Trickle bed reactor for continuously producing calcium chloride solution through reaction of hydrochloric acid and limestone

Abstract

The utility model relates to the technical field of chemical equipment, and mainly discloses a trickle bed reactor for continuously producing calcium chloride solution through reaction of hydrochloric acid and limestone, which comprises an upper cone, a barrel and an eccentric lower cone, an acid inlet pipe supporting grid is arranged below the acid inlet pipe to divide the area below the acid inlet pipe into a plurality of independent compartments, the concentration of hydrochloric acid in the compartments is high, the reaction speed is high, a pulse flow reaction area is formed, and acid liquid can be uniformly distributed; the area below the cells is low in hydrochloric acid concentration and is a trickling reaction area, so that full reaction of hydrochloric acid is facilitated; a limestone supporting grating is arranged between the barrel and the lower cone, and a discharging pipe and a hydraulic control discharging valve assembly are arranged at the bottom of the barrel; the reactor is provided with bottom, middle and top graded exhaust ports to reduce the gas flow rate in the reactor and reduce foam entrainment; the structure obviously improves the hydrochloric acid conversion rate and the reactor productivity, and is suitable for continuous industrial production.

Description

TECHNICAL FIELD

[0001] The utility model relates to a chemical equipment technical field, concretely is a kind of calcium chloride solution's trickling bed reactor of continuous production of hydrochloric acid and limestone reaction. BACKGROUND

[0002] With the development of chemical industry, by-product hydrochloric acid production grows rapidly, and the outlet of by-product hydrochloric acid becomes a major problem restricting the development of related enterprises. Compared with the traditional ammonia alkali method of producing calcium chloride solution (ammonia alkali method), the by-product hydrochloric acid and limestone reaction process (acid-calcium method) has a great cost advantage. In recent years, the production capacity of calcium chloride produced by acid-calcium method has increased rapidly, while the production capacity of calcium chloride produced by ammonia alkali method has decreased year by year. The existing hydrochloric acid and limestone reaction to produce calcium chloride generally uses batch process, which has problems such as low production efficiency, incomplete reaction of raw materials, etc.

[0003] The utility model discloses a kind of continuous liquid discharge moving bed reactors of blocky limestone and hydrochloric acid reaction, and the reactor main body is by upper cylinder and the conical cylinder connected with upper cylinder, upper cylinder upper portion is equipped with limestone feed inlet and exhaust port, hydrochloric acid inlet pipe is arranged in upper cylinder middle part, and the bottom of conical cylinder is continuous liquid discharge discharge port. Hydrochloric acid flows into and limestone reacts from hydrochloric acid inlet pipe, and the generated calcium chloride solution is directly discharged from the continuous liquid discharge discharge port at the bottom of the cylinder, and the reaction is complete. The continuous flow reactor is continuously and stably operated in actual application, the acid-calcium conversion rate is high, and the use effect is good, but there are still the following deficiencies:

[0004] (1) The above-mentioned moving bed reactor discharges calcium chloride liquid and unreacted limestone, and a liquid-solid separation device and a return device are required to recover limestone, resulting in multiple reaction device auxiliary equipment, complex process, and increased production cost;

[0005] (2) The reaction of calcium carbonate and hydrochloric acid to produce calcium chloride itself produces a lot of foam and carbon dioxide, so the core of this process is defoaming. The amount of carbon dioxide is a direct factor affecting the generation of foam, and the carbon dioxide generated by the reactor is directly discharged from the top exhaust port. The rapid upward flow of carbon dioxide gas leads to entrainment of mist. In order to prevent too much foam from being carried out by carbon dioxide gas, the amount of acid entering the reactor must be controlled, reducing the production intensity of the reactor. Most of the space above the acid inlet pipe of the reactor is used for defoaming, and the efficiency of the reactor is low. Utility model content

[0006] The utility model aims at solving the technical problems existing in the prior art, and provides a kind of calcium chloride solution's trickling bed reactor of continuous production of hydrochloric acid and limestone reaction, and the calcium chloride solution generated by reaction is continuously discharged from the lower part of the reactor by optimizing the structure of the reactor;Gas flow rate is reduced by staged exhaust, foam generation is reduced, acid mist is removed, the production intensity of the reactor is high, and the unit cross-sectional area yield is large.

[0007] To achieve the above object, the utility model discloses the following technical scheme: a kind of hydrochloric acid and limestone reaction continuous production calcium chloride solution's trickle bed reactor, including upper cone, cylinder and lower cone which are sequentially arranged from top to bottom.The upper cone is the cone structure of orthosteric, cylinder is cylindrical structure, and the lower cone is the cone structure of inverted;

[0008] The top of the upper cone is provided with a limestone feed inlet and a top exhaust port, the bottom of the lower cone is provided with a calcium chloride solution outlet, and the top of the upper cone is further provided with a pressure sensor and a sight port.

[0009] A manhole is provided below the cylinder for maintenance of the reactor.

[0010] Two or more groups of horizontal hydrochloric acid inlet pipes are provided side by side inside the cylinder, and a plurality of acid inlet holes are horizontally distributed on both sides of the hydrochloric acid inlet pipe.

[0011] A bottom exhaust port is provided on the lower cone, an upper gas inlet is provided on the top of the cylinder, and a middle exhaust port is provided between the hydrochloric acid inlet pipe and the upper gas inlet.

[0012] Through the technical scheme, the limestone raw material is put into and fills the inside of the barrel of the reactor through the limestone feeding port, the hydrochloric acid is continuously introduced through the acid inlet pipe, the hydrochloric acid flows downward in the gap of the limestone filling layer and fully reacts with the limestone, the concentration of the hydrochloric acid in the acid inlet pipe support grid below the acid inlet pipe is high, the reaction speed is fast, a large amount of carbon dioxide gas generated in the reaction flows upward in the form of pulse flow, a pulse flow reaction zone is formed, the acid liquid is uniformly distributed in the cross section of the reaction zone, and most of the hydrochloric acid reacts with the limestone in the area; the concentration of the hydrochloric acid in the area below the acid inlet pipe support grid is reduced, the amount of carbon dioxide gas generated is small, and the gas and the liquid move downward in the limestone filling layer in the same direction, the liquid phase flows in the form of liquid film on the surface of the particles, the gas-liquid two-phase interaction is weak, and a trickling flow reaction zone is formed, thereby continuously ensuring that the hydrochloric acid fully reacts with the limestone. In the area above the acid inlet pipe, the carbon dioxide fully contacts the limestone material layer, and functions as a defoaming zone. The calcium chloride solution, the silt and the acid-insoluble substances generated in the reaction are discharged from the calcium chloride solution outlet, and the limestone consumed in the reaction falls into the automatic supplement through the limestone feeding port.

[0013] Further, through the technical scheme, part of the carbon dioxide gas generated in the pulse flow reaction zone flows upward in the barrel, fully contacts the limestone filling layer above the acid inlet pipe, removes the mist and the acid mist, and is discharged through the upper exhaust port at the top, is divided into two parts through the middle exhaust port, and the other part of the carbon dioxide gas flows downward with the generated calcium chloride solution and is discharged through the lower exhaust port arranged in the lower cone. Since the upward speed of the carbon dioxide in the barrel of the reactor is reduced, the phenomenon that the tail gas mist is seriously entrained due to foaming of the reactor is effectively controlled, the production intensity of the reactor is high, the yield per unit cross-sectional area is large, the upward amount of the carbon dioxide is adjusted by adjusting the opening degree of the valve, and the surface of the limestone material layer in the reactor is ensured to be free of foam.

[0014] Further, the middle exhaust port is arranged on the side close to the upper gas inlet port between the acid inlet pipe and the upper gas inlet port, the middle exhaust port cannot be too close to the acid inlet pipe, and the unreacted acid liquid is prevented from entering the middle exhaust port too early and being discharged with the carbon dioxide.

[0015] Further, the acid inlet pipe is arranged in the middle upper part of the barrel, the volume of the trickling flow reaction zone is large, and the volume of the defoaming zone is small, so that the volume utilization rate of the reactor is improved.

[0016] The further scheme of the utility model lies in, the hydrochloric acid inlet pipe is provided with a baffle above, preferably, the baffle section is inverted V, the center line of the baffle and the axis of the hydrochloric acid inlet pipe are in the same vertical plane, the width of the baffle bottom is 2-5 times of the diameter of the hydrochloric acid inlet pipe, the inverted V-shaped baffle is used to protect the hydrochloric acid inlet pipe from impact and abrasion of limestone on one hand, and to ensure that the acid liquid sprayed from the acid inlet hole directly enters the independent grid of the hydrochloric acid inlet pipe support grid below, and to realize the uniform distribution of the acid liquid in the reactor cross section during the reaction with the rising carbon dioxide gas.

[0017] The further scheme of the utility model lies in, the acid inlet pipe support grid is formed by the separation rib plate, the independent grid close to the inner wall of the cylinder is separated from the inner wall of the cylinder by the separation rib plate, and the acid liquid can be prevented from flowing along the inner wall of the reactor cylinder to form a short circuit.

[0018] Preferably, the hydrochloric acid inlet pipe is provided with two groups, and the two groups of hydrochloric acid inlet pipes are symmetrically distributed along the diameter of the cylinder cross section, the volume of the independent grid in the middle of the cylinder is larger, the volume of the independent grid at the edge of the cylinder is smaller, the number of acid inlet holes of the hydrochloric acid inlet pipe towards the center of the cylinder is larger than that towards the inner wall of the cylinder, and the acid liquid can be further uniformly distributed in the independent grid.

[0019] Preferably, 2-6 acid inlet holes are arranged in each independent grid in the middle of the cylinder between the two groups of hydrochloric acid inlet pipes, and 1-3 acid inlet holes are arranged in each independent grid at the edge of the cylinder of each group of hydrochloric acid inlet pipes, and preferably, the diameter of the acid inlet hole is 12-20 mm.

[0020] Preferably, the bottom of the limestone support grid is supported by the support rib plate, and the spacing between the grid plates of the limestone support grid is 12-30 mm, and the discharge hole in the center of the limestone support grid is connected with the discharge pipe.

[0021] The further scheme of the utility model lies in, the lower cone is an inverted eccentric cone, preferably, the calcium chloride solution outlet is arranged at the lowest point of the lower cone, the flushing liquid port is arranged at the maximum value of the line connecting the calcium chloride solution outlet and the top surface of the lower cone, and the bottom exhaust port is arranged at the minimum value of the line connecting the calcium chloride solution outlet and the top surface of the lower cone. By the above scheme, the silt, acid insoluble matter and calcium chloride solution flow down along the inner wall of the eccentric cone, and there is less silt and acid insoluble matter on the curved surface with smaller slope, and there is basically no residue on the curved surface with larger slope, so that the flushing liquid port is arranged at the position to clean the residue on the curved surface with smaller slope to the maximum extent, and the bottom exhaust port is arranged at the position with the largest slope to facilitate the discharge of carbon dioxide gas.

[0022] The further scheme of the utility model lies in, the blind plate is equipped with the discharge valve assembly in the discharge end of the discharge pipe.

[0023] Preferably, the valve plate has a gap between the upper edge and the lower edge of the limestone supporting grid, and the gap is 5mm-20mm.

[0024] Compared with the prior art, the utility model has the beneficial effects that:

[0025] 1. The utility model discloses a hierarchical exhaust design, which divides the carbon dioxide gas into different heights and discharges, reduces the ascending speed of the gas in the cylinder, avoids the excessive speed of the ascending gas flow to produce a large amount of foam and mist entrainment, improves the stability of the reactor operation, and the bottom exhaust port, the middle exhaust port and the upper gas inlet are connected in series through the gas communication pipe, the valve adjusts the shunt ratio, the hierarchical exhaust system significantly reduces the foam and acid mist entrainment, and improves the output per unit cross-sectional area of the reactor.

[0026] 2. The utility model discloses that the supporting grid of the acid inlet pipe is divided into a plurality of independent compartments by the partitioning rib plate, and the acid inlet holes on both sides of the hydrochloric acid inlet pipe are arranged according to the regional differences; the independent compartments limit the flow path of the acid liquid, avoid the acid liquid flowing along the inner wall of the cylinder to form a "short circuit", and the acid inlet holes in the middle compartment are densely arranged for injection, and the edge holes are supplemented to ensure that the acid liquid uniformly covers the limestone filler layer on the cross section, and the reaction conversion rate is improved to pH>4.0.

[0027] 3. The utility model discloses that the lower cone is an eccentric structure, the calcium chloride solution outlet is located at the lowest point, the flushing liquid port is arranged on the side with the smallest slope, and the bottom exhaust port is located on the side with the largest slope. The calcium chloride solution produced along with the reaction is naturally flowed to the outlet along the eccentric conical surface, the residues on the side with the smaller slope are washed by the flushing liquid port at regular time, and the internal material accumulation of the lower cone is prevented.

[0028] 4. The utility model discloses that the supporting grid of the acid inlet pipe is a pulse flow area, and the lower part is a drop flow area, the pulse flow area forms a turbulent flow through high gas speed, rapidly consumes a large amount of hydrochloric acid, and the drop flow area prolongs the reaction time to ensure that the hydrochloric acid is completely converted.

[0029] 5.The limestone supporting grid of the utility model limestone material layer on the limestone supporting grid plays a filtering role on the reaction generated liquid. With the reaction, the particle size of the blocky limestone gradually decreases, the unreacted limestone small particles are blocked in the winding channel between the filler layer limestone, and continue to react with hydrochloric acid, while the silt and acid-insoluble substances in the limestone flow out with the reaction generated liquid, realizing the continuous slagging of the reactor, and the limestone reaction conversion rate is close to 100%.

[0030] 6.A reverse V-shaped baffle is arranged above the hydrochloric acid inlet pipe, the bottom width is 2-5 times of the pipe diameter, and the center line is aligned with the axis of the hydrochloric acid inlet pipe. The baffle disperses the pressure of the limestone above, prevents the impact and wear of the hydrochloric acid inlet pipe, and the reverse V-shaped structure forms a free space around the hydrochloric acid inlet pipe, so that the acid liquid is horizontally injected into the independent grid, which is beneficial to the rapid distribution of hydrochloric acid in the reactor cross section and improves the utilization rate of the reaction zone. BRIEF DESCRIPTION OF DRAWINGS

[0031] In order to more clearly illustrate the technical scheme in the embodiments of the utility model or the prior art, the drawings needed to be used in the embodiment or the prior art description will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the utility model, and for those skilled in the art, other drawings can also be obtained according to these drawings without creative labor.

[0032] Figure 1 It is the overall structure schematic diagram of the reactor of the utility model;

[0033] Figure 2 It is the top view of the reactor of the utility model;

[0034] Figure 3 It is the utility model Figure 1 Along the direction of A-A section schematic diagram;

[0035] Figure 4 It is the utility model Figure 1 Along the direction of B-B section local schematic diagram;

[0036] Figure 5 It is the utility model Figure 1 Along the direction of C-C section schematic diagram;

[0037] Figure 6 It is the utility model Figure 5 Along the direction of D-D section local schematic diagram.

[0038] In the figure, 1, upper cone; 2, cylinder; 3, lower cone; 4, limestone supporting grid; 5, hydrochloric acid inlet pipe; 6, baffle; 7, acid inlet pipe supporting grid; 8, discharge pipe; 9, discharge valve assembly; 10, bottom exhaust port; 11, middle exhaust port; 12, upper inlet port; 13, gas communication pipe; 14, valve; 15, calcium chloride solution outlet; 16, limestone inlet port; 17, top exhaust port; 18, flushing liquid port; 19, hydrochloric acid inlet port; 20, discharge valve port; 21, manhole; 22, pressure sensor; 23, sight glass port; 24, independent grid; 25, partition rib plate; 26, supporting rib plate; 27, hydraulic cylinder; 28, valve rod; 29, slide; 30, valve plate. DETAILED DESCRIPTION

[0039] In order to better understand the above technical solutions, the above technical solutions will be described in detail below in combination with the drawings of the specification and specific embodiments.

[0040] Figures 1-6 An embodiment of the utility model is shown.

[0041] As Figure 1 shown, the embodiment provides a hydrochloric acid and limestone reaction continuous production calcium chloride solution's trickling bed reactor, including upper cone 1, cylinder 2 and lower cone 3 that are sequentially arranged from top to bottom. Specifically, the upper cone 1 is a right cone structure, the cylinder 2 is a cylindrical structure, and the lower cone 3 is an inverted cone structure.

[0042] As Figure 2 shown, the top of the upper cone 1 is provided with a limestone inlet port 16 and a top exhaust port 17, the bottom of the lower cone 3 is provided with a calcium chloride solution outlet 15, and the top of the upper cone 1 is further provided with a pressure sensor 22 and a sight glass port 23. The pressure sensor 22 is used to monitor the internal pressure of the reactor, and the sight glass port 23 is used to observe the foam condition inside the upper cone 1. A manhole 21 is provided below the cylinder 2 for maintenance of the reactor. Those skilled in the art can change the installation positions of the above-mentioned limestone inlet port, top exhaust port 17, calcium chloride solution outlet 15, pressure sensor 22, sight glass port 23, manhole 21 and other structures according to requirements. The embodiment is only an installation example of the above-mentioned structures, and does not limit the specific installation positions and installation heights.

[0043] As Figure 1 shown, the cylinder 2 and the lower cone 3 are provided with a limestone supporting grid 4 for supporting the limestone layer. The bottom of the limestone supporting grid 4 is provided with an openable and closable discharge pipe 8. The discharge pipe 8 communicates the area above the limestone supporting grid 4 with the external area of the lower cone 3. The discharge pipe 8 is used to discharge the unreacted limestone in the reactor during shutdown.

[0044] AsFigure 3 As shown, in the embodiment, the upper part of the barrel 2 is provided with two or more groups of horizontally arranged hydrochloric acid feeding pipes 5, which are detachably inserted into the barrel 2 through the hydrochloric acid feeding port 19. Preferably, in the embodiment, the hydrochloric acid feeding pipes 5 are arranged at the upper middle part of the barrel 2, which increases the volume of the reaction zone and improves the volume utilization rate of the reactor. A plurality of acid feeding holes are horizontally distributed on both sides of the acid feeding pipe. In the embodiment, the barrel 2 is provided with two groups of hydrochloric acid feeding pipes 5, which are symmetrically distributed along the diameter of the cross section of the barrel 2.

[0045] As shown in the drawings, Figure 3 , Figure 4 The lower part of the hydrochloric acid feeding pipe 5 is provided with an acid feeding pipe supporting grid 7. The acid feeding pipe supporting grid 7 is used to support the hydrochloric acid feeding pipe 5 and divide the lower area of the hydrochloric acid feeding pipe 5 into a plurality of independent cells 24.

[0046] Specifically, the acid feeding pipe supporting grid 7 is formed by a plurality of partitioning ribs 25, and the independent cells 24 close to the inner wall of the barrel 2 are separated from the inner wall of the barrel 2 by the partitioning ribs 25. This scheme can prevent the acid liquid from flowing along the inner wall of the reactor barrel 2 to form a short circuit. Since the cross-sectional area of the independent cells 24 at the middle part of the barrel 2 is larger than that of the independent cells 24 at the edge of the barrel 2, the number of acid feeding holes of the hydrochloric acid feeding pipe 5 towards the center of the barrel 2 is greater than that of the acid feeding holes towards the inner wall of the barrel 2. This scheme can further make the acid liquid uniformly distributed in the independent cells 24.

[0047] Preferably, each independent cell 24 at the middle part of the barrel 2 between the two groups of hydrochloric acid feeding pipes 5 is provided with 2-4 acid feeding holes, and each independent cell 24 at the edge of the barrel 2 of each group of hydrochloric acid feeding pipes 5 is provided with 1-2 acid feeding holes. Preferably, the diameter of the acid feeding hole is 12-20 mm. Preferably, the height of the partitioning rib 25 is 400-800 mm. In the embodiment, the number of acid feeding holes of the hydrochloric acid feeding pipe 5 towards the center of the barrel 2 is 7, and the number of acid feeding holes of the hydrochloric acid feeding pipe 5 towards the inner wall of the barrel 2 is 4. Each independent cell 24 at the middle part of the barrel 2 is provided with 2 acid feeding holes, and each independent cell 24 at the edge of the barrel 2 is provided with 1 acid feeding hole. The diameter of the acid feeding hole is 16 mm, and the height of the partitioning rib 25 is 600 mm.

[0048] As shown in the drawings, Figure 1 The lower part of the barrel 3 is provided with a bottom exhaust port 10, the barrel 2 is provided with a middle exhaust port 11, and the bottom exhaust port 10 and the middle exhaust port 11 are in communication with the top exhaust port 17.

[0049] Specific, the bottom exhaust port 10, middle exhaust port 11 through the gas communication pipe 13 connection, gas communication pipe 13 through the upper inlet 12 and top exhaust port 17 communication, bottom exhaust port 10 and middle exhaust port 11 between the valve 14, bottom exhaust port 10 is located in the limestone support grid 4 below the lower cone 3, the upper exhaust port is located in the cylinder 2 top, the middle exhaust port 11 is located in the cylinder 2 above the hydrochloric acid inlet pipe 5, by adjusting the gas communication pipe 13 bottom exhaust port 10 and middle exhaust port 11 between the valve 14 opening degree adjustment of the rising carbon dioxide gas quantity, ensure that the reactor limestone material layer surface without foam.

[0050] As shown in Figure 4 The upper part of the hydrochloric acid inlet pipe 5 is provided with a baffle 6, preferably, the cross section of the baffle 6 is inverted V-shaped, the center line of the baffle 6 and the axis of the hydrochloric acid inlet pipe 5 are in the same vertical plane, the width of the bottom of the baffle 6 is 2-5 times the diameter of the hydrochloric acid inlet pipe 5, in this embodiment, the diameter of the hydrochloric acid inlet pipe 5 is DN80, the width of the bottom of the baffle 6 is 320mm, the inverted V-shaped baffle 6 is used to protect the hydrochloric acid inlet pipe 5 from the pressure of the limestone, and on the other hand, it ensures that the acid liquid sprayed from the acid inlet hole directly enters the independent grid 24 of the acid inlet pipe supporting grid 7 below the hydrochloric acid inlet pipe 5, and realizes the uniform distribution of the acid liquid in the cross section of the reactor during the action with the rising carbon dioxide gas. Without the inverted V-shaped baffle, the acid liquid of the hydrochloric acid inlet pipe is directly sprayed onto the filled limestone to form a short circuit, and directly flows down along the separation rib of the acid inlet pipe supporting grid. The inverted V-shaped baffle structure forms a free space around the acid inlet pipe, which expands the radiation area of the acid liquid, so that the acid liquid can be sprayed horizontally into the independent grid.

[0051] The working principle of the utility model is: the limestone raw material is put into the inside of the cylinder 2 of the reactor through the limestone inlet, and the hydrochloric acid is continuously introduced through the acid inlet pipe, the hydrochloric acid flows downward in the gap of the limestone packing layer and reacts completely with the limestone, the concentration of the hydrochloric acid in the acid inlet pipe supporting grid 7 below the hydrochloric acid inlet pipe 5 is high, the reaction speed is fast, a large amount of carbon dioxide gas generated by the reaction flows upward, which is in the form of pulse flow, forming a pulse flow reaction zone, realizing the uniform distribution of the acid liquid in the cross section of the reaction zone, and most of the hydrochloric acid reacts with the limestone in this area; the concentration of the hydrochloric acid in the area below the acid inlet pipe supporting grid 7 is reduced, the amount of carbon dioxide gas generated is small, and the gas and liquid move downward in the same direction in the limestone packing layer, the liquid phase flows on the surface of the particles in the form of liquid film, the gas-liquid two-phase action is weak, which is in the form of trickle flow, forming a trickle flow reaction zone, and the hydrochloric acid continues to react with the limestone. In the area above the acid inlet pipe supporting grid 7, the carbon dioxide fully contacts with the limestone material layer, which plays a role in defoaming, and is a defoaming zone. The calcium chloride solution, mud and acid-insoluble substances generated by the reaction are discharged from the calcium chloride solution outlet 15, and the limestone consumed by the reaction falls into the supplement through the limestone inlet.

[0052] By the above technical scheme, the carbon dioxide gas generated in the pulse flow reaction zone flows upward in the cylinder 2, contacts the limestone filler layer at the upper part of the hydrochloric acid inlet pipe 5, removes the mist and acid mist, and is discharged through the upper exhaust port at the top, while being divided into two parts through the middle exhaust port 11, and the other part of the carbon dioxide gas flows downward with the generated calcium chloride solution and is discharged through the lower exhaust port installed at the lower cone, thereby reducing the upward speed of the carbon dioxide in the cylinder 2. The flow rate is related to the flow and the cross-sectional area, the total flow is dispersed to multiple exhaust ports, and the upward speed of the carbon dioxide in the reactor cylinder is reduced. Therefore, the phenomenon of severe entrainment of reaction tail gas mist caused by foaming of the reactor can be effectively controlled, the production intensity of the reactor is high, and the yield per unit cross-sectional area is large.

[0053] Further schemes of the utility model lie in that, as shown in the figure, Figure 1 The lower cone 3 is an inverted eccentric cone (the eccentric cone is a slanting circular cone in mathematical terms), and specifically, the calcium chloride solution outlet 15 is arranged at the lowest point of the lower cone 3 (i.e. the vertex of the slanting circular cone), and the top surface of the lower cone 3 is the bottom surface of the slanting circular cone. A line is drawn from the vertex of the slanting circular cone to the edge of the bottom surface, and it can be found that the length of the line takes the maximum value and the minimum value at two points respectively. The flushing liquid port 18 is arranged at the maximum value of the line from the calcium chloride solution outlet 15 to the top surface of the lower cone 3, and the bottom exhaust port 10 is arranged at the minimum value of the line. By using the above scheme, the silt, acid-insoluble substances and calcium chloride solution flow down along the inner wall of the eccentric cone, and there is less silt and acid-insoluble substances on the curved surface with a smaller slope, and there is basically no residue on the curved surface with a larger slope. Therefore, the flushing liquid port 18 is arranged at the position to clean the residue on the curved surface with a smaller slope to the maximum extent, and the bottom exhaust port 10 is arranged at the position from the calcium chloride solution outlet 15 to the position with the largest slope, so that the carbon dioxide gas is discharged from the position.

[0054] The spacing between the grid plates of the limestone supporting grid 4 is 12mm-30mm. In the embodiment, the spacing is 20mm.

[0055] The bottom of the limestone supporting grid 4 is supported by the supporting rib plate 26, and the discharge pipe 8 is arranged at the center of the limestone supporting grid 4. Specifically, as shown in the figure, Figure 1 The center of the limestone supporting grid 4 is provided with a discharge port, and the shape of the discharge port is not limited, and preferably, the discharge port is a round port or a square port. In the embodiment, the discharge port is a 350mm*350mm square discharge port. The discharge pipe 8 is installed directly below the discharge port at the center of the supporting grid, and the discharge valve assembly 9 is arranged between the discharge port and the discharge pipe 8.

[0056] Specifically, the discharge pipe 8 is controlled to open and close through the discharge valve assembly 9, and the discharge valve assembly 9 is installed in the discharge valve port 20.Figure 5 、 Figure 6 As shown in the figure, the discharge valve assembly 9 comprises a hydraulic cylinder 27, a valve rod 28, a slide 29 and a valve plate 30, the valve plate 30 is arranged between the limestone supporting grid 4 and the discharge pipe 8, the slide 29 is arranged on the supporting beam 26, one end of the valve plate 30 is connected with the valve rod 28, the valve plate 30 is slidingly connected with the slide 29, and the hydraulic cylinder 27 drives the valve rod 28 to move so as to drive the valve plate 30 to move along the slide 29.

[0057] The gap between the valve plate 30 and the lower edge of the limestone supporting grid 4 is 5mm-20mm, and the gap in this embodiment is 20mm.

[0058] When the above embodiment is actually operated, the limestone is continuously added into the cylinder 2 of the reactor through the limestone feeding port. When the reactor is initially charged, the limestone with a particle size of 20-50mm and a relatively uniform particle size is firstly added, the optimal particle size of the limestone is 20-35mm, and a limestone filler layer with a relatively uniform gap characteristic is formed above the limestone supporting grid 4, and the height of the filler layer is >300mm. The particle size of the raw limestone added after the formation of the uniform filler layer can be <100mm. The 31% hydrochloric acid is continuously added into the reactor through the hydrochloric acid feeding pipe 5, and the feeding amount of the hydrochloric acid is 16m 3 / hr. The hydrochloric acid feeding pipe supporting grid 7 is installed below the hydrochloric acid feeding pipe 5 to divide the area below the hydrochloric acid feeding pipe 5 into independent grids 24, the concentration of the hydrochloric acid in the area is high, the reaction speed is fast, a large amount of CO2 gas generated by the reaction flows upward and strongly reacts with the downward flowing acid liquid, the flow type is pulse flow, the acid liquid is uniformly distributed in the cross section of the reactor, and most of the hydrochloric acid reacts with the limestone in the area. The concentration of the hydrochloric acid below the hydrochloric acid feeding pipe supporting grid 7 is low, the amount of CO2 gas generated is small, and the gas and the liquid flow downward in the same direction in the limestone filler bed, the liquid phase flows on the surface of the particles in the form of a liquid film, and the gas-liquid two-phase reaction is weak, which is drop flow type, thereby ensuring that the hydrochloric acid and the limestone are fully reacted. The reaction liquid has been basically fully reacted when it flows to the limestone filler layer with a relatively uniform gap above the limestone supporting grid 4, the limestone in the filler layer basically does not participate in the reaction, the filling characteristics of the filler layer are stable, and this is beneficial to the stable operation of the reactor. The calcium chloride solution generated by the reaction flows into the eccentric lower cone 3 below the limestone supporting grid 4 together with the mud and acid-insoluble substances in the limestone, and is continuously discharged through the calcium chloride solution outlet 15 arranged at the lowest part of the lower cone 3. During the normal operation process, the rising CO2 gas amount is adjusted by adjusting the opening degree of the valve 14 of the gas communication pipe 13 through the observation of the sight glass port 23 arranged on the upper cone of the reactor, so as to ensure that there is no foam on the surface of the limestone layer in the reactor. The hydrochloric acid reaction conversion rate of the utility model is high, the conversion rate of the raw limestone and the hydrochloric acid is close to 100%, and the pH of the calcium chloride solution at the outlet of the reactor is >4.0.

[0059] It is apparent for a person skilled in the art that the present application is not restricted to the details of the above exemplary embodiments, but that it can be implemented in other concrete forms without departing from the spirit or the essential characteristics of the present application. Therefore, the embodiments should be considered as exemplary only, and not limiting, the scope of the present application being defined by the appended claims rather than the above description, and all changes coming within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference signs in the claims should not be construed as limiting the claims concerned.

Claims

1. A trickle bed reactor for the continuous production of calcium chloride solution by reacting hydrochloric acid and limestone, characterized in that: The structure includes an upper cone (1), a cylinder (2), and a lower cone (3) arranged sequentially from top to bottom. The upper cone (1) has a limestone inlet (16) and a top exhaust port (17) at its top. The lower cone (3) has a calcium chloride solution outlet (15) at its bottom. The upper cone (1) also has a pressure sensor (22) and a sight glass (23) at its top. The cylinder (2) has a manhole (21) at its bottom. A limestone support grid (4) is provided between the cylinder (2) and the lower cone (3), and an openable and closable unloading pipe (8) is provided at the bottom of the limestone support grid (4). The cylinder (2) has two or more sets of horizontally arranged hydrochloric acid inlet pipes (5) arranged side by side, and multiple acid inlet holes are horizontally distributed on both sides of the hydrochloric acid inlet pipes (5). The hydrochloric acid inlet pipe (5) is provided with an inlet pipe support grid (7) below it. The inlet pipe support grid (7) divides the area below the inlet pipe into multiple independent compartments (24). The lower cone (3) is provided with a bottom exhaust port (10), the top of the cylinder (2) is provided with an upper air inlet (12), the upper part of the cylinder (2) is provided with a middle exhaust port (11) between the hydrochloric acid inlet pipe (5) and the upper air inlet (12), the bottom exhaust port (10), the middle exhaust port (11) and the upper air inlet (12) are connected by a gas connecting pipe (13), and a valve (14) is provided between the bottom exhaust port (10) and the middle exhaust port (11).

2. The trickle bed reactor for the continuous production of calcium chloride solution by reacting hydrochloric acid and limestone according to claim 1, characterized in that: The middle exhaust port (11) is located between the hydrochloric acid inlet pipe (5) and the upper air inlet (12) on the side near the upper air inlet (12).

3. The trickle bed reactor for the continuous production of calcium chloride solution by reacting hydrochloric acid and limestone according to claim 2, characterized in that: The hydrochloric acid inlet pipe (5) is located in the upper middle part of the cylinder (2).

4. The trickle bed reactor for the continuous production of calcium chloride solution by reacting hydrochloric acid and limestone according to claim 3, characterized in that: A baffle (6) is provided above the hydrochloric acid inlet pipe (5). The cross-section of the baffle (6) is an inverted V shape. The center line of the baffle (6) and the axis of the hydrochloric acid inlet pipe (5) are in the same vertical plane. The width of the bottom of the baffle (6) is 2 to 5 times the diameter of the hydrochloric acid inlet pipe (5).

5. The trickle bed reactor for the continuous production of calcium chloride solution by reacting hydrochloric acid and limestone according to claim 1, characterized in that: The acid inlet pipe support grid (7) forms multiple independent compartments (24) through the partition ribs (25). The independent compartments (24) near the inner wall of the cylinder (2) are separated from the inner wall of the cylinder (2) by the partition ribs (25).

6. The trickle bed reactor for the continuous production of calcium chloride solution by reacting hydrochloric acid and limestone according to claim 5, characterized in that: The hydrochloric acid inlet pipe (5) is provided in two sets, and the two sets of hydrochloric acid inlet pipe (5) are symmetrically distributed along the diameter of the cross section of the cylinder (2).

7. A trickle bed reactor for the continuous production of calcium chloride solution by reacting hydrochloric acid and limestone according to any one of claims 1-6, characterized in that: The lower cone (3) is an inverted eccentric cone. The calcium chloride solution outlet (15) is located at the lowest point of the lower cone (3). The flushing liquid outlet (18) is located at the maximum value of the line connecting the calcium chloride solution outlet (15) to the top surface of the lower cone (3). The bottom exhaust outlet (10) is located at the minimum value of the line connecting the calcium chloride solution outlet (15) to the top surface of the lower cone (3).

8. A trickle bed reactor for the continuous production of calcium chloride solution by reacting hydrochloric acid and limestone according to claim 6, characterized in that: Two to eight acid inlet holes are provided in each independent compartment (24) located in the middle of the cylinder (2) between the two sets of hydrochloric acid inlet pipes (5). One to four acid inlet holes are provided in each independent compartment (24) located at the edge of the cylinder (2) of each set of hydrochloric acid inlet pipes (5). The diameter of the acid inlet holes is 12mm to 20mm, and the height of the partition rib (25) is 400mm to 800mm.

9. A trickle bed reactor for the continuous production of calcium chloride solution by reacting hydrochloric acid and limestone according to claim 7, characterized in that: The spacing between the grid plates of the limestone support grid (4) is 12mm~30mm. The bottom of the limestone support grid (4) is supported by the support rib plate (26). A discharge hole is opened in the center of the limestone support grid (4) and connected to the discharge pipe (8).

10. A trickle bed reactor for the continuous production of calcium chloride solution by reacting hydrochloric acid and limestone according to claim 9, characterized in that: The discharge pipe (8) is controlled to open and close by the discharge valve assembly (9). The discharge valve assembly (9) includes a hydraulic cylinder (27), a valve stem (28), a slide rail (29), and a valve plate (30). The valve plate (30) is located between the limestone support grid (4) and the discharge pipe (8). The slide rail (29) is located on the support rib plate (26). One end of the valve plate (30) is connected to the valve stem (28). The valve plate (30) is slidably connected to the slide rail (29). There is a gap between the upper edge of the valve plate (30) and the lower edge of the limestone support grid (4). The gap is 5mm to 20mm.

Images