Preparation process method for preparing manganese sulfate by absorbing sulfur dioxide through sulfur incineration

Abstract

The invention discloses a preparation process method for preparing manganese sulfate by absorbing sulfur dioxide through sulfur incineration, and particularly relates to the technical field of manganese sulfate preparation, which comprises the following steps: particle grinding, particle combustion, adsorption catalysis, hydrolysis reaction, acid-base neutralization, concentration purification and post-treatment. After the pressure in the absorption tower is controlled to reach a specific range, the activated carbon in the absorption tower achieves the optimal adsorption efficiency on sulfur dioxide, and meanwhile, due to the fact that the temperature in the absorption tower is high, the sulfur dioxide adsorbed by the activated carbon is gradually catalyzed into sulfur trioxide by a vanadium pentoxide and iron-vanadium catalyst mixture; the device effectively promotes the catalytic oxidation of sulfur dioxide to sulfur trioxide, improves the generation rate of sulfur trioxide, ensures the stability of adsorption efficiency, and not only avoids the excessive generation of sulfuric acid, but also ensures the purity of sulfuric acid by spraying water mist from the nozzles in the absorption tower to enable sulfur trioxide to be in full contact with water to perform hydrolysis reaction to generate sulfuric acid.

Description

Technical Field

[0001] The present invention relates to the technical field of manganese sulfate preparation, and more specifically, to a preparation process method for preparing manganese sulfate by burning sulfur and absorbing sulfur dioxide. Background Art

[0002] As an inorganic compound, manganese sulfate is widely used as a microanalysis reagent, a mordant, and a paint dryer. In addition, it can also be used as a raw material for battery cathode materials, high-end trace element fertilizers, feed additives, paint driers, and a catalyst in the synthesis of fatty acids. When preparing manganese sulfate, it is usually prepared by subjecting sulfur dioxide and manganese-containing compounds, such as manganese carbonate ore powder and manganese oxide ore powder, to an oxidation-reduction reaction.

[0003] The existing preparation process method for preparing manganese sulfate by burning sulfur and absorbing sulfur dioxide generally involves passing sulfur dioxide into an absorption solution containing manganese carbonate ore powder or manganese oxide ore powder, causing sulfur dioxide to directly react with the manganese carbonate solution to obtain a manganese sulfate solution. The reaction rate of direct contact between sulfur dioxide and the manganese carbonate solution is relatively slow. Therefore, improvement is needed. Summary of the Invention

[0004] To overcome the above defects, the present invention provides a preparation process method for preparing manganese sulfate by burning sulfur and absorbing sulfur dioxide. The technical problem to be solved by the present invention is: The existing preparation process method for preparing manganese sulfate by burning sulfur and absorbing sulfur dioxide generally involves passing sulfur dioxide into an absorption solution containing manganese carbonate ore powder, causing sulfur dioxide to directly react with the manganese carbonate solution to obtain a manganese sulfate solution, and the problem that the reaction rate of direct contact between sulfur dioxide and the manganese carbonate solution is relatively slow.

[0005] To achieve the above object, the present invention provides the following technical solution: A preparation process method for preparing manganese sulfate by burning sulfur and absorbing sulfur dioxide, comprising the following steps:

[0006] Particle combustion: Putting sulfur particles into a roasting furnace for combustion;

[0007] Adsorption and catalysis: Inputting the desulfurized sulfur dioxide gas into the interior of an absorption tower, enabling the activated carbon inside the absorption tower to adsorb sulfur dioxide. The surface of the activated carbon is evenly filled with a catalyst. Since the temperature of the sulfur dioxide gas is relatively high, the sulfur dioxide adsorbed on the surface of the activated carbon is oxidized into sulfur trioxide. By controlling the temperature and pressure of the absorption tower, the adsorption efficiency of activated carbon for sulfur dioxide is adjusted;

[0008] Hydrolysis reaction: Controlling the spray head inside the absorption tower to liquefy water into a mist and spray it onto the surface of the activated carbon, causing the sulfur trioxide adsorbed on the surface of the activated carbon to react with water, generating sulfuric acid that drips to the bottom of the absorption tower;

[0009] Filtration and purification: The generated sulfuric acid is filtered and purified to filter out impurities such as activated carbon mixed in the sulfuric acid, leaving pure sulfuric acid;

[0010] Acid-base neutralization: The sulfuric acid dripping at the bottom of the absorption tower is led out inside the container, and an appropriate amount of manganese carbonate is put into the container to react sulfuric acid with manganese carbonate to generate manganese sulfate;

[0011] Concentration and purification: After the manganese sulfate generated by the reaction is subjected to solid-liquid separation, it is heated to evaporate and concentrate the manganese sulfate solution to increase the concentration of the manganese sulfate solution. After the concentrated manganese sulfate solution cools, manganese sulfate crystals precipitate out;

[0012] Post-treatment: The precipitated manganese sulfate crystals are collected by filtration, and then washed and dried to obtain dry manganese sulfate crystals.

[0013] As a further solution of the present invention: When the sulfur solid is crushed and ground, the sulfur solid is crushed into 5-10 mm.

[0014] As a further solution of the present invention: The catalyst on the surface of the activated carbon is composed of vanadium pentoxide and iron-vanadium catalyst mixed in a ratio of 1:1.

[0015] As a further solution of the present invention: The sulfur dioxide gas is input into the absorption tower, and the temperature inside the absorption tower is controlled within the range of 60-80 °C, and the pressure inside the absorption tower is controlled at about 10 MPa, so that the activated carbon adsorbs and catalyzes sulfur dioxide.

[0016] As a further solution of the present invention: In the hydrolysis reaction, the concentration of the sulfuric acid dripping at the bottom of the absorption tower is monitored in real time by a sulfuric acid concentration detector. After the sulfuric acid concentration reaches 0.8-1 mol / L, an appropriate amount of sulfuric acid is sucked to react with manganese carbonate to produce a manganese sulfate solution.

[0017] As a further solution of the present invention: When the manganese sulfate solution is heated and concentrated, the temperature is controlled at 80-90 °C to evaporate and crystallize the manganese sulfate solution.

[0018] The beneficial effects of the present invention are as follows: The sulfur particles after crushing and grinding are fully burned, and the sulfur dioxide generated after combustion is input into the absorption tower. After controlling the pressure inside the absorption tower to reach a specific range, the activated carbon inside the absorption tower reaches the best adsorption efficiency for sulfur dioxide. At the same time, due to the relatively high temperature inside the absorption tower, the sulfur dioxide adsorbed by the activated carbon is gradually catalyzed into sulfur trioxide by the mixture of vanadium pentoxide and iron-vanadium catalyst, effectively promoting the catalytic oxidation of sulfur dioxide to sulfur trioxide, improving the production rate of sulfur trioxide, and ensuring the stability of the adsorption efficiency. The spray head inside the absorption tower sprays water mist to make sulfur trioxide fully contact with water for hydrolysis reaction to produce sulfuric acid, which not only avoids the excessive generation of sulfuric acid but also ensures the purity of sulfuric acid. Specific Embodiments

[0019] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0020] Example 1:

[0021] A preparation process method for producing manganese sulfate by burning sulfur and absorbing sulfur dioxide includes the following steps:

[0022] Particle combustion: Put sulfur particles into a roasting furnace for combustion;

[0023] Adsorption and catalysis: The desulfurized sulfur dioxide gas is input into the absorption tower, and the activated carbon inside the absorption tower adsorbs sulfur dioxide. The surface of the activated carbon is evenly filled with a catalyst. Due to the relatively high temperature of the sulfur dioxide gas, the sulfur dioxide adsorbed on the surface of the activated carbon is oxidized into sulfur trioxide. By controlling the temperature and pressure of the absorption tower, the adsorption efficiency of the activated carbon for sulfur dioxide is adjusted;

[0024] Hydrolysis reaction: Control the spray head inside the absorption tower to liquefy water into a mist and spray it onto the surface of the activated carbon, so that the sulfur trioxide adsorbed on the surface of the activated carbon reacts with water, and sulfuric acid droplets fall to the bottom of the absorption tower;

[0025] Filtration and purification: Filter and purify the generated sulfuric acid to filter out impurities such as activated carbon mixed in the sulfuric acid and leave pure sulfuric acid;

[0026] Acid-base neutralization: The sulfuric acid dripping to the bottom of the absorption tower is led out into a container, and an appropriate amount of manganese carbonate is put into the container to react sulfuric acid with manganese carbonate to generate manganese sulfate;

[0027] Concentration and purification: After the solid-liquid separation of the manganese sulfate generated by the reaction, it is heated to evaporate and concentrate the manganese sulfate solution to increase the concentration of the manganese sulfate solution. After the concentrated manganese sulfate solution cools, manganese sulfate crystals precipitate.

[0028] Post-treatment: After the precipitated manganese sulfate crystals are collected by filtration, they are washed and dried to obtain dry manganese sulfate crystals.

[0029] When the sulfur solid is crushed and ground, the sulfur solid is crushed into 10 - 15 mm.

[0030] The catalyst on the surface of the activated carbon is composed of vanadium pentoxide and iron-vanadium catalyst mixed in a ratio of 1:1.

[0031] Sulfur dioxide gas is input into the absorption tower. The temperature inside the absorption tower is controlled in the range of 60 - 80 °C, and the pressure inside the absorption tower is controlled at about 10 MPa, so that the activated carbon adsorbs and catalyzes sulfur dioxide.

[0032] In the hydrolysis reaction, the concentration of sulfuric acid dripping at the bottom of the absorption tower in the hydrolysis reaction is monitored in real time by a sulfuric acid concentration detector. After the sulfuric acid concentration reaches 0.8 - 1 mol / L, an appropriate amount of sulfuric acid is absorbed and reacted with manganese carbonate to produce a manganese sulfate solution.

[0033] When the manganese sulfate solution is heated and concentrated, the temperature is controlled at 80 - 90 °C for the manganese sulfate solution to evaporate and crystallize.

[0034] Example 2:

[0035] A preparation process method for producing manganese sulfate by burning sulfur and absorbing sulfur dioxide includes the following steps:

[0036] Particle combustion: The sulfur particles are put into the roasting furnace for combustion.

[0037] Adsorption and catalysis: The desulfurized sulfur dioxide gas is input into the absorption tower, and the activated carbon inside the absorption tower adsorbs sulfur dioxide. The surface of the activated carbon is evenly filled with a catalyst. Since the sulfur dioxide gas has a high temperature, the sulfur dioxide adsorbed on the surface of the activated carbon is oxidized to sulfur trioxide. By controlling the temperature and pressure of the absorption tower, the adsorption efficiency of the activated carbon for sulfur dioxide is adjusted.

[0038] Hydrolysis reaction: The nozzle inside the absorption tower is controlled to spray the water into a mist onto the surface of the activated carbon, so that the sulfur trioxide adsorbed on the surface of the activated carbon reacts with water, and sulfuric acid is produced and drips to the bottom of the absorption tower.

[0039] Filtration and purification: The generated sulfuric acid is filtered and purified to filter out impurities such as activated carbon mixed in the sulfuric acid, leaving pure sulfuric acid.

[0040] Acid-base neutralization: The sulfuric acid dripped at the bottom of the absorption tower is led out inside the container, and an appropriate amount of manganese carbonate is put into the container to react sulfuric acid with manganese carbonate to produce manganese sulfate.

[0041] Concentration and purification: After the solid-liquid separation of the manganese sulfate produced by the reaction, it is heated to evaporate and concentrate the manganese sulfate solution to increase the concentration of the manganese sulfate solution. After the concentrated manganese sulfate solution cools, manganese sulfate crystals precipitate.

[0042] Post-treatment: The precipitated manganese sulfate crystals are collected by filtration, and then washed and dried to obtain dry manganese sulfate crystals.

[0043] When the sulfur solid is crushed and ground, the sulfur solid is crushed into 5-10 mm.

[0044] The catalyst on the surface of the activated carbon is composed of vanadium pentoxide and iron-vanadium catalyst mixed in a ratio of 1:1.

[0045] Sulfur dioxide gas is input into the absorption tower. The temperature inside the absorption tower is controlled in the range of 60-80 °C, and the pressure inside the absorption tower is controlled at about 10 MPa, so that the activated carbon adsorbs and catalyzes sulfur dioxide.

[0046] In the hydrolysis reaction, the concentration of the sulfuric acid dripping at the bottom of the absorption tower in the hydrolysis reaction is monitored in real time by a sulfuric acid concentration detector. After the sulfuric acid concentration reaches 0.8-1 mol / L, an appropriate amount of sulfuric acid is absorbed and reacted with manganese carbonate to produce a manganese sulfate solution.

[0047] When the manganese sulfate solution is heated and concentrated, the temperature is controlled at 80-90 °C to evaporate and crystallize the manganese sulfate solution.

[0048] The following table is obtained according to Examples 1-2

[0049]

[0050] Example 3:

[0051] A preparation process method for producing manganese sulfate by burning sulfur and absorbing sulfur dioxide includes the following steps:

[0052] Particle combustion: The sulfur particles are put into the roasting furnace for combustion;

[0053] Adsorption and catalysis: The desulfurized sulfur dioxide gas is input into the absorption tower, and the activated carbon inside the absorption tower adsorbs sulfur dioxide. The surface of the activated carbon is evenly filled with a catalyst. Since the sulfur dioxide gas has a high temperature, the sulfur dioxide adsorbed on the surface of the activated carbon is oxidized into sulfur trioxide. By controlling the temperature and pressure of the absorption tower, the adsorption efficiency of the activated carbon for sulfur dioxide is adjusted;

[0054] Hydrolysis reaction: Control the spray heads inside the absorption tower to liquefy water into a mist and spray it onto the surface of activated carbon, causing the sulfur trioxide adsorbed on the surface of the activated carbon to react with water, generating sulfuric acid droplets that fall to the bottom of the absorption tower;

[0055] Filtration and purification: Filter and purify the generated sulfuric acid to filter out impurities such as activated carbon mixed in the sulfuric acid, leaving pure sulfuric acid;

[0056] Acid-base neutralization: The sulfuric acid dripping to the bottom of the absorption tower is led out inside the container, and an appropriate amount of manganese carbonate is put into the container, causing the sulfuric acid to react with manganese carbonate to generate manganese sulfate;

[0057] Concentration and purification: After the manganese sulfate generated by the reaction is separated from solid and liquid, it is heated to evaporate and concentrate the manganese sulfate solution to increase the concentration of the manganese sulfate solution. After the concentrated manganese sulfate solution cools, manganese sulfate crystals precipitate;

[0058] Post-treatment: The precipitated manganese sulfate crystals are collected by filtration, and then washed and dried to obtain dry manganese sulfate crystals.

[0059] When the sulfur solid is crushed and ground, the sulfur solid is crushed into 5 - 10 mm.

[0060] The catalyst on the surface of the activated carbon is composed of vanadium pentoxide and iron-vanadium catalyst mixed in a ratio of 2∶1.

[0061] Sulfur dioxide gas is input into the absorption tower. Control the temperature inside the absorption tower to be in the range of 60 - 80 °C, and control the pressure inside the absorption tower to be about 10 MPa, so that the activated carbon adsorbs and catalyzes sulfur dioxide.

[0062] In the hydrolysis reaction, rely on a sulfuric acid concentration detector to monitor the concentration of the sulfuric acid dripping to the bottom of the absorption tower in real time. After the sulfuric acid concentration reaches 0.8 - 1 mol / L, absorb an appropriate amount of sulfuric acid to react with manganese carbonate to produce a manganese sulfate solution.

[0063] When the manganese sulfate solution is heated and concentrated, control the temperature at 80 - 90 °C to evaporate and crystallize the manganese sulfate solution.

[0064] Example 4:

[0065] A preparation process method for producing manganese sulfate by burning sulfur and absorbing sulfur dioxide includes the following steps:

[0066] Particle combustion: Put sulfur particles into the roasting furnace for combustion;

[0067] Adsorption catalysis: The desulfurized sulfur dioxide gas is input into the absorption tower, and the activated carbon inside the absorption tower adsorbs sulfur dioxide. The surface of the activated carbon is evenly filled with a catalyst. Since the sulfur dioxide gas has a relatively high temperature, the sulfur dioxide adsorbed on the surface of the activated carbon is oxidized to sulfur trioxide. By controlling the temperature and pressure of the absorption tower, the adsorption efficiency of activated carbon for sulfur dioxide is adjusted;

[0068] Hydrolysis reaction: Control the nozzle inside the absorption tower to spray liquefied water in a mist form onto the surface of the activated carbon, so that the sulfur trioxide adsorbed on the surface of the activated carbon reacts with water, and sulfuric acid is produced and drips to the bottom of the absorption tower;

[0069] Filtration and purification: Filter and purify the produced sulfuric acid to filter out impurities such as activated carbon mixed in the sulfuric acid, leaving pure sulfuric acid;

[0070] Acid-base neutralization: The sulfuric acid dripping to the bottom of the absorption tower is led out into a container, and an appropriate amount of manganese carbonate is put into the container, so that sulfuric acid reacts with manganese carbonate to produce manganese sulfate;

[0071] Concentration and purification: After the manganese sulfate produced by the reaction is separated from solid and liquid, it is heated to evaporate and concentrate the manganese sulfate solution to increase the concentration of the manganese sulfate solution. After the concentrated manganese sulfate solution cools, manganese sulfate crystals precipitate;

[0072] Post-treatment: The precipitated manganese sulfate crystals are collected by filtration, and then washed and dried to obtain dry manganese sulfate crystals.

[0073] When the sulfur solid is crushed and ground, the sulfur solid is crushed into 5 - 10 mm.

[0074] The catalyst on the surface of the activated carbon is composed of vanadium pentoxide and iron-vanadium catalyst mixed in a ratio of 1:1.

[0075] The sulfur dioxide gas is input into the absorption tower. Control the temperature inside the absorption tower to be in the range of 60 - 80 °C, and control the pressure inside the absorption tower to be about 10 MPa, so that the activated carbon adsorbs and catalyzes sulfur dioxide.

[0076] In the hydrolysis reaction, rely on a sulfuric acid concentration detector to monitor the concentration of the sulfuric acid dripping to the bottom of the absorption tower in the hydrolysis reaction in real time. After the sulfuric acid concentration reaches 0.8 - 1 mol / L, absorb an appropriate amount of sulfuric acid to react with manganese carbonate to produce a manganese sulfate solution.

[0077] When the manganese sulfate solution is heated and concentrated, control the temperature at 80 - 90 °C to evaporate and crystallize the manganese sulfate solution.

[0078] Example 5:

[0079] A preparation process method for producing manganese sulfate by burning sulfur and absorbing sulfur dioxide includes the following steps:

[0080] Granular combustion: Sulfur granules are put into a roasting furnace for combustion;

[0081] Adsorption catalysis: The desulfurized sulfur dioxide gas is input into the absorption tower, and the activated carbon inside the absorption tower adsorbs sulfur dioxide. The surface of the activated carbon is evenly filled with a catalyst. Due to the relatively high temperature of the sulfur dioxide gas, the sulfur dioxide adsorbed on the surface of the activated carbon is oxidized to sulfur trioxide. By controlling the temperature and pressure of the absorption tower, the adsorption efficiency of activated carbon for sulfur dioxide is adjusted;

[0082] Hydrolysis reaction: Control the nozzle inside the absorption tower to spray liquefied water in a mist form onto the surface of the activated carbon, so that the sulfur trioxide adsorbed on the surface of the activated carbon reacts with water, generating sulfuric acid that drips to the bottom of the absorption tower;

[0083] Filtration and purification: The generated sulfuric acid is filtered and purified to filter out impurities such as activated carbon mixed in the sulfuric acid, leaving pure sulfuric acid;

[0084] Acid-base neutralization: The sulfuric acid dripping to the bottom of the absorption tower is led out into a container, and an appropriate amount of manganese carbonate is put into the container, so that sulfuric acid reacts with manganese carbonate to generate manganese sulfate;

[0085] Concentration and purification: After the manganese sulfate generated by the reaction is separated from solid and liquid, it is heated to evaporate and concentrate the manganese sulfate solution to increase the concentration of the manganese sulfate solution. After the concentrated manganese sulfate solution cools, manganese sulfate crystals precipitate;

[0086] Post-treatment: The precipitated manganese sulfate crystals are collected by filtration, and then washed and dried to obtain dry manganese sulfate crystals.

[0087] When the sulfur solid is crushed and ground, the sulfur solid is crushed into 5 - 10 mm.

[0088] The catalyst on the surface of the activated carbon is composed of vanadium pentoxide and iron-vanadium catalyst mixed in a ratio of 1:2.

[0089] The sulfur dioxide gas is input into the absorption tower. Control the temperature inside the absorption tower to be in the range of 60 - 80 °C, and control the pressure inside the absorption tower to be about 10 MPa, so that the activated carbon adsorbs and catalyzes sulfur dioxide.

[0090] In the hydrolysis reaction, rely on a sulfuric acid concentration detector to monitor the concentration of the sulfuric acid dripping to the bottom of the absorption tower in the hydrolysis reaction in real time. After the sulfuric acid concentration reaches 0.8 - 1 mol / L, absorb an appropriate amount of sulfuric acid to react with manganese carbonate to produce a manganese sulfate solution.

[0091] When the manganese sulfate solution is heated and concentrated, control the temperature at 80 - 90 °C to evaporate and crystallize the manganese sulfate solution.

[0092] The following table is obtained according to Examples 3 - 5

[0093]

[0094] Example 6:

[0095] A preparation process method for producing manganese sulfate by burning sulfur and absorbing sulfur dioxide, comprising the following steps:

[0096] Particle combustion: Put sulfur particles into a roasting furnace for combustion;

[0097] Adsorption and catalysis: The desulfurized sulfur dioxide gas is input into the absorption tower, and the activated carbon inside the absorption tower adsorbs sulfur dioxide. The surface of the activated carbon is evenly filled with a catalyst. Since the temperature of the sulfur dioxide gas is relatively high, the sulfur dioxide adsorbed on the surface of the activated carbon is oxidized into sulfur trioxide. By controlling the temperature and pressure of the absorption tower, the adsorption efficiency of activated carbon for sulfur dioxide is adjusted;

[0098] Hydrolysis reaction: Control the spray head inside the absorption tower to liquefy water into a mist and spray it onto the surface of the activated carbon, so that the sulfur trioxide adsorbed on the surface of the activated carbon reacts with water, and sulfuric acid is produced and drips to the bottom of the absorption tower;

[0099] Filtration and purification: Filter and purify the produced sulfuric acid to filter out impurities such as activated carbon mixed in the sulfuric acid, and leave pure sulfuric acid;

[0100] Acid-base neutralization: The sulfuric acid dripping to the bottom of the absorption tower is led out into a container, and an appropriate amount of manganese carbonate is put into the container, so that sulfuric acid reacts with manganese carbonate to generate manganese sulfate;

[0101] Concentration and purification: After the manganese sulfate produced by the reaction is separated from solid and liquid, it is heated to evaporate and concentrate the manganese sulfate solution to increase the concentration of the manganese sulfate solution. After the concentrated manganese sulfate solution cools, manganese sulfate crystals precipitate;

[0102] Post-treatment: The precipitated manganese sulfate crystals are collected by filtration, and then washed and dried to obtain dry manganese sulfate crystals.

[0103] When the sulfur solid is crushed and ground, the sulfur solid is crushed into 5-10 mm.

[0104] The catalyst on the surface of the activated carbon is composed of vanadium pentoxide and iron-vanadium catalyst mixed in a ratio of 1:1.

[0105] The sulfur dioxide gas is input into the absorption tower, and the temperature inside the absorption tower is controlled in the range of 60-80 °C, and the pressure inside the absorption tower is controlled at about 10 MPa, so that the activated carbon adsorbs and catalyzes sulfur dioxide.

[0106] During the hydrolysis reaction, a sulfuric acid concentration detector is relied on to monitor the concentration of the sulfuric acid dripping at the bottom of the absorption tower in real time. After the sulfuric acid concentration reaches 0.8 - 1 mol / L, an appropriate amount of sulfuric acid is drawn and reacted with manganese carbonate to produce a manganese sulfate solution.

[0107] When the manganese sulfate solution is heated and concentrated, the temperature is controlled at 80 - 90 °C for the manganese sulfate solution to evaporate and crystallize.

[0108] Example 7:

[0109] A preparation process method for producing manganese sulfate by burning sulfur and absorbing sulfur dioxide includes the following steps:

[0110] Particle combustion: The sulfur particles are put into a roasting furnace for combustion;

[0111] Adsorption and catalysis: The desulfurized sulfur dioxide gas is input into the absorption tower, and the activated carbon inside the absorption tower adsorbs sulfur dioxide. The surface of the activated carbon is evenly filled with a catalyst. Since the sulfur dioxide gas has a relatively high temperature, the sulfur dioxide adsorbed on the surface of the activated carbon is oxidized to sulfur trioxide. By controlling the temperature and pressure of the absorption tower, the adsorption efficiency of the activated carbon for sulfur dioxide is adjusted;

[0112] Hydrolysis reaction: Control the spray head inside the absorption tower to liquefy water into a mist and spray it onto the surface of the activated carbon, so that the sulfur trioxide adsorbed on the surface of the activated carbon reacts with water, generating sulfuric acid that drips to the bottom of the absorption tower;

[0113] Filtration and purification: The generated sulfuric acid is filtered and purified to filter out impurities such as activated carbon mixed in the sulfuric acid, leaving pure sulfuric acid;

[0114] Acid-base neutralization: The sulfuric acid dripping to the bottom of the absorption tower is led out into a container, and an appropriate amount of manganese carbonate is put into the container, so that the sulfuric acid reacts with manganese carbonate to form manganese sulfate;

[0115] Concentration and purification: After the manganese sulfate generated by the reaction is separated from solid and liquid, it is heated to evaporate and concentrate the manganese sulfate solution to increase the concentration of the manganese sulfate solution. After the concentrated manganese sulfate solution cools, manganese sulfate crystals precipitate;

[0116] Post-treatment: The precipitated manganese sulfate crystals are collected by filtration and then subjected to washing and drying treatments to obtain dry manganese sulfate crystals.

[0117] When the sulfur solid is crushed and ground, the sulfur solid is crushed into 5 - 10 mm.

[0118] The catalyst on the surface of the activated carbon is composed of vanadium pentoxide and an iron-vanadium catalyst mixed in a ratio of 1:1.

[0119] Sulfur dioxide gas is input into the absorption tower, the temperature inside the absorption tower is controlled within the range of 60 - 80 °C, and the pressure inside the absorption tower is controlled at about 10 MPa, so that activated carbon adsorbs and catalyzes sulfur dioxide.

[0120] In the hydrolysis reaction, rely on a sulfuric acid concentration detector to monitor the concentration of sulfuric acid dripping at the bottom of the absorption tower in real time. After the sulfuric acid concentration reaches 0.8 - 1 mol / L, absorb an appropriate amount of sulfuric acid to react with manganese carbonate to produce a manganese sulfate solution.

[0121] When the manganese sulfate solution is heated and concentrated, control the temperature at 80 - 90 °C so that the manganese sulfate solution evaporates and crystallizes.

[0122] Example 8:

[0123] A preparation process method for producing manganese sulfate by burning sulfur and absorbing sulfur dioxide includes the following steps:

[0124] Particle combustion: Put sulfur particles into the roasting furnace for combustion;

[0125] Adsorption and catalysis: The desulfurized sulfur dioxide gas is input into the absorption tower, and the activated carbon inside the absorption tower adsorbs sulfur dioxide. The surface of the activated carbon is evenly filled with a catalyst. Since the sulfur dioxide gas has a high temperature, the sulfur dioxide adsorbed on the surface of the activated carbon is oxidized to sulfur trioxide. By controlling the temperature and pressure of the absorption tower, the adsorption efficiency of activated carbon for sulfur dioxide is adjusted;

[0126] Hydrolysis reaction: Control the spray head inside the absorption tower to liquefy water into a mist and spray it onto the surface of the activated carbon, so that the sulfur trioxide adsorbed on the surface of the activated carbon reacts with water, and sulfuric acid is produced and drips to the bottom of the absorption tower;

[0127] Filtration and purification: Filter and purify the produced sulfuric acid to filter out impurities such as activated carbon mixed in the sulfuric acid and leave pure sulfuric acid;

[0128] Acid-base neutralization: The sulfuric acid dripping to the bottom of the absorption tower is led out into a container, and an appropriate amount of manganese carbonate is put into the container to react sulfuric acid with manganese carbonate to produce manganese sulfate;

[0129] Concentration and purification: After the manganese sulfate produced by the reaction is separated from solid and liquid, it is heated to evaporate and concentrate the manganese sulfate solution to increase the concentration of the manganese sulfate solution. After the concentrated manganese sulfate solution cools, manganese sulfate crystals precipitate;

[0130] Post-treatment: After the precipitated manganese sulfate crystals are filtered and collected, they are washed and dried to obtain dry manganese sulfate crystals.

[0131] When the sulfur solid is crushed and ground, the sulfur solid is crushed into 5 - 10 mm.

[0132] The catalyst on the surface of activated carbon is composed of vanadium pentoxide and iron-vanadium catalyst mixed in a ratio of 1:1.

[0133] Sulfur dioxide gas is input into the absorption tower. The temperature inside the absorption tower is controlled within the range of 60 - 80 °C, and the pressure inside the absorption tower is controlled at about 10 MPa, enabling the activated carbon to adsorb and catalyze sulfur dioxide.

[0134] In the hydrolysis reaction, the concentration of sulfuric acid dripping at the bottom of the absorption tower in the hydrolysis reaction is monitored in real time by a sulfuric acid concentration detector. After the sulfuric acid concentration reaches 0.8 - 1 mol / L, an appropriate amount of sulfuric acid is absorbed and reacted with manganese carbonate to produce a manganese sulfate solution.

[0135] When the manganese sulfate solution is heated and concentrated, the temperature is controlled at 80 - 90 °C for the manganese sulfate solution to evaporate and crystallize.

[0136] The following table is obtained according to Examples 6 - 8

[0137]

[0138] It can be seen from the comparison in the above table that:

[0139] Through Examples 1 - 2, the sulfur solid is crushed and ground into particles with a size of 5 - 10 mm, and it can be fully burned in a relatively short time during combustion;

[0140] Through Examples 3 - 5, when vanadium pentoxide and iron-vanadium catalyst are mixed in a ratio of 1:1 and filled on the surface of activated carbon, the conversion rate of sulfur dioxide to sulfur trioxide is relatively fast under the same conditions;

[0141] Through Examples 6 - 8, under the same temperature conditions, the cost performance of the sulfur dioxide adsorption capacity on the surface of activated carbon is the highest at a pressure of 10 MPa.

[0142] It can be known from the above that:

[0143] When the sulfur solid is crushed into particles with a size of 5 - 10 mm for combustion, it can avoid incomplete combustion caused by too large particles, while too small particles burn out quickly, affecting the combustion efficiency. At a pressure of 10 MPa, the activated carbon surface has the best adsorption rate for sulfur dioxide. At the same time, the vanadium pentoxide and iron-vanadium catalyst mixed in a ratio of 1:1 has the best catalytic effect on the catalytic oxidation of sulfur dioxide to produce sulfur trioxide.

[0144] The following points should be finally noted: Although the present invention has been described in detail above with general descriptions and specific embodiments, on the basis of the present invention, the above embodiments are only used to illustrate the technical solutions of the present invention, rather than limiting them; Although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A preparation process for manganese sulfate by burning sulfur and absorbing sulfur dioxide, comprising the following steps: Pellet combustion: sulfur pellets are put into the roaster for combustion; Adsorption catalysis: The desulfurized sulfur dioxide gas is input into the absorption tower, and the activated carbon inside the absorption tower adsorbs the sulfur dioxide. The surface of the activated carbon is evenly filled with catalysts. Due to the high temperature of the sulfur dioxide gas, the sulfur dioxide adsorbed on the surface of the activated carbon is oxidized into sulfur trioxide. By controlling the temperature and pressure of the absorption tower, the adsorption efficiency of the activated carbon on sulfur dioxide is adjusted; Hydrolysis reaction: The nozzle inside the absorption tower is controlled to liquefy water into mist and spray it onto the surface of the activated carbon, so that the sulfur trioxide adsorbed on the surface of the activated carbon reacts with water to produce sulfuric acid that drips at the bottom of the absorption tower; Filtration and purification: Filter and purify the generated sulfuric acid, filter out impurities such as activated carbon mixed in the sulfuric acid, and leave pure sulfuric acid; Acid-base neutralization: The sulfuric acid dripping at the bottom of the absorption tower is led out into the container, and a proper amount of manganese carbonate is put into the container to make the sulfuric acid react with manganese carbonate to form manganese sulfate; Concentration and purification: After the manganese sulfate generated by the reaction is separated into solid and liquid, it is heated to evaporate and concentrate the manganese sulfate solution to increase the concentration of the manganese sulfate solution. After the concentrated manganese sulfate solution is cooled, manganese sulfate crystals are precipitated; Post-treatment: The precipitated manganese sulfate crystals are collected by filtration, washed and dried to obtain dry manganese sulfate crystals.

2. The process for preparing manganese sulfate by burning sulfur and absorbing sulfur dioxide according to claim 1, characterized in that: When the sulfur solid is crushed and ground, the sulfur solid is crushed into pieces of 5-10 mm.

3. The process for preparing manganese sulfate by burning sulfur and absorbing sulfur dioxide according to claim 1, characterized in that: The catalyst on the surface of the activated carbon is prepared by mixing vanadium pentoxide and iron-vanadium catalyst in a ratio of 1:

1.

4. The process for preparing manganese sulfate by burning sulfur and absorbing sulfur dioxide according to claim 1, characterized in that: The sulfur dioxide gas is input into the absorption tower, and the temperature inside the absorption tower is controlled to be in the range of 60-80° C., and the pressure inside the absorption tower is controlled to be about 10 MPa, so that the activated carbon can adsorb and catalyze the sulfur dioxide.

5. The process for preparing manganese sulfate by burning sulfur and absorbing sulfur dioxide according to claim 1, characterized in that: In the hydrolysis reaction, the concentration of sulfuric acid dripping at the bottom of the absorption tower is monitored in real time by a sulfuric acid concentration detector. When the sulfuric acid concentration reaches 0.8-1 mol / L, an appropriate amount of sulfuric acid is absorbed to react with manganese carbonate to produce a manganese sulfate solution.

6. The process for preparing manganese sulfate by burning sulfur and absorbing sulfur dioxide according to claim 1, characterized in that: When the manganese sulfate solution is heated and concentrated, the temperature is controlled at 80-90° C. to allow the manganese sulfate solution to evaporate and crystallize.

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