CN-117482735-B - Production method of device for continuously producing ammonium sulfate and calcium carbonate by using carbon dioxide mineralized gypsum

CN117482735BCN 117482735 BCN117482735 BCN 117482735BCN-117482735-B

Abstract

The invention discloses a production method of a device for continuously producing ammonium sulfate and calcium carbonate by utilizing carbon dioxide mineralized gypsum, which comprises a spray tower reaction device and a multi-stage kettle reaction device, wherein the spray tower reaction device sequentially comprises a reaction tank, a first absorption region, a second absorption region and a third absorption region from bottom to top, the upper part of the first absorption region is provided with an ammonia water spray layer, the lower part of the first absorption region is provided with a flue gas inlet positioned above the reaction tank, the upper part of the second absorption region is provided with a circulating spray layer, the circulating spray layer is used for pumping liquid from the reaction tank for spraying through a circulating pipeline and a circulating pump, the upper part of the third absorption region is provided with a gypsum spray layer, the spray tower reaction device sequentially conveys reaction slurry in the reaction tank to the multi-stage kettle reaction device through a conveying pipeline provided with a pressurizing pump, and the multi-stage kettle reaction device comprises a plurality of kettle reactors which are sequentially arranged in series. The invention improves the continuity of the system operation, and reduces ammonia escape through the controllability of the system operation process.

Inventors

XU XIAOLIANG
LIU LONGFEI
TANG CHIZHOU
MA MING

Assignees

三碳(安徽)科技研究院有限公司

Dates

Publication Date: 20260512
Application Date: 20230323

Claims (7)

1. The production method of the device for continuously producing the ammonium sulfate and the calcium carbonate by utilizing the carbon dioxide mineralized gypsum is characterized by comprising a spray tower reaction device (1) and a multi-stage kettle type reaction device, wherein the spray tower reaction device (1) sequentially comprises a reaction tank, a first absorption region, a second absorption region and a third absorption region from bottom to top, an ammonia water spray layer is arranged at the upper part of the first absorption region, a flue gas inlet (4) positioned above the reaction tank is arranged at the lower part of the first absorption region, a circulating spray layer is arranged at the upper part of the second absorption region, liquid is extracted from the reaction tank by the circulating spray layer through a circulating pipeline and a circulating pump (9) for spraying, a gypsum spray layer is arranged at the upper part of the third absorption region for spraying solid waste gypsum slurry, the spray tower reaction device (1) sequentially conveys the reaction slurry in the reaction tank to the multi-stage kettle type reaction device through a conveying pipeline provided with a pressurizing pump (10), and the multi-stage kettle type reaction device comprises a plurality of kettle type reactors (12) which are sequentially connected in series; the kettle-type reactor (12) is internally provided with pH sensors, and the reaction tank is internally and uniformly provided with a plurality of pH sensors from bottom to top; The device detects the liquid level through the liquid level detection device, sequentially conveys mixed slurry with higher reaction degree in the reaction tank to each stage of kettle type reactor (12), detects the reaction degree through the pH sensor, selects whether to change the input quantity of each raw material, and ensures the controllability of the concentration of substances in the mixed slurry and the reaction degree; the production method specifically comprises the following steps: Absorbing carbon dioxide in the flue gas by a spray tower reaction device (1), adding reaction raw material ammonia water and solid waste gypsum slurry, simultaneously realizing primary reaction of raw materials by a reaction tank to form mixed slurry, detecting the reaction conditions of the raw materials in the reaction tanks at different depths by a pH sensor, allowing the solid waste gypsum slurry, the ammonia water and the spray absorbed carbon dioxide to enter from above the reaction tank, wherein the top of the liquid in the reaction tank is a concentrated reaction area of reactants, and the carbon dioxide in the flue gas is absorbed as much as possible, so that the ammonia water is generally excessive, the solution in the reaction is alkaline, the common reaction among the ammonia water, the absorbed carbon dioxide and calcium sulfate occurs after the solid waste gypsum slurry is added, the pH value is detected by the pH sensor, judging the consumption condition of the ammonia water in the reaction process at different depths, and extracting ammonia-rich mixed solution from the reaction tank at a higher alkalinity depth and circularly spraying in a second absorption area to absorb the carbon dioxide in the flue gas as much as possible; The flue gas is continuously introduced into the spray tower reaction device (1), raw materials are also continuously added, the multi-stage kettle type reaction device is utilized to sequentially convey mixed slurry with higher reaction degree in the reaction tank to each stage of kettle type reactor (12), more raw materials are newly added and are fully mixed, more raw materials and more reaction products are contained, the multi-stage kettle type reaction device quantitatively acquires the mixed slurry from the upper layer of the reaction tank according to the capacity and the reaction speed of the kettle type reactor (12), the acquisition of the mixed slurry is matched with the addition amount of ammonia water and solid waste gypsum slurry, and the controllable change of the mass of the matters in the reaction tank in a certain range in the continuous operation process is ensured; In each kettle reactor (12), mixing slurry to obtain a certain reaction time, reacting raw materials to obtain a certain amount of product, further changing the pH value of the slurry towards the pH value after complete reaction, transferring and reacting the mixed slurry in each kettle reactor (12), reducing the injection amount of the mixed slurry in each single kettle reactor (12), ensuring that the raw materials can fully react after multistage reaction, completely converting the raw materials into ammonium sulfate solution and calcium carbonate in the final kettle reactor (12), and outputting the final product and then carrying out subsequent separation and drying treatment; The insufficiently reacted mixed slurry can be detected by a pH sensor to determine the reaction degree, whether the input amount of each raw material is changed or not is selected, the concentration of substances in the mixed slurry and the reaction degree are controllable, then when the total amount of liquid in the reaction tank reaches a certain degree, namely the liquid level exceeds a certain height of a slurry overflow port (11), the mixed slurry at the top of the reaction tank is conveyed to a subsequent multi-stage kettle-type reaction device, the mixed slurry is reacted completely by utilizing multi-stage treatment, the volume of the mixed slurry which is input from the reaction tank each time and transferred between different kettle-type reactors (12) is relatively small, and the raw material transfer and reaction can be carried out at shorter time intervals.
2. The method for continuously producing ammonium sulfate and calcium carbonate by utilizing carbon dioxide mineralized gypsum according to claim 1, wherein a bubbler (2) for outputting flue gas upwards is arranged at the lower part of the reaction tank, the bubbler (2) is provided with evenly distributed air nozzles, and the bubbler (2) and the flue gas inlet (4) are connected in parallel to a flue gas input pipe of flue gas to be treated.
3. The method for continuously producing ammonium sulfate and calcium carbonate by utilizing carbon dioxide mineralized gypsum according to claim 2, wherein the lower part of the reaction tank is further provided with a jet device (3) positioned above the bubbler (2), the jet device (3) is provided with a plurality of jet nozzles for spraying ammonia downwards towards the bubbler (2), the jet nozzles are uniformly distributed on the lower surface of the jet device (3), the ammonia spraying layer comprises a first sprayer (5), and the first sprayer (5) and the jet device (3) are connected to an ammonia water input pipe in parallel.
4. The method for continuously producing ammonium sulfate and calcium carbonate by using carbon dioxide mineralized gypsum according to claim 3, wherein the circulating spray layer comprises a second sprayer (6), the second sprayer (6) is connected to an outlet of the circulating pipeline, the circulating pipeline is connected to a circulating liquid inlet (8) of the spray tower reaction device (1) through the circulating pump (9), and the circulating liquid inlet (8) is lower than a slurry overflow port (11) communicated with the conveying pipeline and higher than the position of the sprayer (3).
5. The method for continuously producing ammonium sulfate and calcium carbonate by using carbon dioxide mineralized gypsum according to claim 4, wherein the reaction slurry is conveyed between the kettle-type reactors (12) through conveying pipelines provided with pressurizing pumps (10), the kettle-type reactors (12) are provided with feeding pipes connected with the conveying pipelines, the feeding pipes extend to the bottom of the inner side of the kettle-type reactors (12) and are provided with jet nozzles (13) at the discharging ends, and the jet nozzles (13) are arranged obliquely upwards.
6. The method for continuously producing ammonium sulfate and calcium carbonate by utilizing carbon dioxide mineralized gypsum according to claim 5, wherein solid waste gypsum slurry, ammonia water and spray absorbed carbon dioxide enter from the upper part of the reaction tank, so that the top of liquid in the reaction tank is a concentrated reaction area of reactants, the ammonia water is excessively input to ensure that the carbon dioxide is fully absorbed, the pH value is detected by a pH sensor to judge the consumption condition of the ammonia water in the reaction process at different depths, and the ejector (3) is utilized to supplement the ammonia water below the circulating liquid inlet (8), so that the liquid in the area where the circulating liquid inlet (8) is located is continuously rich in ammonia mixed solution.
7. The method for continuously producing ammonium sulfate and calcium carbonate by using carbon dioxide mineralized gypsum according to claim 6, wherein the first sprayer (5) and the second sprayer (6) are arranged in at least two layers from top to bottom, the gypsum spraying layer comprises a third sprayer (7) for adding solid waste gypsum slurry and absorbing escaped ammonia, and the third sprayer (7) is arranged in at least one layer from top to bottom.

Description

Production method of device for continuously producing ammonium sulfate and calcium carbonate by using carbon dioxide mineralized gypsum Technical Field The invention belongs to the technical field of carbon absorption, and particularly relates to a production method of a device for continuously producing ammonium sulfate and calcium carbonate by utilizing carbon dioxide mineralized gypsum. Background In the prior art, one carbon dioxide absorption and utilization mode is that ammonia water is used for absorbing carbon dioxide, then an ammonium carbonate solution formed after absorbing carbon dioxide is further treated, and a solid waste gypsum component is added to realize the reaction of calcium sulfate and ammonium carbonate in a reactor, so that recycled products of ammonium sulfate and calcium carbonate are obtained, the calcium carbonate can be further used as a raw material of a cement production system, and ammonium sulfate obtained by drying and crystallizing the ammonium sulfate solution is used as a chemical fertilizer. In the reaction, on one hand, carbon dioxide is fully absorbed, on the other hand, the reaction of calcium sulfate and ammonium carbonate is difficult to separate a reaction product from raw materials in time from a reaction container before the reaction is complete, so that the prior art generally adopts the steps of fully absorbing carbon dioxide, fully reacting the reaction product with a corresponding amount of solid waste gypsum, separating the reaction product, and judging the reaction degree through the pH value change in the reaction process. However, the reaction process can only be realized by adopting intermittent reaction, the system operation is stopped after a certain amount of reaction raw materials are fully reacted, and the next reaction can be continued after the product is taken out. Therefore, the system cannot continuously run, the raw material input amount and the raw material speed are difficult to adjust in time in the running process, the system can be adjusted only after one-time reaction is completed, and the continuity and the controllability of the running of the system are still further improved. Disclosure of Invention The invention aims to provide a production method of a device for continuously producing ammonium sulfate and calcium carbonate by utilizing carbon dioxide mineralized gypsum, which is used for solving the technical problems of insufficient continuity and controllability of system operation in the process from carbon dioxide absorption to reaction with solid waste gypsum to obtain an available product in a carbon dioxide absorption system in the prior art. The production method of the device for continuously producing the ammonium sulfate and the calcium carbonate by utilizing the carbon dioxide mineralized gypsum comprises a spray tower reaction device and a multi-stage kettle type reaction device, wherein the spray tower reaction device sequentially comprises a reaction tank, a first absorption area, a second absorption area and a third absorption area from bottom to top, an ammonia water spray layer is arranged at the upper part of the first absorption area, a smoke inlet positioned above the reaction tank is arranged at the lower part of the first absorption area, a circulating spray layer is arranged at the upper part of the second absorption area, liquid is extracted from the reaction tank through a circulating pipeline and a circulating pump for spraying, a gypsum spray layer is arranged at the upper part of the third absorption area for spraying solid waste gypsum slurry, the spray tower reaction device sequentially conveys the reaction slurry in the reaction tank to the multi-stage kettle type reaction device through a conveying pipeline provided with a pressurizing pump, and the multi-stage kettle type reaction device comprises a plurality of kettle type reactors which are sequentially connected in series. Preferably, the kettle-type reactor is internally provided with pH sensors for detecting the reaction degree, and the reaction tank is internally and uniformly provided with a plurality of pH sensors from bottom to top. Preferably, a bubbler for outputting the flue gas upwards is arranged at the lower part of the reaction tank, the bubbler is provided with evenly distributed air nozzles, and the bubbler and the flue gas inlet are connected in parallel to a flue gas input pipe of the flue gas to be treated. Preferably, the lower part of the reaction tank is also provided with a jet device positioned above the bubbler, the jet device is provided with a plurality of jet nozzles which are downwards opposite to the bubbler and spray ammonia water, the jet nozzles are uniformly distributed on the lower surface of the jet device, the ammonia water spraying layer comprises a first sprayer, and the first sprayer and the jet device are connected in parallel to an ammonia water input pipe. Preferably, the circulating spraying layer co