CN216303285U - System for utilize desulfurized gypsum preparation potassium sulfate - Google Patents
System for utilize desulfurized gypsum preparation potassium sulfate Download PDFInfo
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- CN216303285U CN216303285U CN202121130909.0U CN202121130909U CN216303285U CN 216303285 U CN216303285 U CN 216303285U CN 202121130909 U CN202121130909 U CN 202121130909U CN 216303285 U CN216303285 U CN 216303285U
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Abstract
The utility model discloses a system for preparing potassium sulfate by utilizing desulfurized gypsum, which comprises the following steps: comprises a recrystallization kettle, a hydrochloric acid tank, a recrystallization liquid delivery pump, a potassium carbonate solution tank, a potassium carbonate solution metering pump, a neutralization reaction kettle, a neutralization liquid delivery pump, an ammoniation reaction kettle, a potassium sulfate liquid delivery pump and a potassium sulfate centrifuge; the hydrochloric acid tank is connected with the recrystallization kettle, the recrystallization liquid delivery pump is respectively connected with the recrystallization kettle and the neutralization reaction kettle, the potassium carbonate solution tank is connected with the neutralization reaction kettle, the neutralization liquid delivery pump is respectively connected with the neutralization reaction kettle and the ammonification reaction kettle, and the potassium sulfate liquid delivery pump is respectively connected with the ammonification reaction kettle and the potassium sulfate centrifugal machine. The utility model is suitable for chemical enterprises with thermoelectric devices and ammonia synthesis devices.
Description
Technical Field
The utility model belongs to the technical field of environmental protection, and particularly relates to a system for preparing potassium sulfate by utilizing desulfurized gypsum.
Background
The potassium sulfate is an excellent chlorine-repellent crop potassium fertilizer and is of great importance to influence on the quality of economic crops such as tobacco, tea and the like. The demand of high-quality potassium sulfate fertilizer in China is large, and a considerable part of the high-quality potassium sulfate fertilizer is imported from foreign countries. The currently common potassium sulfate production method is the Mannheim method, which utilizes potassium chloride and concentrated sulfuric acid as raw materials and produces hydrochloric acid as a byproduct. At the temperature of 500-530 ℃, potassium chloride reacts with concentrated sulfuric acid to firstly generate potassium bisulfate and hydrogen chloride, further potassium bisulfate reacts with potassium chloride to generate potassium sulfate and hydrogen chloride, and the potassium sulfate generated by the reaction is discharged from an outlet of a reaction chamber to enter the next working procedure. However, the Mannheim method has high corrosion to equipment, high energy consumption and high capital investment for equipment operation and maintenance.
The desulfurized gypsum is a byproduct of the thermoelectric flue gas desulfurization process, and the main component of the desulfurized gypsum is calcium sulfate dihydrate like natural gypsum. The flue gas desulfurization gypsum is in a shape of fine particles, the average particle size is 40-60 mu m, the particles are in a short column shape, the diameter-length ratio is 1.5-2.5, the color is gray and yellow, the content of calcium sulfate dihydrate is higher and is generally more than 90%, the content of free water is generally 10-15%, and the flue gas desulfurization gypsum also contains impurities such as fly ash, organic carbon, calcium carbonate, calcium sulfite, soluble salt consisting of sulfate or chloride of sodium, potassium and magnesium and the like. At present, the desulfurized gypsum is mostly added into cement or concrete as an admixture, and is also partially used for producing building materials. Because the output of the desulfurized gypsum is very large, the digestion capacity of the market for the desulfurized gypsum cannot completely meet the productivity of the desulfurized gypsum, and the desulfurized gypsum of many thermoelectric enterprises is accumulated.
The prior art has the following defects that 1, the process equipment for producing the potassium sulfate by the Mannheim method has large corrosion, high energy consumption and large investment for equipment operation and maintenance. 2. The existing desulfurization gypsum treatment method has low added value and single treatment method.
SUMMERY OF THE UTILITY MODEL
The utility model aims to overcome the defects in the prior art and provides a system for preparing potassium sulfate by utilizing desulfurized gypsum. The additive value of the desulfurized gypsum is fully utilized, the desulfurized gypsum is converted into potassium sulfate, the application direction of the desulfurized gypsum is widened, and the valuable product is produced by utilizing the solid waste.
The purpose of the utility model is realized by the following technical scheme.
The utility model relates to a system for preparing potassium sulfate by utilizing desulfurized gypsum, which comprises a recrystallization kettle, a hydrochloric acid tank, a recrystallization liquid delivery pump, a potassium carbonate solution tank, a potassium carbonate solution metering pump, a neutralization reaction kettle, a neutralization liquid delivery pump, an ammoniation reaction kettle, a potassium sulfate liquid delivery pump and a potassium sulfate centrifuge;
the top of the recrystallization kettle is provided with an emptying pipeline, a hydrochloric acid adding port and a solid adding port, and the hydrochloric acid adding port is connected with a hydrochloric acid tank through a pipeline; a bottom sludge outlet and a recrystallization liquid outlet are formed in the bottom of the recrystallization kettle; a solid feeding port at the top of the recrystallization kettle is manually opened, and desulfurized gypsum and potassium chloride are added into the recrystallization kettle through the solid feeding port; the hydrochloric acid tank is arranged higher than the recrystallization kettle, and hydrochloric acid in the hydrochloric acid tank is added into the recrystallization kettle in a gravity-fed manner;
a recrystallization liquid inlet, a potassium carbonate solution feeding port and a carbon dioxide emptying pipeline are arranged at the upper part of the neutralization reaction kettle, the recrystallization liquid inlet and the recrystallization liquid outlet are connected with a recrystallization liquid delivery pump through pipelines, and the potassium carbonate solution feeding port is connected with a potassium carbonate solution tank through a potassium carbonate solution metering pump; a neutralization liquid outlet is formed in the lower part of the neutralization reaction kettle;
a neutralization solution inlet and an ammonia gas recovery pipeline are arranged at the upper part of the ammonification reaction kettle, the neutralization solution inlet and the neutralization solution outlet are connected with a neutralization solution delivery pump through pipelines, and the ammonia gas recovery pipeline is connected to an ammonia gas recovery process; an ammonia gas inlet is formed in the side surface of the ammonification reaction kettle; the lower part of the ammonification reaction kettle is provided with a potassium sulfate liquid outlet, the potassium sulfate liquid outlet is connected with an inlet of a potassium sulfate centrifuge through a potassium sulfate liquid delivery pump, and the liquid outlet of the potassium sulfate centrifuge is connected with an ammonia water recovery process.
The bottom mud outlet is connected with the bottom mud neutralizing tank through a flexible connecting pipeline; the bottom sediment neutralizing tank is internally provided with a bottom sediment stirring device, the upper part of the bottom sediment neutralizing tank is provided with an AII waste liquid adding port, and the lower part of the bottom sediment neutralizing tank is provided with a recrystallization bottom sediment outlet connected with the plate-and-frame filter press.
The inside recrystallization kettle stirring device that is provided with of recrystallization kettle, the outside is provided with recrystallization kettle heating device.
The neutralization reaction kettle is internally provided with a neutralization reaction kettle stirring device, and the outside is provided with a neutralization reaction kettle heating device.
And an ammonification reaction kettle stirring device is arranged in the ammonification reaction kettle.
Compared with the prior art, the technical scheme of the utility model has the following beneficial effects:
(1) the desulfurized gypsum obtained in the flue gas desulfurization process of the thermal power plant is used for preparing the potassium sulfate, so that the problem of overstocked desulfurized gypsum is solved, the application channel of the desulfurized gypsum is widened, and the added value of the desulfurized gypsum is improved.
(2) The utility model adds the bottom mud neutralizing tank and the like, effectively solves the problem of acid bottom mud generated during the recrystallization of the desulfurized gypsum, and simultaneously makes full use of AII waste liquid.
(3) The utility model avoids the reaction condition of concentrated sulfuric acid and high temperature, and reduces the corrosion of equipment and the energy consumption of reaction.
Drawings
FIG. 1 is a schematic diagram of a system for preparing potassium sulfate by using desulfurized gypsum according to the utility model.
FIG. 2 is a flow chart of the system for preparing potassium sulfate by using desulfurized gypsum according to the utility model.
Reference numerals: 1 recrystallization vessel, 2 recrystallization vessel stirring apparatus, 3 hydrochloric acid tank, 5 emptying pipeline, 6 hydrochloric acid inlet, 7 solid inlet, 8 bottom mud outlet, 9 recrystallization liquid outlet, 10 recrystallization vessel heating apparatus, 11 bottom mud neutralization tank, 12 AII waste liquid inlet, 13 bottom mud stirring apparatus, 14 recrystallization bottom mud outlet, 15 recrystallization liquid delivery pump, 16 recrystallization liquid inlet, 17 neutralization reaction vessel, 18 neutralization reaction vessel stirring apparatus, 19 potassium carbonate solution tank, 21 potassium carbonate solution metering pump, 22 potassium carbonate solution inlet, 23 carbon dioxide emptying pipeline, 24 neutralization liquid outlet, 25 neutralization reaction vessel heating apparatus, 26 neutralization liquid delivery pump, 27 neutralization liquid inlet, 28 ammonification reaction vessel, 29 potassium carbonate stirring apparatus, 30 ammonia inlet, 31 ammonia recovery pipeline, 32 potassium sulfate liquid outlet, 33 potassium sulfate liquid delivery pump, 34 potassium sulfate centrifuge, 35 plate and frame filter press.
Detailed Description
The utility model is further described below with reference to the accompanying drawings.
As shown in fig. 1, the system for preparing potassium sulfate by using desulfurized gypsum of the present invention comprises a recrystallization vessel 1, a hydrochloric acid tank 3, a recrystallization liquid delivery pump 15, a potassium carbonate solution tank 19, a potassium carbonate solution metering pump 21, a neutralization reaction vessel 17, a neutralization liquid delivery pump 26, an ammoniation reaction vessel 28, a potassium sulfate liquid delivery pump 33, and a potassium sulfate centrifuge 34.
The recrystallization kettle 1 is internally provided with a recrystallization kettle stirring device 2, and the outside is provided with a recrystallization kettle heating device 10. The top of the recrystallization kettle 1 is provided with an emptying pipeline 5, a hydrochloric acid adding port 6 and a solid adding port 7, and the hydrochloric acid adding port 6 is connected with the hydrochloric acid tank 3 through a pipeline. The hydrochloric acid tank 3 is arranged higher than the recrystallization kettle 1, and hydrochloric acid in the hydrochloric acid tank 3 is added into the recrystallization kettle 1 in a gravity-fed manner. The solid inlet 7 is opened manually, and desulfurized gypsum and potassium chloride are added into the recrystallization vessel 1 through the solid inlet 7.
The bottom of the recrystallization kettle 1 is provided with a bottom sediment outlet 8 and a recrystallization liquid outlet 9, and the bottom sediment outlet 8 is connected with a bottom sediment neutralizing tank 11 through a flexible connecting pipeline. The bottom sediment neutralizing tank 11 is internally provided with a bottom sediment stirring device 13, the upper part of the bottom sediment neutralizing tank is provided with an AII waste liquid adding port 12, the lower part of the bottom sediment neutralizing tank is provided with a recrystallization bottom sediment outlet 14, and the recrystallization bottom sediment outlet 14 is connected with the plate-and-frame filter press 35. Wherein the recrystallization liquid transfer pump 15 is a gear pump.
The neutralization reaction kettle 17 is internally provided with a neutralization reaction kettle stirring device 18, and the outside is provided with a neutralization reaction kettle heating device 25. The upper part of the neutralization reaction kettle 17 is provided with a recrystallization liquid inlet 16, a potassium carbonate solution feeding port 22 and a carbon dioxide emptying pipeline 23. The recrystallization liquid inlet 16 and the recrystallization liquid outlet 9 are connected with a recrystallization liquid delivery pump 15 through pipelines, and the potassium carbonate solution inlet 22 is connected with a potassium carbonate solution tank 19 through a potassium carbonate solution metering pump 21. The lower part of the neutralization reaction kettle 17 is provided with a neutralization liquid outlet 24. Wherein, the potassium carbonate solution metering pump 21 has a metering function.
An ammonification reaction kettle stirring device 29 is arranged in the ammonification reaction kettle 28. The upper part of the ammoniation reaction kettle 28 is provided with a neutralization solution inlet 27 and an ammonia gas recovery pipeline 31. The neutralization liquid inlet 27 is connected with the neutralization liquid outlet 24 through a pipeline, a neutralization liquid conveying pump 26 is connected between the neutralization liquid inlet and the neutralization liquid outlet, and the ammonia gas recovery pipeline 31 is connected to an ammonia gas recovery process. The lateral surface of the ammonification reaction kettle 28 is provided with an ammonia gas inlet 30, and the ammonia gas inlet 30 is arranged at the lateral surface of the ammonification reaction kettle 28 close to the kettle bottom. The lower part of the ammoniation reaction kettle 28 is provided with a potassium sulfate liquid outlet 32, the potassium sulfate liquid outlet 32 is connected with an inlet of a potassium sulfate centrifuge 34 through a potassium sulfate liquid delivery pump 33, and the liquid outlet of the potassium sulfate centrifuge 34 is connected with an ammonia water recovery process.
The utility model relates to a manufacturing method of a system for preparing potassium sulfate by utilizing desulfurized gypsum, in particular to a method for recrystallizing desulfurized gypsum and reducing the solubility of potassium sulfate under an ammoniation condition. The desulfurized gypsum is recrystallized in the presence of hydrochloric acid and potassium chloride under heating, and at the moment, impurities in the desulfurized gypsum covering the surface of the calcium sulfate crystals are separated and precipitated out of the system. Impurities leaving the system can form acidic bottom mud, and the acidity reaches the environmental standard by utilizing the acid-base waste liquid mixed with the bottom mud to neutralize the acidity of the bottom mud. Neutralizing the recrystallized liquid with potassium carbonate solution to obtain neutral solution and excessive H+Will react with CO3 2Reaction to water and CO2. And further introducing ammonia gas into the neutralized liquid obtained by the neutralization reaction to ensure that the ammonia concentration in the system reaches more than 30 percent, so that the solubility of the potassium sulfate in the system is greatly reduced. The potassium sulfate will precipitate out of the system, and the system containing the potassium sulfate crystal precipitate is centrifugally filtered to obtain potassium sulfate crystals. The method mainly comprises the following steps of desulfurization gypsum recrystallization, neutralization reaction, ammoniation reactionIt should be centrifuged and dried as shown in FIG. 2.
Step one, recrystallizing desulfurized gypsum
Sending hydrochloric acid from a hydrochloric acid tank 3 into a recrystallization kettle 1, starting a recrystallization kettle stirring device 2 and a recrystallization kettle heating device 10, then adding desulfurized gypsum and potassium chloride to perform recrystallization reaction, wherein the duration time of the recrystallization reaction is 50-90 min, and the recrystallization temperature is 95-105 ℃; reacting to obtain a recrystallization solution and bottom mud; the recrystallization liquid is conveyed to a neutralization reaction kettle 17 through a recrystallization liquid conveying pump 15, the bottom sludge is discharged into a bottom sludge neutralization tank 11 through a bottom sludge outlet 8, wherein the mass ratio of the desulfurized gypsum to the potassium chloride added into the recrystallization kettle 1 is 1.6: 1-2.6: 1;
and (3) recrystallizing bottom mud for neutralization: after the recrystallized bottom mud enters the bottom mud neutralizing tank 11, starting a bottom mud stirring device 13; introducing AII waste liquid, testing the pH value in the bottom mud neutralization tank 11 in the mixing process, and stopping adding AII waste liquid when the pH value is neutral; opening a recrystallized bottom mud outlet 14 at the lower part of the bottom mud neutralization tank 11, enabling the bottom mud to enter a plate and frame filter press 35 to obtain wastewater and sludge, carrying out a sewage treatment process on the wastewater, and conveying the sludge to a brick firing factory. The waste liquid A pi is a liquid part obtained by performing solid-liquid separation on the mud A pi, the liquid is alkaline waste liquid, the main component of the liquid is the same as the combined alkaline A pi liquid, and the liquid contains NH4 +、Na+、Mg2+、Ca2+、NH3、CO3 2-、HCO3-、Cl-、OH-、SO4 2-and the like.
Step two: neutralization reaction
After the recrystallized liquid enters a neutralization reaction kettle 17, starting a neutralization reaction kettle stirring device 18 and a neutralization reaction kettle heating device 25, and then adding a potassium carbonate solution into the neutralization reaction kettle 17 to perform neutralization reaction at the temperature of 90-100 ℃; carbon dioxide gas generated by the reaction is discharged through a carbon dioxide emptying pipeline 23, the pH value in the neutralization reaction kettle 17 is sampled and detected, if the pH value is 7-8, the potassium carbonate solution is stopped to be added, the neutralization reaction is finished, and the obtained neutralization reaction liquid is introduced into an ammoniation reaction kettle 28 through a neutralization liquid conveying pump 26;
step three: ammoniation reaction
After the neutralization reaction liquid enters an ammonification reaction kettle 28, introducing ammonia gas into the ammonification reaction kettle 28 to enable the neutralization reaction liquid to carry out ammonification reaction, wherein the ammonia gas introduction time is 50-110 min; the ammonia gas discharged by the reaction is sent to an ammonia gas recovery process through an ammonia gas recovery pipeline 31, and the obtained potassium sulfate crystal and the ammoniation reaction liquid are sent to a potassium sulfate centrifuge 34 through a potassium sulfate liquid delivery pump 33;
step four: centrifuging, and drying
Separating the potassium sulfate crystal and the ammoniation reaction liquid by a potassium sulfate centrifuge 34, then sending the separated liquid to an ammonia water recovery process, collecting the obtained potassium sulfate crystal, and then sending the collected potassium sulfate crystal to a drying process for drying.
While the present invention has been described in terms of its functions and operations with reference to the accompanying drawings, it is to be understood that the utility model is not limited to the precise functions and operations described above, and that the above-described embodiments are illustrative rather than restrictive, and that various changes and modifications may be effected therein by one skilled in the art without departing from the scope or spirit of the utility model as defined by the appended claims.
Claims (5)
1. A system for preparing potassium sulfate by utilizing desulfurized gypsum is characterized by comprising a recrystallization kettle (1), a hydrochloric acid tank (3), a recrystallization liquid delivery pump (15), a potassium carbonate solution tank (19), a potassium carbonate solution metering pump (21), a neutralization reaction kettle (17), a neutralization liquid delivery pump (26), an ammoniation reaction kettle (28), a potassium sulfate liquid delivery pump (33) and a potassium sulfate centrifuge (34);
the top of the recrystallization kettle (1) is provided with an emptying pipeline (5), a hydrochloric acid adding port (6), and a solid adding port (7) which is opened manually and used for adding desulfurized gypsum and potassium chloride into the recrystallization kettle (1), the hydrochloric acid adding port (6) is connected with the hydrochloric acid tank (3) through a pipeline, and the bottom of the recrystallization kettle (1) is provided with a bottom sludge outlet (8) and a recrystallization liquid outlet (9); the hydrochloric acid tank (3) is arranged at a position higher than the recrystallization kettle (1), and hydrochloric acid in the hydrochloric acid tank (3) is added into the recrystallization kettle (1) in a gravity-fed manner;
a recrystallization liquid inlet (16), a potassium carbonate solution feeding port (22) and a carbon dioxide emptying pipeline (23) are arranged at the upper part of the neutralization reaction kettle (17), the recrystallization liquid inlet (16) and the recrystallization liquid outlet (9) are connected with a recrystallization liquid conveying pump (15) through pipelines, and the potassium carbonate solution feeding port (22) is connected with a potassium carbonate solution tank (19) through a potassium carbonate solution metering pump (21); a neutralizing liquid outlet (24) is arranged at the lower part of the neutralizing reaction kettle (17);
a neutralization liquid inlet (27) and an ammonia gas recovery pipeline (31) are arranged at the upper part of the ammoniation reaction kettle (28), the neutralization liquid inlet (27) and the neutralization liquid outlet (24) are connected with a neutralization liquid delivery pump (26) through pipelines, and the ammonia gas recovery pipeline (31) is connected to an ammonia gas recovery process; an ammonia gas inlet (30) is formed in the side surface of the ammoniation reaction kettle (28); the lower part of the ammoniation reaction kettle (28) is provided with a potassium sulfate liquid outlet (32), the potassium sulfate liquid outlet (32) is connected with an inlet of a potassium sulfate centrifuge (34) through a potassium sulfate liquid delivery pump (33), and the liquid outlet of the potassium sulfate centrifuge (34) is connected with an ammonia water recovery process.
2. The system for preparing potassium sulfate by using desulfurized gypsum according to claim 1, wherein said bottom sludge outlet (8) is connected with a bottom sludge neutralization tank (11) through a flexible connecting line; the bottom sediment neutralizing tank (11) is internally provided with a bottom sediment stirring device (13), the upper part of the bottom sediment neutralizing tank is provided with an AII waste liquid adding port (12), and the lower part of the bottom sediment neutralizing tank is provided with a recrystallization bottom sediment outlet (14) connected with a plate-and-frame filter press (35).
3. The system for preparing potassium sulfate by using desulfurized gypsum according to claim 1, wherein the recrystallization vessel (1) is internally provided with a recrystallization vessel stirring device (2), and externally provided with a recrystallization vessel heating device (10).
4. The system for preparing potassium sulfate by using desulfurized gypsum according to claim 1, wherein a neutralization reaction kettle stirring device (18) is arranged inside the neutralization reaction kettle (17), and a neutralization reaction kettle heating device (25) is arranged outside the neutralization reaction kettle.
5. The system for preparing potassium sulfate by using desulfurized gypsum according to claim 1, wherein an ammonification reaction kettle stirring device (29) is arranged inside the ammonification reaction kettle (28).
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| CN202121130909.0U CN216303285U (en) | 2021-05-25 | 2021-05-25 | System for utilize desulfurized gypsum preparation potassium sulfate |
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| CN202121130909.0U CN216303285U (en) | 2021-05-25 | 2021-05-25 | System for utilize desulfurized gypsum preparation potassium sulfate |
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