodiment is unanimous with the theory of operation, the process of first embodiment generally, and the difference lies in, considers that reaction time is long, and reaction heat load is big, for increase heat transfer area, extension dwell time adopts the operation mode of a plurality of tubular reactor series connection, and wherein, the heating method is for adopting heating medium to heat outside the tubes, and of course, regenerative reactor also can adopt the operation mode that a plurality of reactors parallel, no longer gives details here.
As a specific example, the decomposition reactor is the same as that of example III, or may be only thatThe first decomposition reactor 110(1) is provided with a solid particle feeding device 114. The regeneration reactor adopts two sections of tubular reactors connected in series, and the volume of each section of tubular reactor is 1.25m3The diameter was 0.5m and the length was 6.37 m. The molar ratio of the ammonium bisulfate to the ammonium chloride is fixed to be 2:1, namely the molar flow rate of the ammonium chloride is 8.233kmol/h, and the addition amount of the ammonium bisulfate is 16.466 kmol. The reaction temperatures of the two decomposition reactors 110(1) and 110(2) were 240 ℃ and the reaction temperatures of the two regeneration reactors 120(1) and 120(2) were 300 ℃, and the contents of generated hydrogen chloride and ammonia gas were measured, and the conversion was calculated and the measurement results are shown in table 7, in which: the regeneration conversion rate is a decomposition conversion rate of ammonia gas with respect to the produced ammonium sulfate.
TABLE 7 results of a regenerative reactor with two tubular reactors in series
| Categories | HCl/kmol/h | NH3/kmol/h | Decomposition conversion rate/%) | Regeneration conversion rate/%) |
| Results | 7.9 | 7.6 | 96 | 96.2 |
Fig. 5 is a schematic view of a preparation system according to a fifth embodiment of the present invention. The preparation system of the fifth embodiment comprises: a decomposition reactor 110, regeneration reactors 120(1) and 120(2), a desorption device 130, a molten salt pump 140, and a connecting line 150.
In this embodiment, the decomposition reactors 110 are stirred tank reactors, each including: a liquid inlet 111, an outlet 112, a liquid outlet 113, and a solid particle feeder 114. Wherein the solid particle feeding device 114 comprises: the feeding pipe 101 extends from the wall of the decomposition reactor to a position below the liquid level of the liquid material inside the decomposition reactor, and the quantitative conveying device is communicated with the feeding pipe 101 through a pipeline. The regeneration reactors 120(1) and 120(2) are tubular reactors, each comprising: a liquid inlet 121, an air outlet 122, a liquid outlet 123, and a heat conducting oil outlet/inlet 124. The desorption apparatus 130 is a bubble column including: a liquid inlet 131, a carrier gas inlet 132, an exhaust 133, and a liquid outlet 134.
In this example, the number of decomposition reactors was 1, and the number of regeneration reactors was plural. The liquid outlet 113 of the decomposition reactor is connected to the inlet 131 of the desorption device via a connecting line 150. The plurality of regeneration reactors are connected in series, that is, the liquid outlet 123 of the previous regeneration reactor is communicated with the liquid inlet 121 of the next regeneration reactor through a connecting pipe 125, the liquid inlet 121 of the first regeneration reactor is communicated with the outlet 134 of the desorption device through a connecting pipe 150, and the liquid outlet 123 of the last regeneration reactor is communicated with the liquid inlet 111 of the decomposition reactor through a connecting pipe 150.
The fifth embodiment of the present invention is basically the same as the fourth embodiment in terms of the operation principle and process, except that the number of the decomposition reactors is 1.
As a specific example, the decomposition reactor 110 has a volume of 4m3The diameter is 1.5m, the height is 2.25m, the filling coefficient is 0.7, the regeneration reactor adopts two sections of tubular reactors which are connected in series, and the volume of each section of tubular reactor is 1.25m3The diameter was 0.5m and the length was 6.37 m. The molar ratio of the ammonium bisulfate to the ammonium chloride is fixed to be 2:1, namely the molar flow rate of the ammonium chloride is 8.233kmol/h, and the addition amount of the ammonium bisulfate is 16.466 kmol. Decomposition reactorThe reaction temperature of (2) was 240 ℃ and the reaction temperatures of the two regeneration reactors 120(1) and 120(2) were 300 ℃, the contents of generated hydrogen chloride and ammonia gas were measured, the conversion was calculated, and the measurement results are shown in table 8, in which: the regeneration conversion rate is a decomposition conversion rate of ammonia gas with respect to the produced ammonium sulfate.
TABLE 8 decomposition reaction 1, regeneration reactor with two-stage tubular reactor series
| Categories | HCl/kmol/h | NH3/kmol/h | Decomposition conversion rate/%) | Regeneration conversion rate/%) |
| Results | 7.6 | 7.2 | 92.3 | 94.7 |
Fig. 6 is a schematic view of a manufacturing system according to a sixth embodiment of the present invention. The production system of the sixth embodiment includes: a decomposition reactor 110, regeneration reactors 120(1) and 120(2), a desorption device 130, a molten salt pump 140, and a connecting line 150.
In this embodiment, the decomposition reactors 110 are stirred tank reactors, each including: a liquid inlet 111, an outlet 112, a liquid outlet 113, and a solid particle feeder 114. Wherein the solid particle feeding device 114 comprises: the feeding pipe 101 extends from the wall of the decomposition reactor to a position below the liquid level of the liquid material inside the decomposition reactor, and the quantitative conveying device is communicated with the feeding pipe 101 through a pipeline. The regeneration reactors 120(1) and 120(2) are stirred tank reactors, each comprising: a liquid inlet 121, an air outlet 122 and a liquid outlet 123. The desorption apparatus 130 is a bubble column including: a liquid inlet 131, a carrier gas inlet 132, an exhaust 133, and a liquid outlet 134.
In this example, the number of decomposition reactors was 1, and the number of regeneration reactors was plural. The liquid outlet 113 of the decomposition reactor is connected to the inlet 131 of the desorption device via a connecting line 150. The plurality of regeneration reactors are connected in parallel, that is, the liquid inlet 121 of each regeneration reactor is communicated with the outlet 134 of the desorption device through a connecting pipeline 150, and the liquid outlet 123 of each regeneration reactor is communicated with the liquid inlet 111 of the decomposition reactor through a connecting pipeline 150.
The utility model discloses the theory of operation, the process of preparation system of sixth embodiment and fifth embodiment are generally unanimous, and the difference lies in, and the regeneration reactor is the cauldron formula reactor.
As a specific example, the decomposition reactor 110 has a volume of 4m3The diameter is 1.5m, the height is 2.25m, the filling coefficient is 0.7, the regeneration reactor adopts two kettle type reactors which are connected in parallel, and the volume of each reactor is 1.25m3The diameter was 0.84m, the height was 1.26m, and the packing factor was 0.7. The molar ratio of the ammonium bisulfate to the ammonium chloride is fixed to be 2:1, namely the molar flow rate of the ammonium chloride is 8.233kmol/h, and the addition amount of the ammonium bisulfate is 16.466 kmol. The reaction temperature of the decomposition reactor was 240 ℃ and the reaction temperatures of the two regeneration reactors 120(1) and 120(2) were 300 ℃, the contents of generated hydrogen chloride and ammonia gas were measured, the conversion was calculated, and the measurement results are shown in table 9, in which: the regeneration conversion rate is a decomposition conversion rate of ammonia gas with respect to the produced ammonium sulfate.
TABLE 9 results of the regenerative reactor using two tank reactors in parallel
| Categories | HCl/kmol/h | NH3/kmol/h | Decomposition conversion rate/%) | Regeneration conversion rate/%) |
| Results | 7.7 | 7.4 | 93.5 | 96.1 |
It should be noted that, according to the general knowledge of those skilled in the art, the decomposition reactor and the regeneration reactor are also provided with corresponding temperature, liquid level, etc. measurement, control system and corresponding valves, which are not shown in the drawings, and this does not indicate that the process of the present invention does not include these conventional designs. The adjustment of the feed rate of the raw materials in the present invention based on the conversion and material balance is also a conventional design of the general knowledge of the skilled person in the art, and is not described one by one in the present invention, which does not mean that the process of the present invention does not include such a conventional design.
In accordance with the embodiments of the present invention as set forth above, these embodiments are not exhaustive and do not limit the invention to the precise embodiments described. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and its practical application, to thereby enable others skilled in the art to best utilize the invention and its various embodiments with various modifications as are suited to the particular use contemplated.
Claims (19)
1. A preparation system for preparing hydrogen chloride gas and ammonia gas by utilizing ammonium chloride is characterized in that,
the preparation system comprises at least one reactor;
in the reactor, the ammonium chloride and ammonium bisulfate are subjected to decomposition reaction to output the hydrogen chloride gas and obtain an intermediate material;
the intermediate material is subjected to a regeneration reaction to output the ammonia gas and obtain the ammonium bisulfate;
wherein the decomposition reaction and the regeneration reaction occur in different working stages of the same reactor or in a plurality of reactors which can be communicated, and the ammonium chloride is continuously added into at least one reactor in the form of solid particles,
the reactor comprises a stirred tank reactor and/or a rotary drum reactor.
2. The system of claim 1, wherein the ammonium bisulfate is in a molten state.
3. A production system according to claim 2, wherein at least one of the reactors comprises a solid particle feed for continuously feeding the ammonium chloride into the reactor.
4. The system of claim 3, wherein the solid particulate feed device comprises:
the feeding pipe extends from the wall of the reactor to a position below the liquid level of the liquid material in the reactor; and
and the quantitative conveying device is communicated with the feeding pipe through a pipeline.
5. The production system according to claim 4, wherein when the decomposition reaction and the regeneration reaction occur in a plurality of the reactors that are communicable, the at least one reactor includes:
at least one decomposition reactor for decomposition reactions to occur, at least one of the decomposition reactors comprising: the device comprises a solid particle feeding device, a liquid feeding port, a liquid discharging port and an exhaust port;
at least one regeneration reactor for a regeneration reaction to occur, at least one of the regeneration reactors comprising: a liquid inlet, a liquid outlet and an exhaust port;
the liquid discharge port of at least one decomposition reactor is communicated with the liquid feeding port of at least one regeneration reactor through a connecting pipeline, and the liquid feeding port of at least one decomposition reactor is communicated with the liquid discharge port of at least one regeneration reactor through a connecting pipeline.
6. The production system according to claim 5, further comprising at least one desorption apparatus connected to the at least one decomposition reactor,
the desorption apparatus includes: a liquid feeding port, a carrier gas inlet, a liquid discharging port and an exhaust port,
the liquid feeding port of the desorption device is connected with the liquid discharging port of at least one decomposition reactor, the liquid discharging port of the desorption device is connected with the liquid feeding port of at least one regeneration reactor,
and in the desorption device, the hydrogen chloride gas dissolved in the intermediate material is separated out and is discharged through an exhaust port of the desorption device.
7. The system of claim 6, wherein the decomposition reactor and the regeneration reactor further comprise a heating device and a temperature control device.
8. The manufacturing system of claim 7, further comprising:
at least one molten salt pump, which is positioned at the connection position of the liquid discharge port of the decomposition reactor and the liquid feed port of the regeneration reactor and/or at the connection position of the liquid feed port of the decomposition reactor and the liquid discharge port of the regeneration reactor; and
and the heat preservation device is positioned at the joint between the reactors.
9. The production system according to any one of claims 5 to 8, wherein the number of the decomposition reactors and the regeneration reactors is 1.
10. The production system according to any one of claims 6 to 8, wherein the at least one decomposition reactor is provided in plural, and the plural decomposition reactors are connected in series,
namely, the liquid discharge port of the former decomposition reactor is connected with the liquid feed port of the latter decomposition reactor;
the liquid discharge port of the last decomposition reactor is connected with the feed port of the desorption device;
at least a first decomposition reactor comprises said solid particle feeding means;
at least the first decomposition reactor comprises heating means;
each of the decomposition reactors includes a temperature control device.
11. The production system according to claim 10, wherein the reaction temperature of the latter decomposition reactor is not higher than the reaction temperature of the former decomposition reactor.
12. A production system according to claim 10, wherein each of the decomposition reactors comprises the solid particle feeding device.
13. The system for preparing a catalyst according to claim 10, wherein the number of the decomposition reactors is in the range of 2 to 3.
14. The system of claim 10, wherein the number of the at least one regeneration reactor is 1, and the liquid outlet of the regeneration reactor is in communication with at least the liquid inlet of the first decomposition reactor.
15. The production system according to claim 10, wherein the at least one regeneration reactor is provided in plural number, and the plural regeneration reactors are connected in series,
namely, the liquid discharge port of the previous regeneration reactor is connected with the liquid feed port of the next regeneration reactor;
the liquid feeding port of the first regeneration reactor is connected with the liquid discharging port of at least one decomposition reactor;
and the liquid discharge port of the last regeneration reactor is at least connected with the liquid feed port of the first decomposition reactor.
16. The production system according to any one of claims 5 to 8, wherein the at least one decomposition reactor is 1 in number, the at least one regeneration reactor is plural in number, and the plural regeneration reactors are connected in series,
namely, the liquid discharge port of the previous regeneration reactor is connected with the liquid feed port of the next regeneration reactor;
the liquid feeding port of the first regeneration reactor is connected with the liquid discharging port of the decomposition reactor;
and the liquid discharge port of the last regeneration reactor is connected with the liquid feed port of the decomposition reactor.
17. The production system according to any one of claims 5 to 8, wherein the at least one decomposition reactor is 1 in number, the at least one regeneration reactor is plural in number, and the plural regeneration reactors are connected in parallel,
namely, the liquid discharge port of each regeneration reactor is connected with the liquid feed port of the decomposition reactor,
and the liquid feeding port of each regeneration reactor is connected with the liquid discharging port of the decomposition reactor.
18. The production system according to any one of claims 5 to 8, wherein the decomposition reactor comprises a stirred tank reactor and/or a rotary drum reactor;
the regeneration reactor comprises a tubular reactor, a stirred tank reactor and/or a rotary drum reactor.
19. The production system according to any one of claims 1 to 4, wherein the reactor is a stirred reactor or a rotary drum reactor when the decomposition reaction and the regeneration reaction occur in different stages of operation of the same reactor.
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