CN111054279A - Catalytic oxidation process device and method for magnesium sulfite - Google Patents
Catalytic oxidation process device and method for magnesium sulfite Download PDFInfo
- Publication number
- CN111054279A CN111054279A CN201911415097.1A CN201911415097A CN111054279A CN 111054279 A CN111054279 A CN 111054279A CN 201911415097 A CN201911415097 A CN 201911415097A CN 111054279 A CN111054279 A CN 111054279A
- Authority
- CN
- China
- Prior art keywords
- slurry
- oxidation
- pipe
- magnesium sulfite
- crystallization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1872—Details of the fluidised bed reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
- B01J8/224—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement
- B01J8/228—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement externally, i.e. the particles leaving the vessel and subsequently re-entering it
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及化工技术领域，公开了一种用于亚硫酸镁的催化氧化工艺装置，该工艺装置包括通过管道依次连接的制浆装置、氧化装置、蒸发装置、结晶装置以及收集装置，所述氧化装置内散装有颗粒型催化剂，催化剂在反应溶液中呈自由悬浮状态，氧化装置外侧设置有连通其底部和侧部的回流装置，用于对氧化装置内的反应溶液起到搅拌作用。本发明的工艺装置设计合理，各装置相互串联，能高效地将亚硫酸镁催化氧化生成硫酸镁，并通过蒸发浓缩和冷却结晶最终制得七水硫酸镁，运行效率高、耗能低；本发明提供的用于亚硫酸镁的催化氧化工艺方法简单易行，反应条件温和，耗能低，反应周期短，运行成本低，适合推广应用。
The invention relates to the technical field of chemical industry, and discloses a catalytic oxidation process device for magnesium sulfite. The process device comprises a pulping device, an oxidation device, an evaporation device, a crystallization device and a collection device which are connected in sequence through pipelines. Granular catalysts are scattered in the device, and the catalysts are freely suspended in the reaction solution. The outside of the oxidation device is provided with a reflux device connecting the bottom and the side of the oxidation device, which is used to stir the reaction solution in the oxidation device. The process device of the invention is reasonably designed, and the devices are connected in series, which can efficiently catalyze the oxidation of magnesium sulfite to generate magnesium sulfate, and finally obtain magnesium sulfate heptahydrate through evaporation concentration and cooling crystallization, with high operation efficiency and low energy consumption; The catalytic oxidation process method for magnesium sulfite provided by the invention is simple and feasible, has mild reaction conditions, low energy consumption, short reaction period and low operation cost, and is suitable for popularization and application.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a catalytic oxidation process device and method for magnesium sulfite.
Background
The tonnage of coal-fired boilers in China is the largest in the world at present, and boiler flue gas desulfurization is more and more important along with the stricter environmental protection policies and the implementation of energy-saving and emission-reduction strategies in various places. In the current mainstream flue gas desulfurization process, the magnesium oxide wet flue gas desulfurization process is widely popularized and used due to the advantages of high desulfurization efficiency, simple operation, difficult scaling, low operation and maintenance cost and the like. In recent years, numerous magnesium-method flue gas desulfurization devices are built in China, and the devices remove sulfur dioxide in flue gas discharged by a coal-fired boiler by using abundant magnesium resources in China, so that the standard discharge of the sulfur dioxide in the flue gas of the coal-fired boiler is realized.
However, magnesium desulfurization produces a large amount of magnesium sulfite (MgSO)3) The direct application range and the use amount of the magnesium sulfite are limited, so that a plurality of enterprises directly abandon the recovery of the magnesium sulfite and treat or discard the magnesium sulfite as waste residue, thereby not only wasting a large amount of magnesium resources, but also causing secondary pollution to the environment.
In fact, magnesium sulfate generated by magnesium sulfite oxidation can be concentrated and crystallized to obtain magnesium sulfate heptahydrate (MgSO)4·7H2O), as a domestic common magnesium fertilizer, the magnesium sulfate heptahydrate has higher economic value, so the magnesium sulfate heptahydrate is the best product for recycling the magnesium sulfite, and is beneficial to improving the recycling value. However, in the conventional magnesium sulfite recovery technology, the magnesium sulfite is oxidized into magnesium sulfate by mainly adopting a non-catalytic forced oxidation and concentration crystallization method, and the problems of large device volume, large floor area, high operation energy consumption, incapability of continuous production, high recovery cost and the like are caused due to the low oxidation rate.
Therefore, it is necessary to provide a catalytic oxidation process device and method for magnesium sulfite, which can solve the above problems.
Disclosure of Invention
The invention provides a catalytic oxidation process device and a catalytic oxidation process method for magnesium sulfite, which are mainly used for solving the problems of low oxidation rate, large device volume, high operation energy consumption, incapability of continuous production and high operation cost in the recycling of magnesium sulfite which is a boiler flue gas desulfurization byproduct at present.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a catalytic oxidation process unit for magnesium sulfite comprises the following components which are connected in sequence through a pipeline:
the pulping device is used for adding water into the magnesium sulfite raw material to prepare magnesium sulfite slurry;
the oxidizing device is positioned at the downstream of the pulping device, a mutually communicated slurry conveying pipe is arranged between the oxidizing device and the pulping device, a slurry conveying pump is arranged on the slurry conveying pipe, a gas conveying pipe is arranged at the outer side of the oxidizing device and is used for providing oxidizing air required by oxidation reaction for the inside of the device, and magnesium sulfite slurry is conveyed into the oxidizing device through the slurry conveying pipe for oxidation reaction to generate magnesium sulfate solution;
the evaporation device is positioned at the downstream of the oxidation device, a solution conveying pipe which is communicated with each other is arranged between the evaporation device and the oxidation device, a solution conveying pump is arranged on the solution conveying pipe, and the evaporation device carries out evaporation concentration on the magnesium sulfate solution from the oxidation device to form a magnesium sulfate concentrated solution;
the crystallizing device is positioned at the downstream of the evaporating device, the crystallizing device and the evaporating device are provided with mutually communicated concentrated solution conveying pipes, a concentrated solution conveying pump is arranged on the concentrated solution conveying pipe, and the crystallizing device cools and crystallizes the magnesium sulfate concentrated solution from the evaporating device to form a crystallizing mixture;
the collecting device is positioned at the downstream of the crystallizing device and is used for filtering and separating the crystallized mixture from the crystallizing device to obtain magnesium sulfate heptahydrate crystals, and the filtrate obtained by separation is sent back to the evaporating device for re-evaporation and concentration;
the oxidation device is internally provided with a granular catalyst in a bulk manner, and the catalyst is in a free suspension state in a reaction solution in the device and is used for improving the oxidation reaction rate;
and a reflux device communicated with the bottom and the side of the oxidation device is arranged outside the oxidation device and used for pumping the reaction solution at the bottom of the oxidation device to reflux into the device and playing a role in circularly stirring the reaction solution in the oxidation device.
When the catalytic oxidation process device for the magnesium sulfite is put into operation, a certain amount of solid magnesium sulfite raw materials and water are added into a pulping device, the mixture is stirred and prepared into required slurry, then the slurry is conveyed into an oxidation device through a slurry conveying pipe to be oxidized, air is introduced into the oxidation device, the oxidation device is internally dispersed with a particle type catalyst, the magnesium sulfite slurry is efficiently and catalytically oxidized to generate magnesium sulfate solution under the action of the catalyst, and a reflux device can perform a circulating stirring action on the reaction solution in the oxidation device, so that the reaction rate is improved;
then, the high-concentration magnesium sulfate solution generated in the oxidation device is quantitatively conveyed into an evaporation device through a solution conveying pipe, water is evaporated by heating and raising the temperature, the magnesium sulfate solution is concentrated to be close to the saturated concentration, and then is discharged into a crystallization device through a concentrated solution conveying pipe, natural cooling crystallization is carried out, the obtained crystallization mixture flows into a collection device according to gravity for filtration and separation, magnesium sulfate heptahydrate crystals are obtained, and the obtained filtrate is conveyed back to the evaporation device for re-evaporation and concentration.
Further, the catalyst is a molecular sieve supported catalyst, the supported active components are cobalt nitrate and manganese nitrate, the molar ratio of cobalt to manganese in the catalyst is 0.5-1.5: 1, the catalyst is spherical, and the diameter of the catalyst is 2-8 mm. The molecular sieve has a uniform microporous structure, strong adsorption capacity, high mechanical strength and good thermal stability, can effectively adsorb active ingredients, and enables the catalyst to have a lasting and efficient catalytic function. The catalyst is made into a spherical structure, so that the catalyst has a large surface area, is ensured to be fully contacted with magnesium sulfite, promotes the oxidation reaction rate, and can reduce the resistance of free suspension flow of the catalyst in a reaction solution, so that the catalyst can reach each position in the device to be contacted with the magnesium sulfite, the magnesium sulfite in the device is fully oxidized, and magnesium sulfate is generated.
Further, the reflux device comprises a reflux pipe, a jet pump and a venturi ejector:
the inlet end of the return pipe is communicated with the bottom of the oxidation device;
the jet pump is arranged on the return pipe and used for pressurizing and accelerating the return liquid, so that the return liquid enters the oxidation device at a certain speed and generates turbulence disturbance on the reaction solution, thereby playing a role in stirring;
the venturi ejector is vertically installed, a top inlet of the venturi ejector is connected with an outlet end of the return pipe, a side inlet of the venturi ejector is communicated with the gas conveying pipe, a drainage pipe extending into the oxidation device is arranged at the bottom end of the venturi ejector, an outlet of the drainage pipe faces downwards, air and reflux from the gas conveying pipe are fully contacted and mixed in the venturi ejector and then are introduced into the oxidation device through the drainage pipe, and a circulating stirring effect is achieved on reaction solution in the oxidation device.
Further, the oxidation device is tank structure, and the oxidation device top is provided with the oxidation device inlet of connecting the thick liquid conveyer pipe, and the oxidation device bottom is provided with the first drain outlet of connecting the solution conveyer pipe and the second drain outlet of intercommunication back flow entry end, first drain outlet department is provided with first filter, second drain outlet department is provided with the second filter, and the mesh size of first filter and second filter is 0.05 ~ 1 mm. The arrangement of the first filter and the second filter can prevent catalyst particles in the device from flowing out of the device along with liquid to cause the blockage of an external pipeline, and can also reduce the loss rate of the catalyst and reduce the operation cost.
Furthermore, the solution conveying pipe is provided with a solution filter, the solution filter is positioned in front of the solution conveying pump, the mesh size of the solution filter is 0.01-0.5 mm, and the solution filter is used for filtering and removing fine particles or impurities carried in the reaction solution, so that the purity of a final product is improved.
Further, install heating device in the oxidation unit, the preferred electrical heating stick of heating device, the electrical heating stick sets up three altogether to be 120 contained angles distribution each other on the coplanar in the oxidation unit, electrical heating stick installation convenient operation directly contacts with reaction solution, and the heating is even, helps improving oxidation reaction rate.
Furthermore, the pulping device comprises a slurry preparation tank and a slurry buffer tank, wherein the slurry preparation tank can prepare the magnesium sulfite solid raw material into slurry with required concentration in advance, and then the slurry is transferred into the slurry buffer tank for standby;
the top of the slurry preparation tank is provided with a raw material feeding port for feeding a magnesium sulfite raw material, the raw material feeding port is provided with a raw material screen for impurity removal, and the bottom of the slurry preparation tank is provided with a slurry discharge pipe;
the top of the slurry buffer tank is provided with a buffer tank liquid inlet, slurry discharged from the bottom of the slurry preparation tank flows into the slurry buffer tank through a slurry discharge pipe and the buffer tank liquid inlet, a slurry filter screen is arranged at the liquid inlet of the buffer tank and used for filtering undissolved solid raw materials, and the bottom of the slurry buffer tank is communicated with a slurry conveying pipe;
the slurry preparation tank is internally provided with a first stirrer, the slurry buffer tank is internally provided with a second stirrer, and because the magnesium sulfite is slightly soluble in water, the raw materials are ensured to be fully dissolved by continuous stirring to form suspension slurry, so that the concentration of the slurry is kept uniform.
Furthermore, a first exhaust pipe is arranged at the top of the oxidation device, a second exhaust pipe is arranged at the top of the evaporation device, the first exhaust pipe and the second exhaust pipe are communicated with the slurry preparation tank, and outlet ends of the first exhaust pipe and the second exhaust pipe extend below the liquid level of the slurry preparation tank, so that gas volatilized by heating in the oxidation device and the evaporation device can be intensively recycled into slurry in the slurry preparation tank for condensation and recovery, and meanwhile, heat carried in the gas can be transferred to the slurry to promote dissolution of magnesium sulfite raw materials, so that the whole process device is free of waste gas emission in operation, and is energy-saving and environment-friendly.
Furthermore, the evaporation device is an evaporation kettle, a heat jacket is arranged on the outer side of the evaporation kettle, circulating heat conduction oil is introduced into the heat jacket to heat and preserve heat of the evaporation device, high-temperature heat conduction oil enters from the lower portion of the heat jacket, low-temperature heat conduction oil after heat exchange flows out from the upper portion of the heat jacket, and the circulating heat conduction oil continuously and stably supplies heat to the evaporation device to promote evaporation and concentration of the magnesium sulfate solution.
Further, the crystallization device is provided with three sets side by side, because the cooling crystallization needs a certain time, consequently three sets of crystallization device alternate use, ensure that whole process units can run lastingly, be provided with the crystallization agitator in the crystallization device, can be through stirring magnesium sulfate concentrate for the heat gives off, improve cooling crystallization efficiency, the bottom design of crystallization device is the toper structure and is equipped with the unloading pipe, be favorable to the crystallization mixture to collect in the device bottom, and rely on gravity to flow into collection device along the unloading pipe.
Furthermore, a filter cylinder corresponding to the crystallization device is arranged in the collection device, a filtrate conveying pipe communicated with the evaporation device is arranged at the bottom of the collection device, a filtrate conveying pump and a heater are arranged on the filtrate conveying pipe, a crystallization mixture flowing out of the bottom of the crystallization device enters the filter cylinder for filtration and separation, magnesium sulfate heptahydrate crystals are collected in the filter cylinder and can be continuously dried to obtain a required finished product, and filtrate obtained by filtration and separation is sent to the evaporation device for re-evaporation and concentration after being pressurized by the filtrate conveying pump and heated by the heater along the filtrate conveying pipe.
Furthermore, a filtrate filter is arranged on the filtrate conveying pipe and is positioned in front of the filtrate conveying pump, the mesh size of the filtrate filter is 0.01-0.5 mm, and the filtrate filter is used for filtering and removing fine particles or impurities carried in filtrate, so that the purity of a final product is improved.
Furthermore, the bottom of the collecting device is provided with a waste liquid discharge pipe, and part of the deposition liquid at the bottom of the collecting device can be discharged through the waste liquid discharge pipe periodically and sent to a sewage treatment system for treatment, so that the accumulation amount of other chemical components such as chloride ions in the whole device is reduced, and the corrosion of the chemical components to equipment pipelines is reduced.
The invention also aims to provide a process method for carrying out magnesium sulfite catalytic oxidation by using the catalytic oxidation process device, which comprises the following steps:
s1, slurry preparation: adding a magnesium sulfite raw material and water into a pulping device to prepare a magnesium sulfite slurry, wherein the concentration of the slurry is 30-40%;
s2, catalytic oxidation: feeding the magnesium sulfite slurry prepared in the step S1 into an oxidation device through a slurry conveying pipe, and introducing oxidation air to perform catalytic oxidation reaction to generate a magnesium sulfate solution;
s3, evaporation and concentration: conveying the magnesium sulfate solution generated in the reaction in the step S2 into an evaporation device through a solution conveying pipe, and carrying out evaporation concentration to enable the magnesium sulfate solution to be close to the saturated concentration so as to obtain a magnesium sulfate concentrated solution;
s4, cooling and crystallizing: conveying the magnesium sulfate concentrated solution obtained in the step S3 into a crystallizing device through a concentrated solution conveying pipe, naturally cooling and crystallizing, cooling to normal temperature, and gradually separating out crystals in the cooling process to obtain a crystallized mixture;
s5, finished product collection: the crystallization mixture from the crystallization apparatus was filtered, separated and dried in a collection apparatus to obtain magnesium sulfate heptahydrate crystals.
Further, in step S2, the temperature of the catalytic oxidation reaction is 50 to 60 ℃, the pressure is normal pressure, and the used oxidation air is normal pressure air.
Further, in step S2, the volume ratio of the catalyst addition amount in the oxidation device to the reaction solution in the device is 50-100 g: 1L, and the molar ratio of the magnesium sulfite to the air is 1: 2-3.
Further, in step S3, the operation temperature of evaporation concentration is 60-65 ℃, and the pressure is normal pressure.
Further, in step S4, the cooling crystallization time is 6-10 h.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1. the catalytic oxidation process device for the magnesium sulfite has reasonable design and small quantity, is connected in series, is beneficial to continuous production and operation, can efficiently perform catalytic oxidation on the magnesium sulfite to generate the magnesium sulfate, and finally prepares the magnesium sulfate heptahydrate through evaporation concentration and cooling crystallization, and has small volume, small occupied area, high operation efficiency and low energy consumption;
2. the oxidation device is internally and bulk-loaded with the granular catalyst, the granular catalyst has a large surface area and can be fully contacted with magnesium sulfite to promote the oxidation reaction rate, the catalyst is in a free suspension state in a reaction solution in the device and can reach each position in the device to be contacted with the magnesium sulfite, so that the magnesium sulfite in the device is fully oxidized to generate magnesium sulfate, the high-efficiency catalytic oxidation is realized, the reaction time is shortened, and the reaction efficiency is improved;
3. the reflux device communicated with the bottom and the side of the oxidation device is arranged outside the oxidation device, so that the reaction solution at the bottom of the oxidation device can be pumped and then flows back into the device, the reaction solution is circularly disturbed and stirred, the reaction speed is accelerated, an additional stirrer is not required for the oxidation device, energy is saved, consumption is reduced, the collision damage of mechanical stirring to the catalyst is reduced, and the service life of the catalyst is prolonged;
4. the catalytic oxidation process method for the magnesium sulfite provided by the invention is simple and feasible, the reaction conditions of each step are mild, the operation energy consumption is low, each step is closely linked, the continuous operation can be realized, the reaction period of the whole operation process is short, the efficiency is favorably improved, the operation cost is saved, and the catalytic oxidation process method is suitable for popularization and application.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic diagram of a catalytic oxidation process unit for magnesium sulfite in accordance with the present invention;
FIG. 2 is a flow diagram of a catalytic oxidation process unit for magnesium sulfite in accordance with the present invention;
FIG. 3 is a schematic view of a pulping apparatus according to the invention;
FIG. 4 is a schematic view of an oxidation apparatus of the present invention;
FIG. 5 is a schematic view of an evaporation apparatus of the present invention;
FIG. 6 is a schematic view of a crystallization apparatus and a collection apparatus of the present invention;
FIG. 7 is a flow chart of a process for the catalytic oxidation of magnesium sulfite.
In the figure: 1-pulping device, 10-slurry delivery pipe, 101-slurry delivery pump, 11-slurry preparation tank, 111-raw material input port, 112-raw material screen, 113-slurry discharge pipe, 114-first stirrer, 12-slurry buffer tank, 121-buffer tank inlet, 122-slurry filter screen, 123-second stirrer, 2-oxidation device, 20-solution delivery pipe, 201-solution delivery pump, 202-solution filter, 21-gas delivery pipe, 22-catalyst, 23-reflux device, 231-reflux pipe, 232-jet pump, 233-venturi ejector, 234-drainage pipe, 24-oxidation device inlet, 25-first discharge port, 251-first filter, 26-second discharge port, 261-a second filter, 27-an electric heating rod, 28-a first exhaust pipe, 3-an evaporation device, 30-a concentrated solution conveying pipe, 301-a concentrated solution conveying pump, 31-a second exhaust pipe, 32-a heat jacket, 321-high-temperature heat conducting oil, 322-low-temperature heat conducting oil, 4-a crystallization device, 40-a discharging pipe, 41-a crystallization stirrer, 5-a collection device, 51-a filter cartridge, 52-a filtrate conveying pipe, 521-a filtrate conveying pump, 522-a heater, 523-a filtrate filter and 53-a waste liquid discharging pipe.
Detailed Description
The drawings are for illustrative purposes only and are not to be construed as limiting the patent; for better illustration of the present embodiment, some parts of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; it will be understood by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted.
The description of "first" and "second" referred to in the embodiments of the present invention is for descriptive purposes only and is not to be construed as indicating or implying any relative importance or implicit indication of the number of technical features indicated, whereby the features defined as "first" and "second" may explicitly or implicitly include at least one such feature.
Meanwhile, the terms "upper", "lower", "front", "rear", "inner", "outer", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted" and "connected" are to be interpreted broadly, e.g., as being either fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be directly connected or indirectly connected through an intermediate member, so to speak, connected internally to the two elements. The specific meaning of the above terms in the present invention can be understood according to specific situations by those skilled in the art.
In order to more clearly understand the technical features, objects and effects of the present invention, embodiments of the present invention will now be described in detail with reference to the accompanying drawings, but the embodiments of the present invention are not limited thereto.
Example 1:
as shown in fig. 1-6, a catalytic oxidation process unit for magnesium sulfite comprises the following components which are connected in sequence through pipelines:
the pulping device 1 is used for adding water into a magnesium sulfite raw material to prepare magnesium sulfite slurry;
the oxidizing device 2 is positioned at the downstream of the pulping device 1, a mutually communicated slurry conveying pipe 10 is arranged between the oxidizing device 2 and the pulping device 1, a slurry conveying pump 101 is arranged on the slurry conveying pipe 10, a gas conveying pipe 21 is arranged at the outer side of the oxidizing device 2, the gas conveying pipe 21 is used for introducing air required by oxidation reaction into the oxidizing device 2, and magnesium sulfite slurry is conveyed into the oxidizing device 2 through the slurry conveying pipe 10 for oxidation reaction to generate magnesium sulfate solution;
the evaporation device 3 is positioned at the downstream of the oxidation device 2, a solution conveying pipe 20 which is communicated with each other is arranged between the evaporation device 3 and the oxidation device 2, a solution conveying pump 201 is arranged on the solution conveying pipe 20, and the evaporation device 3 carries out evaporation concentration on the magnesium sulfate solution from the oxidation device 2 to form a magnesium sulfate concentrated solution;
a crystallizing device 4 which is positioned at the downstream of the evaporating device 3, wherein the crystallizing device 4 and the evaporating device 3 are provided with a concentrated solution conveying pipe 30 which is communicated with each other, a concentrated solution conveying pump 301 is arranged on the concentrated solution conveying pipe 30, and the crystallizing device 4 cools and crystallizes the magnesium sulfate concentrated solution from the evaporating device 3 to form a crystallizing mixture;
the collecting device 5 is positioned at the downstream of the crystallizing device 4, the collecting device 5 is used for filtering and separating the crystallized mixture from the crystallizing device 4 to obtain magnesium sulfate heptahydrate crystals, and the filtrate obtained by separation is sent back to the evaporating device 3 for re-evaporation and concentration;
the oxidation device 2 is internally provided with a granular catalyst 22 in bulk, and the catalyst 22 is in a free suspension state in a reaction solution in the device and is used for improving the oxidation reaction rate;
and a reflux device 23 communicated with the bottom and the side of the oxidation device 2 is arranged outside the oxidation device 2 and used for pumping the reaction solution at the bottom of the oxidation device 2 to reflux into the device and playing a role in circularly stirring the reaction solution in the oxidation device 2.
The catalyst 22 in the oxidation device 2 is a molecular sieve supported catalyst, the supported active components are cobalt nitrate and manganese nitrate, the molar ratio of cobalt to manganese in the catalyst 22 is 0.5-1.5: 1, the catalyst is spherical, and the diameter of the catalyst is 2-8 mm. The molecular sieve has a uniform microporous structure, strong adsorption capacity, high mechanical strength and good thermal stability, and can effectively adsorb active ingredients, so that the catalyst 22 has a lasting and efficient catalytic function. The catalyst 22 is made into a spherical structure, which not only can make the catalyst have a larger surface area to ensure that the catalyst is fully contacted with the magnesium sulfite to promote the oxidation reaction rate, but also can reduce the resistance of the free suspension flow of the catalyst 22 in the reaction solution, so that the catalyst 22 can reach each position in the oxidation device 2 to be contacted with the magnesium sulfite, and the magnesium sulfite in the device is fully oxidized to generate the magnesium sulfate.
The reflux unit 23 includes a reflux pipe 231, a jet pump 232, and a venturi ejector 233: the inlet end of the return pipe 231 is communicated with the bottom of the oxidation device 2; the jet pump 232 is installed on the return pipe 231 and used for pressurizing and accelerating the return liquid, so that the return liquid enters the oxidation device 2 at a certain speed and generates turbulence disturbance on the reaction solution, thereby playing a role in stirring; the venturi ejector 233 is vertically installed, an inlet at the top end of the venturi ejector 233 is connected with an outlet end of the return pipe 231, an inlet at the side portion of the venturi ejector 233 is communicated with the gas delivery pipe 21, a drain pipe 234 extending into the oxidation device 2 is arranged at the bottom end of the venturi ejector 233, an outlet of the drain pipe 234 faces downwards, the venturi ejector 233 can suck air from the gas delivery pipe 21 by utilizing an internal and external pressure difference principle, the air and return liquid from the return pipe 231 are fully mixed in the venturi ejector 233 and then are introduced into the oxidation device 2 through the drain pipe 234, and therefore the quick fusion effect of the air and magnesium sulfite can be enhanced, and the circulating stirring effect on reaction solution in the oxidation device 2 can be achieved.
The oxidation device 2 is of a tank structure, the top of the oxidation device 2 is provided with an oxidation device liquid inlet 24 connected with the slurry conveying pipe 10, the bottom of the oxidation device 2 is provided with a first liquid outlet 25 connected with the solution conveying pipe 20 and a second liquid outlet 26 communicated with the inlet end of the return pipe 231, the first liquid outlet 25 is provided with a first filter 251, the second liquid outlet 26 is provided with a second filter 261, and the mesh sizes of the first filter 251 and the second filter 261 are 0.05-1 mm. The first drain port 25 and the second drain port 26 are arranged to facilitate connection and fixation of the oxidation device 2 with an external pipeline, and the first filter 251 and the second filter 261 are arranged to prevent particles of the catalyst 22 in the device from blocking the external pipeline along with the liquid flowing out of the device, so that the loss rate of the catalyst 22 can be reduced, and the operation cost can be reduced.
The solution delivery pipe 20 is provided with a solution filter 202, the solution filter 202 is positioned in front of the solution delivery pump 201, the mesh size of the solution filter 202 is 0.01-0.5 mm, two sets of the solution filters 202 can be arranged in parallel, one set is used, the other set is prepared, the switching and the use are convenient, and the solution filter 202 is used for filtering and removing fine particles or impurities carried in the reaction solution, so that the purity of the final product is improved.
Install heating device in the oxidation unit 2, heating device adopts electrical heating rod 27, and electrical heating rod 27 sets up three altogether to be 120 contained angles distribution each other on the coplanar in oxidation unit 2, electrical heating rod 27 installation easy operation is convenient, direct and reaction solution contact, and heat transfer efficiency is high, and the heating is even, is used for heating for the reaction solution in the device, can effectively improve reaction rate.
The pulping device 1 comprises a slurry preparation tank 11 and a slurry buffer tank 12, wherein a solid magnesium sulfite raw material can be prepared into slurry with required concentration in advance in the slurry preparation tank 11, and then the slurry is transferred into the slurry buffer tank 12 for standby;
the top of the slurry preparation tank 11 is provided with a raw material feeding port 111 for feeding a magnesium sulfite raw material, the raw material feeding port 111 is provided with a raw material screen 112 for impurity removal, and the bottom of the slurry preparation tank 11 is provided with a slurry discharge pipe 113;
a slurry inlet 121 is arranged at the top of the slurry buffer tank 12, slurry discharged from the bottom of the slurry preparation tank 11 flows into the slurry buffer tank 12 through a slurry discharge pipe 113 and the buffer tank inlet 121, a slurry filter screen 122 is arranged at the buffer tank inlet 121, the slurry filter screen 122 is used for filtering undissolved solid raw materials, and the bottom of the slurry buffer tank 12 is communicated with the slurry conveying pipe 10;
the first stirrer 114 is arranged in the slurry preparation tank 11, the second stirrer 123 is arranged in the slurry buffer tank 12, and because the magnesium sulfite is slightly soluble in water, the raw materials are ensured to be fully dissolved by continuous stirring, and suspension slurry is formed, so that the concentration of the slurry is kept uniform.
The top of the oxidation device 2 is provided with a first exhaust pipe 28, the top of the evaporation device 3 is provided with a second exhaust pipe 31, the first exhaust pipe 28 and the second exhaust pipe 31 are both communicated with the slurry preparation tank 11, and the outlet ends of the first exhaust pipe 28 and the second exhaust pipe 31 extend below the liquid level of the slurry preparation tank 11, so that the gas volatilized by heating in the oxidation device 2 and the evaporation device 3 can be intensively recovered into the slurry in the slurry preparation tank 11 for condensation and recovery, and meanwhile, the heat carried in the gas can be transferred to the slurry to promote the dissolution of magnesium sulfite raw materials, so that the whole process device has no waste gas emission in operation, and is energy-saving and environment-friendly.
The evaporation device 3 is an evaporation kettle, a heat jacket 32 is arranged on the outer side of the evaporation kettle, circulating heat conduction oil is introduced into the heat jacket 32 to heat and keep warm for the evaporation device 3, high-temperature heat conduction oil 321 enters from the lower portion of the heat jacket 32, low-temperature heat conduction oil 322 after heat exchange flows out from the upper portion of the heat jacket 32, heat conduction oil conducts heat stably and can be recycled, heat can be continuously and stably supplied to the evaporation device 3, and evaporation and concentration of magnesium sulfate solution are promoted.
The crystallization device 4 is provided with three sets in parallel, because the cooling crystallization needs a certain time, therefore three sets of crystallization devices 4 alternate use, ensure that whole process units can run lastingly, be provided with crystallization agitator 41 in the crystallization device 4, can be through stirring magnesium sulfate concentrate, accelerate heat dissipation, improve cooling crystallization efficiency, the bottom design of crystallization device 4 is the toper structure and is equipped with down pipe 40, be favorable to the crystallization mixture to collect in crystallization device 4 bottom, and rely on gravity to flow into collection device 5 along down pipe 40.
A stainless steel filter cylinder 51 corresponding to the crystallization device 4 is arranged in the collection device 5, a filtrate conveying pipe 52 communicated with the evaporation device 3 is arranged at the bottom of the collection device 5, and a filtrate conveying pump 521 and a heater 522 are arranged on the filtrate conveying pipe 52. And (3) filtering and separating the crystallization mixture flowing out from the bottom of the crystallization device 4 in a filter cylinder 51, collecting magnesium sulfate heptahydrate crystals in the filter cylinder 51, continuously drying to obtain a required finished product, pressurizing filtrate obtained by filtering and separating along a filtrate conveying pipe 52 by a filtrate conveying pump 521 and heating the filtrate to above 50 ℃ by a heater 522, and then conveying the filtrate into the evaporation device 3 for re-evaporation and concentration.
The filtrate conveying pipe 52 is provided with a filtrate filter 523, the filtrate filter 523 is positioned in front of the filtrate conveying pump 521, the mesh size of the filtrate filter 523 is 0.01-0.5 mm, two sets of the filtrate filters 523 can be arranged in parallel, one set is used, the other set is prepared, the switching use is convenient, the filtrate filter 523 is used for filtering and removing fine particles or impurities carried in the filtrate, and the purity of a final product is improved.
The bottom of the collecting device 5 is provided with a waste liquid discharge pipe 53, and part of the deposition liquid at the bottom of the collecting device 5 can be periodically discharged through the waste liquid discharge pipe 53 and sent to a sewage treatment system for treatment, so that the accumulation amount of other chemical components such as chloride ions in the whole device is reduced, and the corrosion of the chemical components to equipment pipelines is reduced.
When the catalytic oxidation process device for the magnesium sulfite is put into operation, quantitative magnesium sulfite solid raw materials and water are added into the pulping device 1, the mixture is stirred and prepared into required slurry, then the slurry is sent into the oxidation device 2 through the slurry conveying pipe 10 to be oxidized, air is introduced into the oxidation device 2, the granular catalyst 22 is scattered in the oxidation device 2 in bulk, the magnesium sulfite slurry is efficiently and catalytically oxidized under the action of the catalyst 22 to generate magnesium sulfate solution, and the reflux device 23 can perform a circulating stirring action on the reaction solution in the oxidation device 2, so that the reaction rate is improved;
then, the high concentration magnesium sulfate solution generated in the oxidation apparatus 2 is quantitatively fed into the evaporation apparatus 3 through the solution delivery pipe 20, water is evaporated by heating and raising the temperature, the magnesium sulfate solution is concentrated to a concentration close to a saturated concentration, and is discharged into the crystallization apparatus 4 through the concentrated solution delivery pipe 30, natural cooling and crystallization are performed, the obtained crystallization mixture flows into the collection apparatus 5 by gravity for filtration and separation, magnesium sulfate heptahydrate crystals are obtained, and the obtained filtrate is returned to the evaporation apparatus 3 for re-evaporation and concentration.
Example 2:
as shown in fig. 1-2 and fig. 7, the catalytic oxidation process device of the present invention is used to perform catalytic oxidation on solid magnesium sulfite, and the process method specifically comprises the following steps:
s1, slurry preparation: adding a solid magnesium sulfite raw material and water into a slurry preparation tank 11 to prepare a magnesium sulfite slurry with the slurry concentration of 35%;
s2, catalytic oxidation: the magnesium sulfite slurry prepared in the S1 is sent into an oxidation device 2 through a slurry conveying pipe 10, the conveying flow is 300kg/h, air is introduced, and catalytic oxidation reaction is carried out at the temperature of 60 ℃ and under normal pressure to generate magnesium sulfate solution;
in step S2, the ratio of the amount of catalyst added to the reaction solution in the oxidation apparatus 2 was 80 g: 1L, and the molar ratio of magnesium sulfite to air was 1: 2.5.
S3, evaporation and concentration: feeding the magnesium sulfate solution generated in the reaction in the step S2 into an evaporation device 3 through a solution delivery pipe 20, and carrying out evaporation concentration at the temperature of 65 ℃ and normal pressure to make the magnesium sulfate solution approach to a saturated concentration, thereby obtaining a magnesium sulfate concentrated solution;
s4, cooling and crystallizing: the magnesium sulfate concentrated solution obtained in the step S3 is conveyed into a crystallizing device 4 through a concentrated solution conveying pipe 30, natural cooling and crystallization are carried out for 8 hours, the temperature is reduced to normal temperature, and crystals are gradually separated out in the cooling process to obtain a crystallization mixture;
s5, finished product collection: the crystallization mixture from the crystallization apparatus 4 was filtered and separated in the collection apparatus 5 to obtain magnesium sulfate heptahydrate crystals, dried at 45 ℃ and weighed.
The yield of the magnesium sulfate heptahydrate is 120kg/h and the purity is more than 99 percent through weighing calculation and detection.
Example 3:
as shown in fig. 1-2 and fig. 7, the catalytic oxidation process device of the present invention is used to perform catalytic oxidation on solid magnesium sulfite, and the process method specifically comprises the following steps:
s1, slurry preparation: adding a solid magnesium sulfite raw material and water into a slurry preparation tank 11 to prepare a magnesium sulfite slurry with the slurry concentration of 40%;
s2, catalytic oxidation: the magnesium sulfite slurry prepared in the S1 is sent into an oxidation device 2 through a slurry conveying pipe 10, the conveying flow is 300kg/h, air is introduced, and catalytic oxidation reaction is carried out at the temperature of 55 ℃ and under normal pressure to generate magnesium sulfate solution;
in step S2, the ratio of the amount of catalyst added to the reaction solution in the oxidation apparatus 2 was 100 g: 1L, and the molar ratio of magnesium sulfite to air was 1: 3.
S3, evaporation and concentration: feeding the magnesium sulfate solution generated in the reaction in the step S2 into an evaporation device 3 through a solution delivery pipe 20, and carrying out evaporation concentration at a temperature of 62 ℃ under normal pressure to make the magnesium sulfate solution approach a saturated concentration, thereby obtaining a magnesium sulfate concentrated solution;
s4, cooling and crystallizing: the magnesium sulfate concentrated solution obtained in the step S3 is conveyed into a crystallizing device 4 through a concentrated solution conveying pipe 30, natural cooling crystallization is carried out for 10 hours, the temperature is reduced to normal temperature, and crystals are gradually separated out in the cooling process to obtain a crystallization mixture;
s5, finished product collection: the crystallization mixture from the crystallization apparatus 4 was filtered and separated in the collection apparatus 5 to obtain magnesium sulfate heptahydrate crystals, dried at 45 ℃ and weighed.
The yield of the magnesium sulfate heptahydrate is 132kg/h and the purity is more than 99 percent through weighing calculation and detection.
Example 4:
as shown in fig. 1-2 and fig. 7, the catalytic oxidation process device of the present invention is used to perform catalytic oxidation on solid magnesium sulfite, and the process method specifically comprises the following steps:
s1, slurry preparation: adding a solid magnesium sulfite raw material and water into a slurry preparation tank 11 to prepare a magnesium sulfite slurry with the slurry concentration of 30%;
s2, catalytic oxidation: feeding the magnesium sulfite slurry prepared in the step S1 into an oxidation device 2 through a slurry conveying pipe 10, wherein the conveying flow rate is 300kg/h, introducing air, and carrying out catalytic oxidation reaction at the temperature of 50 ℃ and under normal pressure to generate a magnesium sulfate solution;
in step S2, the volume ratio of the catalyst to the reaction solution in the oxidation apparatus 2 was 50 g: 1L, and the molar ratio of the magnesium sulfite to air was 1: 2.
S3, evaporation and concentration: feeding the magnesium sulfate solution generated in the reaction in the step S2 into an evaporation device 3 through a solution delivery pipe 20, and carrying out evaporation concentration at a temperature of 60 ℃ and normal pressure to make the magnesium sulfate solution approach a saturated concentration, thereby obtaining a magnesium sulfate concentrated solution;
s4, cooling and crystallizing: the magnesium sulfate concentrated solution obtained in the step S3 is conveyed into a crystallizing device 4 through a concentrated solution conveying pipe 30, natural cooling and crystallization are carried out for 6 hours, the temperature is reduced to the normal temperature, and crystals are gradually separated out in the cooling process to obtain a crystallization mixture;
s5, finished product collection: the crystallization mixture from the crystallization apparatus 4 was filtered and separated in the collection apparatus 5 to obtain magnesium sulfate heptahydrate crystals, dried at 45 ℃ and weighed.
The yield of the magnesium sulfate heptahydrate is 108kg/h and the purity is more than 99 percent through weighing calculation and detection.
In the drawings, the positional relationship is described for illustrative purposes only and is not to be construed as limiting the present patent; it should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A catalytic oxidation process unit for magnesium sulfite comprises the following components which are connected in sequence through a pipeline:
the pulping device is used for preparing magnesium sulfite slurry;
the oxidizing device is positioned at the downstream of the pulping device, a mutually communicated slurry conveying pipe is arranged between the oxidizing device and the pulping device, and a gas conveying pipe is arranged at the outer side of the oxidizing device and used for providing oxidizing air for the oxidizing device;
the evaporation device is positioned at the downstream of the oxidation device, and a solution conveying pipe communicated with the oxidation device is arranged between the evaporation device and the oxidation device;
the crystallizing device is positioned at the downstream of the evaporating device and is provided with a concentrated solution conveying pipe communicated with the evaporating device;
a collection device located downstream of the crystallization device;
the method is characterized in that a granular catalyst is bulk-loaded in the oxidation device, and the catalyst is in a free suspension state in a reaction solution in the oxidation device;
and a reflux device communicated with the bottom and the side of the oxidation device is arranged outside the oxidation device and used for pumping the reaction solution at the bottom of the oxidation device to reflux into the device again and stirring the reaction solution.
2. The catalytic oxidation process unit for magnesium sulfite of claim 1, wherein the reflux unit comprises a reflux pipe, a jet pump and a venturi ejector:
the inlet end of the return pipe is communicated with the bottom of the oxidation device;
the jet pump is arranged on the return pipe and is used for pressurizing and accelerating the return liquid;
the top inlet of the venturi ejector is connected with the outlet end of the return pipe, the lateral inlet of the venturi ejector is communicated with the gas delivery pipe, the bottom end of the venturi ejector is provided with a drainage pipe extending into the oxidation device, and air and reflux from the gas delivery pipe are mixed in the venturi ejector and then are introduced into the oxidation device through the drainage pipe.
3. The catalytic oxidation process unit for the magnesium sulfite according to the claim 2, wherein the top of the oxidation unit is provided with a liquid inlet connected with a slurry conveying pipe;
the oxidation device bottom is provided with the first leakage fluid dram of connecting the solution conveyer pipe and the second leakage fluid dram that communicates the back flow entry end, first leakage fluid dram department is provided with first filter, second leakage fluid dram department is provided with the second filter, be provided with the solution filter on the solution conveyer pipe.
4. The catalytic oxidation process unit for the magnesium sulfite of claim 3, wherein the oxidation unit is provided with a heating unit, the heating unit is an electric heating rod, the number of the electric heating rods is three, and the electric heating rods are distributed on the same plane in the oxidation unit at an included angle of 120 degrees.
5. The catalytic oxidation process unit for magnesium sulfite of claim 1, wherein the pulping apparatus comprises a slurry preparation tank and a slurry buffer tank:
the top of the slurry preparation tank is provided with a raw material feeding port, the raw material feeding port is provided with a raw material screen, and the bottom of the slurry preparation tank is provided with a slurry discharge pipe;
the top of the slurry buffer tank is provided with a buffer tank liquid inlet, slurry discharged from the bottom of the slurry preparation tank flows into the slurry buffer tank through the buffer tank liquid inlet, a slurry filter screen is arranged at the liquid inlet of the buffer tank, and the bottom of the slurry buffer tank is communicated with a slurry conveying pipe;
the slurry preparation tank is internally provided with a first stirrer, and the slurry buffer tank is internally provided with a second stirrer.
6. The catalytic oxidation process unit for magnesium sulfite of claim 5, wherein a first exhaust pipe is arranged on the top of the oxidation unit;
a second exhaust pipe is arranged at the top of the evaporation device;
and the first exhaust pipe and the second exhaust pipe are communicated with the slurry preparation groove.
7. The catalytic oxidation process unit for the magnesium sulfite of claim 1, wherein the crystallization devices are arranged in three sets in parallel, and a crystallization stirrer is arranged in each crystallization device;
the crystallization device is characterized in that a filter cylinder corresponding to the crystallization device is arranged in the collection device, a filtrate conveying pipe communicated with the evaporation device is arranged at the bottom of the collection device, a filtrate conveying pump and a heater are arranged on the filtrate conveying pipe, a crystallization mixture flowing out of the bottom of the crystallization device enters the filter cylinder for filtration and separation, magnesium sulfate heptahydrate crystals are collected by the filter cylinder, and filtrate is conveyed into the evaporation device through the filtrate conveying pipe for evaporation and concentration again.
8. The catalytic oxidation process unit for the magnesium sulfite according to any one of claims 1 to 7, wherein the catalyst is a molecular sieve supported catalyst, the supported active components are cobalt nitrate and manganese nitrate, and the molar ratio of cobalt to manganese in the catalyst is 0.5-1.5: 1;
the catalyst is spherical and has a diameter of 2-8 mm.
9. A catalytic oxidation process method for magnesium sulfite, which is characterized by being carried out by using the catalytic oxidation process device as claimed in any one of claims 1 to 8, and comprising the following steps:
s1, slurry preparation: adding a magnesium sulfite raw material and water into a pulping device to prepare a magnesium sulfite slurry, wherein the concentration of the slurry is 30-40%;
s2, catalytic oxidation: feeding the magnesium sulfite slurry prepared in the step S1 into an oxidation device through a slurry conveying pipe, and introducing oxidation air to perform catalytic oxidation reaction to generate a magnesium sulfate solution;
s3, evaporation and concentration: conveying the magnesium sulfate solution generated in the reaction in the step S2 into an evaporation device through a solution conveying pipe, and carrying out evaporation concentration at the temperature of 60-65 ℃ and under normal pressure to obtain a magnesium sulfate concentrated solution;
s4, cooling and crystallizing: conveying the magnesium sulfate concentrated solution obtained in the step S3 into a crystallizing device through a concentrated solution conveying pipe, and naturally cooling and crystallizing for 6-10 hours to obtain a crystallized mixture;
s5, finished product collection: the crystallization mixture from the crystallization apparatus was filtered, separated and dried in a collection apparatus to obtain magnesium sulfate heptahydrate crystals.
10. The catalytic oxidation process method for magnesium sulfite according to claim 9, wherein in step S2, the temperature of the catalytic oxidation reaction is 50-60 ℃ and the pressure is normal pressure;
wherein the volume ratio of the addition amount of the catalyst to the reaction solution is 50-100 g: 1L, and the molar ratio of the usage amount of the magnesium sulfite to the usage amount of air is 1: 2-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911415097.1A CN111054279A (en) | 2019-12-31 | 2019-12-31 | Catalytic oxidation process device and method for magnesium sulfite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911415097.1A CN111054279A (en) | 2019-12-31 | 2019-12-31 | Catalytic oxidation process device and method for magnesium sulfite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111054279A true CN111054279A (en) | 2020-04-24 |
Family
ID=70305693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911415097.1A Pending CN111054279A (en) | 2019-12-31 | 2019-12-31 | Catalytic oxidation process device and method for magnesium sulfite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111054279A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114751475A (en) * | 2022-03-24 | 2022-07-15 | 中国华冶科工集团有限公司 | Desulfurization waste water evaporation and concentration device |
| CN114768498A (en) * | 2022-05-05 | 2022-07-22 | 重庆远达烟气治理特许经营有限公司科技分公司 | Magnesium desulfurization system and method |
| CN116738768A (en) * | 2023-08-14 | 2023-09-12 | 中国恩菲工程技术有限公司 | Modeling method of link unit, generating method, device and medium of link unit |
| CN117160367A (en) * | 2023-08-17 | 2023-12-05 | 山东天润资源综合利用有限公司 | A kind of magnesium sulfite oxidation reaction tower |
Citations (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1179714A (en) * | 1966-05-25 | 1970-01-28 | Rhone Poulenc Sa | Gas-Liquid Contact Apparatus |
| US20040147623A1 (en) * | 2001-05-25 | 2004-07-29 | Front Freide Johannes Helena Maria | Fischer-tropsch process |
| CN2791044Y (en) * | 2004-10-19 | 2006-06-28 | 浙江大学 | Device for producing terephthalic acid |
| CN1846843A (en) * | 2005-01-08 | 2006-10-18 | 戈尔德施米特有限公司 | Equilibrium reactions and gas/liquid reactions in loop reactors |
| CN101035632A (en) * | 2004-09-30 | 2007-09-12 | 埃欧金能量有限公司 | Continuous Flow Pretreatment System with Vapor Recovery |
| CN101434414A (en) * | 2008-12-12 | 2009-05-20 | 嘉兴市环科化工有限公司 | Preparation of polymeric ferric sulfate |
| CN202621147U (en) * | 2012-05-08 | 2012-12-26 | 江苏兄弟维生素有限公司 | Gas-liquid reactor device |
| WO2013023254A1 (en) * | 2011-08-16 | 2013-02-21 | Newamu Ip Holdings Pty Ltd | Method for the recovery of magnesium sulphate and production of magnesium oxide |
| CN103585877A (en) * | 2013-11-28 | 2014-02-19 | 北京世能中晶能源科技有限公司 | System for preparing magnesium sulfate by using slurry obtained after flue gas desulphurization |
| CN103787541A (en) * | 2014-01-24 | 2014-05-14 | 王辛平 | Method and device for recycling wet desulfurization wastewater in thermal power plant |
| CN203648503U (en) * | 2013-12-10 | 2014-06-18 | 华东理工大学工程设计研究院有限公司 | Spray circuit reaction device for gas-liquid-solid three-phase catalytic reaction |
| CN103977832A (en) * | 2014-04-28 | 2014-08-13 | 华北电力大学（保定） | Loaded solid phase metal catalyst for magnesium desulfurization process, and preparation method thereof |
| CN104926008A (en) * | 2014-03-18 | 2015-09-23 | 王辛平 | Wet desulfurization wastewater zero emission process and device thereof |
| CN205528225U (en) * | 2016-03-24 | 2016-08-31 | 武汉凯迪水务有限公司 | Desulfurization waste water zero release processing system |
| CN106277520A (en) * | 2016-08-30 | 2017-01-04 | 河北镁神科技有限公司 | In a kind of carbonizatin method magnesium oxide production process, washings recycle and the method for by-product magnesium ammonium fertilizer |
| JP2017173241A (en) * | 2016-03-25 | 2017-09-28 | 三菱ケミカル株式会社 | Method for measuring density of reaction liquid slurry, method for oxidation reaction, and method for producing aromatic carboxylic acid |
| CN206843088U (en) * | 2017-06-27 | 2018-01-05 | 河北纽思泰伦环保科技有限公司 | Magnesium desulfurization byproduct refines the processing system of epsom salt technique |
| CN109761784A (en) * | 2019-03-04 | 2019-05-17 | 刘禹超 | A kind of industrial process of food-grade benzoic acid |
| CN109772427A (en) * | 2019-02-22 | 2019-05-21 | 浙江大学 | It is a kind of for the catalyst of sulphur nitrogen recycling in magnesium processes simultaneous SO_2 and NO removal technique absorbing liquid and its preparation and application |
| CN110420659A (en) * | 2019-08-15 | 2019-11-08 | 华北电力大学（保定） | A kind of device and method for catalytic oxidation of magnesium sulfite, a kind of cobalt nitrate/ZSM-5 molecular sieve catalyst and preparation method thereof |
| CN212328241U (en) * | 2019-12-31 | 2021-01-12 | 广东雪迪龙环境科技有限公司 | Catalytic oxidation process unit for magnesium sulfite |
-
2019
- 2019-12-31 CN CN201911415097.1A patent/CN111054279A/en active Pending
Patent Citations (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1179714A (en) * | 1966-05-25 | 1970-01-28 | Rhone Poulenc Sa | Gas-Liquid Contact Apparatus |
| US20040147623A1 (en) * | 2001-05-25 | 2004-07-29 | Front Freide Johannes Helena Maria | Fischer-tropsch process |
| CN101035632A (en) * | 2004-09-30 | 2007-09-12 | 埃欧金能量有限公司 | Continuous Flow Pretreatment System with Vapor Recovery |
| CN2791044Y (en) * | 2004-10-19 | 2006-06-28 | 浙江大学 | Device for producing terephthalic acid |
| CN1846843A (en) * | 2005-01-08 | 2006-10-18 | 戈尔德施米特有限公司 | Equilibrium reactions and gas/liquid reactions in loop reactors |
| CN101434414A (en) * | 2008-12-12 | 2009-05-20 | 嘉兴市环科化工有限公司 | Preparation of polymeric ferric sulfate |
| WO2013023254A1 (en) * | 2011-08-16 | 2013-02-21 | Newamu Ip Holdings Pty Ltd | Method for the recovery of magnesium sulphate and production of magnesium oxide |
| CN202621147U (en) * | 2012-05-08 | 2012-12-26 | 江苏兄弟维生素有限公司 | Gas-liquid reactor device |
| CN103585877A (en) * | 2013-11-28 | 2014-02-19 | 北京世能中晶能源科技有限公司 | System for preparing magnesium sulfate by using slurry obtained after flue gas desulphurization |
| CN203648503U (en) * | 2013-12-10 | 2014-06-18 | 华东理工大学工程设计研究院有限公司 | Spray circuit reaction device for gas-liquid-solid three-phase catalytic reaction |
| CN103787541A (en) * | 2014-01-24 | 2014-05-14 | 王辛平 | Method and device for recycling wet desulfurization wastewater in thermal power plant |
| CN104926008A (en) * | 2014-03-18 | 2015-09-23 | 王辛平 | Wet desulfurization wastewater zero emission process and device thereof |
| CN103977832A (en) * | 2014-04-28 | 2014-08-13 | 华北电力大学（保定） | Loaded solid phase metal catalyst for magnesium desulfurization process, and preparation method thereof |
| CN205528225U (en) * | 2016-03-24 | 2016-08-31 | 武汉凯迪水务有限公司 | Desulfurization waste water zero release processing system |
| JP2017173241A (en) * | 2016-03-25 | 2017-09-28 | 三菱ケミカル株式会社 | Method for measuring density of reaction liquid slurry, method for oxidation reaction, and method for producing aromatic carboxylic acid |
| CN106277520A (en) * | 2016-08-30 | 2017-01-04 | 河北镁神科技有限公司 | In a kind of carbonizatin method magnesium oxide production process, washings recycle and the method for by-product magnesium ammonium fertilizer |
| CN206843088U (en) * | 2017-06-27 | 2018-01-05 | 河北纽思泰伦环保科技有限公司 | Magnesium desulfurization byproduct refines the processing system of epsom salt technique |
| CN109772427A (en) * | 2019-02-22 | 2019-05-21 | 浙江大学 | It is a kind of for the catalyst of sulphur nitrogen recycling in magnesium processes simultaneous SO_2 and NO removal technique absorbing liquid and its preparation and application |
| CN109761784A (en) * | 2019-03-04 | 2019-05-17 | 刘禹超 | A kind of industrial process of food-grade benzoic acid |
| CN110420659A (en) * | 2019-08-15 | 2019-11-08 | 华北电力大学（保定） | A kind of device and method for catalytic oxidation of magnesium sulfite, a kind of cobalt nitrate/ZSM-5 molecular sieve catalyst and preparation method thereof |
| CN212328241U (en) * | 2019-12-31 | 2021-01-12 | 广东雪迪龙环境科技有限公司 | Catalytic oxidation process unit for magnesium sulfite |
Non-Patent Citations (2)
| Title |
|---|
| 史利芳: "镁法脱硫副产物亚硫酸镁处理现状", 环境工程, vol. 32, 30 December 2014 (2014-12-30), pages 533 - 536 * |
| 张峰: "镁法脱硫副产物亚硫酸镁处置方式", 山东电力技术, vol. 45, no. 249, 30 December 2018 (2018-12-30), pages 69 - 80 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114751475A (en) * | 2022-03-24 | 2022-07-15 | 中国华冶科工集团有限公司 | Desulfurization waste water evaporation and concentration device |
| CN114751475B (en) * | 2022-03-24 | 2023-09-15 | 中国华冶科工集团有限公司 | Desulfurization waste water evaporation concentration device |
| CN114768498A (en) * | 2022-05-05 | 2022-07-22 | 重庆远达烟气治理特许经营有限公司科技分公司 | Magnesium desulfurization system and method |
| CN116738768A (en) * | 2023-08-14 | 2023-09-12 | 中国恩菲工程技术有限公司 | Modeling method of link unit, generating method, device and medium of link unit |
| CN116738768B (en) * | 2023-08-14 | 2024-01-26 | 中国恩菲工程技术有限公司 | Link unit modeling method, link unit generation method, device and medium |
| CN117160367A (en) * | 2023-08-17 | 2023-12-05 | 山东天润资源综合利用有限公司 | A kind of magnesium sulfite oxidation reaction tower |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111054279A (en) | Catalytic oxidation process device and method for magnesium sulfite | |
| CN105948364A (en) | Desulfurization wastewater zero discharging treatment system based on bypass flue evaporation | |
| CN110171859B (en) | Gypsum Magnetic Seed Scale Inhibition and Scale Removal System and Evaporative Crystallization System | |
| CN103787542B (en) | The wastewater recovery processing technique that a kind of Preparation of Sebacic Acid From Castor Oil produces and device | |
| CN205856232U (en) | A kind of desulfurization wastewater zero-discharge treatment system based on bypass flue evaporation | |
| CN102974188A (en) | Device and method for processing high temperature selenium-containing flue gas | |
| CN212328241U (en) | Catalytic oxidation process unit for magnesium sulfite | |
| CN212370800U (en) | Resourceful and harmless disposal system for low-chlorine fly ash | |
| CN108706557A (en) | A kind of sulfur waste acid-restoring plant and its recovery method | |
| CN202962208U (en) | High-temperature selenium-containing flue gas treatment device | |
| CN213408706U (en) | Furfuryl alcohol dead catalyst processing apparatus | |
| CN211078673U (en) | PTA refined mother liquor processing apparatus based on membrane filtration technology | |
| CN111389038A (en) | Anti-scaling evaporation concentration system and evaporation concentration method | |
| CN214990386U (en) | Resource treatment system for paranitroanisole wastewater | |
| CN213609823U (en) | Even evaporimeter of sulphuric acid | |
| CN212440083U (en) | Mechanically-assisted self-cleaning evaporation concentrator | |
| CN219209495U (en) | Demister flushing system for adjusting water balance of desulfurization system | |
| CN212924461U (en) | A waste sulfuric acid concentration evaporation and scale prevention system | |
| CN111747470A (en) | Waste sulfuric acid concentration evaporation and scale prevention system | |
| CN208995320U (en) | Environment friendly washing Intergration system | |
| CN212924618U (en) | Water quality purification system of fly ash washing liquid | |
| CN113786648A (en) | Electrolytic dehydrogenation device and integrated cabinet type sodium hypochlorite generator for large-scale chlorine production | |
| CN118359324B (en) | A flue gas method low nitrate high magnesium calcium type brine purification system | |
| CN216799033U (en) | Environment-friendly continuous washing device | |
| CN222173616U (en) | Water balance desulfurizing tower system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20250905 |
|
| AD01 | Patent right deemed abandoned |