CN112850752A - Method and system for preparing potassium sulfate and co-producing hydrochloric acid by using potassium chloride and sulfuric acid - Google Patents

Method and system for preparing potassium sulfate and co-producing hydrochloric acid by using potassium chloride and sulfuric acid Download PDF

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Publication number
CN112850752A
CN112850752A CN202110172892.3A CN202110172892A CN112850752A CN 112850752 A CN112850752 A CN 112850752A CN 202110172892 A CN202110172892 A CN 202110172892A CN 112850752 A CN112850752 A CN 112850752A
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Prior art keywords
potassium
hydrochloric acid
sulfuric acid
hydrogen
potassium sulfate
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CN202110172892.3A
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Chinese (zh)
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张飞龙
张光荣
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Guizhou Rongfulong Engineering Technology Co ltd
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Guizhou Rongfulong Engineering Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C01D5/02Preparation of sulfates from alkali metal salts and sulfuric acid or bisulfates; Preparation of bisulfates
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00Halogens; Halogen acids
    • C01B7/01Chlorine; Hydrogen chloride
    • C01B7/03Preparation from chlorides
    • C01B7/035Preparation of hydrogen chloride from chlorides

Abstract

The invention relates to a method and a system for preparing potassium sulfate and co-producing hydrochloric acid by potassium chloride and sulfuric acid, which comprises the following steps: s1: pressurizing a raw material sulfuric acid by a sulfuric acid pump, and then feeding the raw material sulfuric acid into a potassium sulfate reactor to react with potassium ions to respectively generate hydrogen ions and potassium sulfate; s2: pressurizing the potassium chloride solution by a potassium chloride solution pump, then feeding the potassium chloride solution into a hydrochloric acid analysis tower, feeding purchased hydrogen ion liquid into the hydrochloric acid analysis tower, and carrying out analysis reaction on hydrogen ions and the potassium chloride solution in the hydrochloric acid analysis tower to generate potassium ion liquid and hydrogen chloride gas; s3: the hydrogen chloride gas is extracted from the top of the hydrochloric acid analysis tower and enters a hydrochloric acid absorption tower to be absorbed by water to generate a hydrochloric acid product; s4: potassium ion liquid and raw material sulfuric acid enter a potassium sulfate reactor, reactants discharged from the potassium sulfate reactor are separated by a centrifugal machine to obtain a potassium sulfate product and hydrogen ion mother liquor, and the hydrogen ion mother liquor is circulated to a salt dissolving tank. The method and the system of the invention can shorten the process, reduce the investment and the operation cost, improve the product quality and improve the economic benefit of enterprises.

Description

Method and system for preparing potassium sulfate and co-producing hydrochloric acid by using potassium chloride and sulfuric acid
Technical Field
The invention relates to the technical field of inorganic chemical industry, in particular to a method and a system for preparing potassium sulfate and co-producing hydrochloric acid by using potassium chloride and sulfuric acid.
Background
The potassium sulfate is a widely used high-quality potassium fertilizer, and particularly, with the upgrading of the agricultural industry, the demand of the potassium sulfate is larger, and the national agricultural production safety strategy is concerned. The classic potassium sulfate manhammethod production process has high energy consumption, heavy equipment corrosion, large pollution and high cost, and the capacity of a single furnace is difficult to expand; the association method has small production scale, large loss of the association agent and high operation cost; the double decomposition method has long production flow, large investment, low potassium conversion rate, poor product quality and poor economic benefit.
Disclosure of Invention
Aiming at the defects of the prior art, the technical problem to be solved by the patent application is how to provide a method and a system for co-producing hydrochloric acid by potassium chloride and potassium sulfate prepared by sulfuric acid, which have the advantages of short flow, reduced investment and production operation cost, improved product quality, improved production environment and reduced safety risk.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing potassium sulfate and co-producing hydrochloric acid by potassium chloride and sulfuric acid comprises the following steps:
s1: conveying raw material sulfuric acid into a sulfuric acid storage tank (1), pressurizing the raw material sulfuric acid by a sulfuric acid pump (2), and then allowing the raw material sulfuric acid to enter a potassium sulfate reactor (7) to react with potassium ions to respectively generate hydrogen ions and potassium sulfate;
s2: conveying potassium chloride to a salt dissolving tank (3) to dissolve the potassium chloride to prepare a potassium chloride solution, pressurizing the potassium chloride solution by a potassium chloride solution pump (4) and then entering a hydrochloric acid analysis tower (5), entering outsourced hydrogen ion liquid into the hydrochloric acid analysis tower (5), wherein the outsourced hydrogen ion liquid is required to be used only when the original vehicle is started, circularly providing hydrogen ion mother liquid after the process is completed, and carrying out an analysis reaction on hydrogen ions and the potassium chloride solution in the hydrochloric acid analysis tower (5) to generate potassium ion liquid and hydrogen chloride gas;
s3: the hydrogen chloride gas is extracted from the top of the hydrochloric acid desorption tower (5) and enters the hydrochloric acid absorption tower (6) to be absorbed by water to generate a hydrochloric acid product;
s4: potassium ion liquid and raw material sulfuric acid enter a potassium sulfate reactor (7), reactants discharged from the potassium sulfate reactor (7) are separated by a centrifuge (8) to obtain a potassium sulfate product and hydrogen ion mother liquor, and the hydrogen ion mother liquor is circulated to a salt dissolving tank (3).
In step S1, the concentration of the raw material sulfuric acid is 70-98%, the pressure of the potassium sulfate reactor is normal pressure, and the temperature is normal temperature.
In step S2, the concentration of hydrogen ions in the purchased hydrogen ion liquid and hydrogen ion mother liquid is 1-5%, and the balance is water.
In the step S2, the hydrochloric acid desorption tower (5) is filled with filler, the operation pressure of the top of the tower is normal pressure, the temperature is 80-90 ℃, the operation temperature of the bottom of the tower is 120-130 ℃, and the content of potassium ions in the bottom liquid of the tower is 35-45%.
In step S4, the potassium ion concentration in the potassium ion solution is 35-45%, the chloride ion content is less than 2%, and the potassium sulfate product concentration is greater than 45%.
The invention also discloses a system for preparing potassium sulfate and co-producing hydrochloric acid by using potassium chloride and sulfuric acid, which comprises the following steps:
a sulfuric acid storage tank (1) for storing raw sulfuric acid;
the sulfuric acid pump (2) is used for conveying sulfuric acid;
a salt dissolving tank (3) for dissolving potassium chloride to prepare a potassium chloride solution;
a potassium chloride solution pump (4) for conveying the potassium chloride solution;
the hydrochloric acid analysis tower (5) is used for reacting hydrogen ions with the potassium chloride solution to produce potassium ion solution and hydrogen chloride gas;
the hydrochloric acid absorption tower (6) is used for absorbing water and producing hydrochloric acid products by hydrogen chloride;
a potassium sulfate reactor (7) for reacting potassium ion liquid with sulfuric acid;
and the centrifugal machine (8) is used for separating the hydrogen ion mother liquor and the potassium sulfate product.
In conclusion, the invention takes hydrogen ion liquid as a starting reagent for reaction to perform an analytical reaction with potassium chloride solution under a high temperature condition to obtain potassium ions and hydrogen chloride gas, the hydrogen chloride gas is absorbed by water to obtain hydrochloric acid products, the potassium ions and sulfuric acid perform a double decomposition reaction to obtain potassium sulfate products and hydrogen ion mother liquor, and the hydrogen ion mother liquor is recycled. The invention realizes the co-production of hydrochloric acid by potassium sulfate prepared from potassium chloride and sulfuric acid, changes the traditional potassium sulfate production process, improves the production environment, reduces the safety risk, shortens the industrial flow, reduces the investment and the production operation cost, improves the product quality and improves the economic benefit of enterprises.
The reaction principle is as follows: (1) h + + KCl → K + + HCl ↓
(2)2K++H2SO4→2H++K2SO4
The co-production of hydrochloric acid by potassium chloride and sulfuric acid for preparing potassium sulfate disclosed by the patent application changes the traditional potassium sulfate production process, improves the production environment, reduces the safety risk, shortens the industrial flow, reduces the investment and production operation cost, improves the product quality, improves the economic benefit of enterprises, and has higher economic value and social benefit. In addition, the method has the advantages of short flow, high potassium yield of 99.5%, high byproduct of high-quality hydrochloric acid (or high-purity hydrogen chloride gas), high quality of potassium sulfate products, low operation cost and the like, improves economic benefits of potassium sulfate production, and reduces safety risks and environmental pollution.
Drawings
FIG. 1 is a process flow diagram of a method and a system for co-producing hydrochloric acid by potassium sulfate prepared from potassium chloride and sulfuric acid according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings. In the description of the present invention, it is to be understood that the orientation or positional relationship indicated by the orientation words such as "upper, lower" and "top, bottom" etc. are usually based on the orientation or positional relationship shown in the drawings, and are only for convenience of description and simplicity of description, and in the case of not making a reverse description, these orientation words do not indicate and imply that the device or element referred to must have a specific orientation or be constructed and operated in a specific orientation, and therefore, should not be interpreted as limiting the scope of the present invention; the terms "inner and outer" refer to the inner and outer relative to the profile of the respective component itself.
As shown in fig. 1, a method for co-producing hydrochloric acid by potassium sulfate prepared from potassium chloride and sulfuric acid comprises the following steps:
s1: conveying raw material sulfuric acid into a sulfuric acid storage tank 1, pressurizing the raw material sulfuric acid by a sulfuric acid pump 2, and then allowing the raw material sulfuric acid to enter a potassium sulfate reactor 7 to react with potassium ions to respectively generate hydrogen ions and potassium sulfate;
s2: conveying potassium chloride to a salt dissolving tank 3 to dissolve the potassium chloride to prepare a potassium chloride solution, pressurizing the potassium chloride solution by a potassium chloride solution pump 4, then feeding the potassium chloride solution into a hydrochloric acid analysis tower 5, feeding outsourced hydrogen ion liquid into the hydrochloric acid analysis tower 5, circularly providing the outsourced hydrogen ion liquid by using hydrogen ion mother liquid only when the original driving is required, completing the process, and carrying out an analysis reaction on hydrogen ions and the potassium chloride solution in the hydrochloric acid analysis tower 5 to generate potassium ion liquid and hydrogen chloride gas;
s3: the hydrogen chloride gas is extracted from the top of the hydrochloric acid analysis tower 5 and enters the hydrochloric acid absorption tower 6 to be absorbed by water to generate a hydrochloric acid product;
s4: the potassium ion liquid and the raw material sulfuric acid enter a potassium sulfate reactor 7, reactants discharged from the potassium sulfate reactor 7 are separated by a centrifuge 8 to obtain a potassium sulfate product and hydrogen ion mother liquor, and the hydrogen ion mother liquor is circulated to a salt dissolving tank 3.
In step S1, the concentration of the raw material sulfuric acid is 70-98%, the pressure of the potassium sulfate reactor is normal pressure, and the temperature is normal temperature.
In step S2, hydrogen ions (H) in the hydrogen ion liquid and hydrogen ion mother liquid are purchased+) The concentration is 1-5%, the rest is water, and no other impurities exist.
In step S2, the hydrochloric acid desorption tower 5 is filled with filler, the operation pressure at the top of the tower is normal pressure, the temperature is 80-90 ℃, the operation temperature at the bottom of the tower is 120-130 ℃, and the potassium ion content in the bottom liquid of the tower is 35-45%.
In step S4, the potassium ion concentration in the potassium ion solution is 35-45%, the chloride ion content is less than 2%, and the potassium sulfate product concentration is greater than 45%.
The invention also discloses a system for preparing potassium sulfate and co-producing hydrochloric acid by using potassium chloride and sulfuric acid, which comprises the following steps:
a sulfuric acid storage tank 1 for storing raw sulfuric acid;
the sulfuric acid pump 2 is used for conveying sulfuric acid;
a salt dissolving tank 3 for dissolving potassium chloride to prepare a potassium chloride solution;
a potassium chloride solution pump 4 for conveying a potassium chloride solution;
the hydrochloric acid analysis tower 5 is used for reacting hydrogen ions with the potassium chloride solution to produce potassium ion solution and hydrogen chloride gas;
the hydrochloric acid absorption tower 6 is used for absorbing water and producing hydrochloric acid products by hydrogen chloride;
a potassium sulfate reactor 7 for reacting potassium ion liquid with sulfuric acid;
and the centrifugal machine 8 is used for separating the hydrogen ion mother liquor and the potassium sulfate product.
The first embodiment is as follows:
referring to the attached figure 1, controlling the potassium chloride solution to be 100kg/h and the potassium chloride content to be 25 percent according to the requirements of the process flow of the attached figure 1;
the concentration of hydrogen ions is 5 percent, and the flow rate is 6.7 kg/h;
the temperature of the bottom of the desorption tower is 120 ℃, the temperature of the top of the desorption tower is 90 ℃, and the concentration of potassium ions is 40%;
the hydrochloric acid absorption tower is operated at normal temperature and normal pressure;
the potassium sulfate reactor is operated at normal temperature and normal pressure;
the sulfuric acid concentration is 98 percent, and the flow rate is 16.5 kg/h;
according to the process conditions, the reaction is controlled to be continuously carried out, and after 4 hours of reaction:
separating by a centrifuge to obtain a potassium sulfate product, wherein the main content of the product is 97.2, and the content of chloride ions is 0.23%;
the hydrochloric acid absorption tower obtains a hydrochloric acid product, and the concentration of the hydrochloric acid is 32.1%.
Example two:
referring to the attached figure 1, controlling the potassium chloride solution to be 100kg/h and the potassium chloride content to be 25 percent according to the requirements of the process flow of the attached figure 1;
the concentration of hydrogen ions is 5 percent, and the flow rate is 6.7 kg/h;
the temperature of the bottom of the desorption tower is 110 ℃, the temperature of the top of the desorption tower is 80 ℃, and the concentration of potassium ions is 35%;
the hydrochloric acid absorption tower is operated at normal temperature and normal pressure;
the potassium sulfate reactor is operated at normal temperature and normal pressure;
the sulfuric acid concentration is 98 percent, and the flow rate is 16.5 kg/h;
according to the process conditions, the reaction is controlled to be continuously carried out, and after 4 hours of reaction:
separating by a centrifuge to obtain a potassium sulfate product, wherein the main content of the product is 96.2, and the content of chloride ions is 0.56%;
the hydrochloric acid absorption tower obtains a hydrochloric acid product, and the concentration of the hydrochloric acid is 30.3%.
Example three:
referring to the attached figure 1, controlling the potassium chloride solution to be 100kg/h and the potassium chloride content to be 25 percent according to the requirements of the process flow of the attached figure 1;
the concentration of hydrogen ions is 5 percent, and the flow rate is 6.7 kg/h;
the temperature of the bottom of the desorption tower is 130 ℃, the temperature of the top of the desorption tower is 95 ℃, and the concentration of potassium ions is 45 percent;
the hydrochloric acid absorption tower is operated at normal temperature and normal pressure;
the potassium sulfate reactor is operated at normal temperature and normal pressure;
the sulfuric acid concentration is 98 percent, and the flow rate is 16.5 kg/h;
according to the process conditions, the reaction is controlled to be continuously carried out, and after 4 hours of reaction:
separating by a centrifuge to obtain a potassium sulfate product, wherein the main content of the product is 98.5 percent, and the content of chloride ions is 0.15 percent;
the hydrochloric acid absorption tower obtains a hydrochloric acid product, and the concentration of the hydrochloric acid is 31.6%.
The method has the advantages of short flow, high potassium yield of 99.5%, high byproduct high-quality hydrochloric acid (or high-purity hydrogen chloride gas), high quality of the potassium sulfate product, low operation cost and the like, improves economic benefits of potassium sulfate production, and reduces safety risks and environmental pollution.
Finally, it should be noted that: various modifications and alterations of this invention may be made by those skilled in the art without departing from the spirit and scope of this invention. Thus, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.

Claims (6)

1. A method for preparing potassium sulfate and co-producing hydrochloric acid by potassium chloride and sulfuric acid is characterized by comprising the following steps:
s1: conveying raw material sulfuric acid into a sulfuric acid storage tank (1), pressurizing the raw material sulfuric acid by a sulfuric acid pump (2), and then allowing the raw material sulfuric acid to enter a potassium sulfate reactor (7) to react with potassium ions to respectively generate hydrogen ions and potassium sulfate;
s2: conveying potassium chloride to a salt dissolving tank (3) to dissolve the potassium chloride to prepare a potassium chloride solution, pressurizing the potassium chloride solution by a potassium chloride solution pump (4) and then entering a hydrochloric acid analysis tower (5), entering outsourced hydrogen ion liquid into the hydrochloric acid analysis tower (5), wherein the outsourced hydrogen ion liquid is required to be used only when the original vehicle is started, circularly providing hydrogen ion mother liquid after the process is completed, and carrying out an analysis reaction on hydrogen ions and the potassium chloride solution in the hydrochloric acid analysis tower (5) to generate potassium ion liquid and hydrogen chloride gas;
s3: the hydrogen chloride gas is extracted from the top of the hydrochloric acid desorption tower (5) and enters the hydrochloric acid absorption tower (6) to be absorbed by water to generate a hydrochloric acid product;
s4: potassium ion liquid and raw material sulfuric acid enter a potassium sulfate reactor (7), reactants discharged from the potassium sulfate reactor (7) are separated by a centrifuge (8) to obtain a potassium sulfate product and hydrogen ion mother liquor, and the hydrogen ion mother liquor is circulated to a salt dissolving tank (3).
2. The method for co-production of hydrochloric acid from potassium chloride and sulfuric acid to potassium sulfate according to claim 1, wherein in step S1, the concentration of the raw material sulfuric acid is 70-98%, the pressure of the potassium sulfate reactor is normal pressure, and the temperature is normal temperature.
3. The method for co-production of hydrochloric acid from potassium chloride and sulfuric acid to potassium sulfate according to claim 2, wherein in step S2, the concentration of hydrogen ions in the purchased hydrogen ion liquid and hydrogen ion mother liquid is 1-5%, and the balance is water.
4. The method for co-producing hydrochloric acid from potassium chloride and sulfuric acid to prepare potassium sulfate according to claim 3, wherein in step S2, the hydrochloric acid desorption tower (5) is filled with filler, the operation pressure at the top of the tower is normal pressure, the temperature is 80-90 ℃, the operation temperature at the bottom of the tower is 120-130 ℃, and the potassium ion content in the tower bottom liquid is 35-45%.
5. The method of claim 4, wherein in step S4, the concentration of potassium ions in the potassium ion solution is 35-45%, the content of chloride ions is less than 2%, and the concentration of potassium sulfate products is greater than 45%.
6. A system for preparing potassium sulfate and co-producing hydrochloric acid by potassium chloride and sulfuric acid is characterized by comprising:
a sulfuric acid storage tank (1) for storing raw sulfuric acid;
the sulfuric acid pump (2) is used for conveying sulfuric acid;
a salt dissolving tank (3) for dissolving potassium chloride to prepare a potassium chloride solution;
a potassium chloride solution pump (4) for conveying the potassium chloride solution;
the hydrochloric acid analysis tower (5) is used for reacting hydrogen ions with the potassium chloride solution to produce potassium ion solution and hydrogen chloride gas;
the hydrochloric acid absorption tower (6) is used for absorbing water and producing hydrochloric acid products by hydrogen chloride;
a potassium sulfate reactor (7) for reacting potassium ion liquid with sulfuric acid;
and the centrifugal machine (8) is used for separating the hydrogen ion mother liquor and the potassium sulfate product.
CN202110172892.3A 2021-02-08 2021-02-08 Method and system for preparing potassium sulfate and co-producing hydrochloric acid by using potassium chloride and sulfuric acid Pending CN112850752A (en)

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Application publication date: 20210528