CN218232020U - Device for treating organic phosphine in glufosinate-ammonium waste salt through photocatalytic degradation - Google Patents
Device for treating organic phosphine in glufosinate-ammonium waste salt through photocatalytic degradation Download PDFInfo
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- CN218232020U CN218232020U CN202222641142.9U CN202222641142U CN218232020U CN 218232020 U CN218232020 U CN 218232020U CN 202222641142 U CN202222641142 U CN 202222641142U CN 218232020 U CN218232020 U CN 218232020U
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Abstract
The application provides a device of organic phosphine in useless salt of photocatalytic degradation processing glufosinate-ammonium, includes: a photocatalytic degradation reaction tank, wherein the photocatalytic degradation reaction tank is filled with glufosinate-ammonium waste salt solution to be degraded; the stirring shaft is arranged in the photocatalytic degradation reaction tank; the stirring paddle is fixed on the stirring shaft; the stirring blade is in a hollow structure and is filled with a solid catalyst; the aeration pipe is arranged in the photocatalytic degradation reaction tank and is used for providing oxygen for photocatalytic degradation reaction; one end of the aeration pipe is communicated with the aeration equipment through an air inlet pipe; and the light source is fixed in the photocatalytic degradation reaction tank. The utility model provides a device of organic phosphine among useless salt of photocatalysis degradation processing glufosinate-ammonium structure simple relatively, the equipment is convenient, can reduce the cost of manufacture, and can realize the high-efficient degradation to organic phosphine among the useless salt solution of glufosinate-ammonium.
Description
Technical Field
The application belongs to the technical field of phosphine-containing waste salt treatment equipment, and more particularly relates to a device for treating organic phosphine in glufosinate-ammonium waste salt through photocatalytic degradation.
Background
Glufosinate belongs to organic phosphorus herbicide, is glutamine synthesis inhibitor, and is non-selective contact herbicide. The glufosinate-ammonium can be used for weeding in orchards, vineyards and uncultivated areas, and can also be used for preventing and removing annual or perennial dicotyledons, gramineous weeds, nutgrass flatsedge and the like in potato fields.
The strecker method is one of common methods for synthesizing glufosinate-ammonium, and a large amount of byproduct glufosinate-ammonium mixed salt can be generated in a production process for preparing glufosinate-ammonium by the strecker method, wherein the glufosinate-ammonium mixed salt contains about 80-85 wt% of ammonium chloride, 15-20 wt% of sodium chloride and a small amount of organic phosphine impurities. CN 2019216997464.7 discloses a separation system of glufosinate-ammonium byproduct mixed salt, which can separate sodium chloride and ammonium chloride in the mixed salt to obtain industrial-grade sodium chloride and ammonium chloride products. After the industrial-grade sodium chloride is prepared into a 25% aqueous solution, 200-300 ppm of organic phosphine impurities still exist, and the industrial-grade sodium chloride brine cannot be used as raw material brine for a chlor-alkali ion membrane method due to the existence of the organic phosphine impurities (the organic matter content in the raw material brine is required to be lower than 5 ppm), so that the organic phosphine impurities in the glufosinate-ammonium waste salt need to be removed.
In the method for removing organic phosphine impurities, a large amount of chemical reagents are consumed in the traditional Fenton oxidation method, chloride ions in waste salt can restrict the oxidation effect and have poor degradation effect on low organic matter content, and the high-temperature calcination method is not economical in the calcination mode of low organic matter content and complex in operation of high-temperature calcination equipment.
The photocatalytic degradation is an efficient organic matter removal method researched at present, for example, chinese patent CN202020603545.2 discloses a photocatalytic degradation system for treating organic matters in printing and dyeing wastewater, which comprises a filter device and a photocatalytic reaction device, wherein an inlet of the filter device is connected with a water supply device for supplying the printing and dyeing wastewater to be treated, an outlet of the filter device is connected with the photocatalytic reaction device through a water inlet pipeline, the photocatalytic reaction device comprises a photocatalytic reaction chamber, an ultraviolet light-emitting device, a photocatalytic composite material degradation layer, a stirring device and a microporous aeration device, the ultraviolet light-emitting device is installed in the middle of the photocatalytic reaction chamber, the photocatalytic composite material degradation layers are sequentially installed in the photocatalytic reaction chamber from top to bottom, the microporous aeration device is arranged at the bottom of the photocatalytic reaction chamber, the top of the photocatalytic reaction chamber is provided with a plurality of spray headers connected with the water inlet pipeline, and a water outlet pipeline with a third valve is arranged on the side surface of the bottom of the photocatalytic reaction chamber. In order to improve photocatalytic degradation efficiency, this patent is through setting up multilayer photocatalytic composite material degradation layer in the photocatalytic reaction indoor, and all is equipped with agitating unit between the adjacent photocatalytic composite material degradation layer. Because the (mixing) shaft respectively is equipped with one in the left and right sides of luminescent light source, and every (mixing) shaft from supreme running through between multilayer photocatalysis composite degradation layer down, need set up a plurality of corresponding through holes on the photocatalysis composite degradation layer that runs through like this, increased the preparation degree of difficulty of photocatalysis composite degradation layer, overall structure is comparatively complicated.
SUMMERY OF THE UTILITY MODEL
An object of this application embodiment is to provide a device of organic phosphine among the photocatalysis degradation processing glufosinate-ammonium waste salt that simple structure, photocatalysis degradation are efficient.
In order to achieve the purpose, the technical scheme adopted by the application is as follows: the utility model provides a device of organic phosphine in useless salt of photocatalysis degradation processing glufosinate-ammonium, includes:
a photocatalytic degradation reaction tank, wherein the photocatalytic degradation reaction tank is filled with glufosinate-ammonium waste salt solution to be degraded;
the stirring shaft is arranged in the photocatalytic degradation reaction tank;
the stirring paddle is fixed on the stirring shaft; the stirring blade is in a hollow structure, and a solid catalyst is filled in the stirring blade;
the aeration pipe is arranged in the photocatalytic degradation reaction tank and used for providing oxygen for photocatalytic degradation reaction; one end of the aeration pipe is communicated with aeration equipment through an air inlet pipe; and
and the light source is fixed in the photocatalytic degradation reaction tank.
Further, the device also comprises a dissolving tank, wherein the dissolving tank is used for containing dissolved glufosinate ammonium waste salt aqueous solution; the dissolving tank is internally provided with a first stirrer, and a discharge port of the dissolving tank is communicated with the photocatalytic degradation reaction tank through a first discharge pipe.
Furthermore, a filter screen is arranged at the discharge port of the dissolving tank.
Furthermore, a slag discharge port is formed in the bottom of the dissolving tank.
Further, the aeration pipe is of a spiral structure, a plurality of air outlet holes are formed in the aeration pipe, and the aeration pipe is arranged at the bottom of the photocatalytic degradation reaction tank.
Furthermore, a plurality of stirring blades are arranged on the stirring shaft.
Further, the light source is provided with a plurality of, a plurality of the light source is evenly arranged on the inner wall of the photocatalytic degradation reaction tank.
Further, the light source is arranged along the height direction of the photocatalytic degradation reaction tank.
Further, the device also comprises an inorganic phosphorus removal reaction tank which is communicated with the photocatalytic degradation reaction tank through a second discharge pipe; the inorganic phosphorus removal reaction tank is filled with a solid phosphorus removal agent.
Further, a second stirrer is arranged in the inorganic phosphorus removal reaction tank.
Compared with the prior art, the method has the following technical effects:
the utility model provides a device of organic phosphine in photocatalysis degradation processing glufosinate-ammonium waste salt is through designing into hollow out construction with the stirring paddle, and it has solid catalyst to pack in the stirring paddle, can realize like this that the stirring paddle drives solid catalyst and rotates in photocatalysis degradation retort simultaneously in the pivoted, the purpose of stirring has not only been reached, pivoted solid catalyst can also promote the abundant contact of glufosinate-ammonium waste salt aqueous solution and solid catalyst and take place the photocatalysis degradation reaction, the realization is to the high-efficient degradation of organic phosphine in the glufosinate-ammonium waste salt, and the device structure of organic phosphine in the photocatalysis degradation processing glufosinate-ammonium waste salt of this application is simple relatively, and convenient for assembly, and can reduce the cost of manufacture.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required to be used in the embodiments or the prior art description will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and for those skilled in the art, other drawings may be obtained according to these drawings without inventive labor.
Fig. 1 is a schematic diagram of an overall structure of an apparatus for treating organic phosphine in glufosinate-ammonium waste salt through photocatalytic degradation according to an embodiment of the present disclosure;
FIG. 2 is a schematic view of the stirring blade of FIG. 1;
fig. 3 is a schematic structural view of the aeration pipe in fig. 1.
Wherein, in the figures, the respective reference numerals:
1. photocatalytic degradation retort, 2, (mixing) shaft, 3, stirring paddle leaf, 4, solid catalyst, 5, aeration pipe, 6, intake pipe, 7, aeration equipment, 8, light source, 9, dissolving tank, 10, first agitator, 11, first discharging pipe, 12, filter screen, 13, row's cinder notch, 14, remove inorganic phosphorus retort, 15, second discharging pipe, 16, solid phosphorus removal agent, 17, second agitator, 501, venthole.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application clearer, the present application is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of and not restrictive on the broad application.
It will be understood that when an element is referred to as being "secured to" or "disposed on" another element, it can be directly on the other element or be indirectly on the other element. When an element is referred to as being "connected to" another element, it can be directly connected to the other element or be indirectly connected to the other element.
It will be understood that the terms "length," "upper," "lower," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in an orientation or positional relationship indicated in the drawings for ease of description and simplicity of description, and do not indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be considered limiting of the present application.
Furthermore, the terms "first", "second", "third", "fourth", "fifth" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, features defined as "first", "second", "third", "fourth", "fifth" may explicitly or implicitly include one or more of the features. In the description of the present application, "a plurality" means two or more unless specifically limited otherwise.
Referring to fig. 1 to fig. 3, a device for treating organophosphines in glufosinate waste salt through photocatalytic degradation according to an embodiment of the present application will be described.
In an embodiment of the present application, an apparatus for treating organophosphines in glufosinate-ammonium waste salt through photocatalytic degradation in the embodiment of the present application includes a photocatalytic degradation reaction tank 1, a stirring shaft 2, a stirring blade 3, an aeration pipe 5 and a light source 8. The photocatalytic degradation reaction tank 1 is filled with a glufosinate ammonium waste salt solution to be degraded, and the stirring shaft 2 is arranged in the photocatalytic degradation reaction tank 1; the stirring paddle 3 is fixed on the stirring shaft 2, and specifically, the stirring paddle 3 and the stirring shaft 2 are in a detachable connection design; the stirring paddle 3 is in a hollow structure, the solid catalyst 4 is filled in the stirring paddle 3, one structure of the stirring paddle 3 is shown in fig. 2, the hollow structure is designed to enable the glufosinate-ammonium waste salt water solution to freely pass through the solid catalyst 4 filled in the stirring paddle, and the solid catalyst 4 can be fully contacted with the glufosinate-ammonium waste salt water solution; the aeration pipe 5 is arranged in the photocatalytic degradation reaction tank 1 and is used for providing oxygen for photocatalytic degradation reaction; one end of the aeration pipe 5 is communicated with an aeration device 7 through an air inlet pipe 6, and the aeration device 7 can be a blower; the light source 8 is fixed in the photocatalytic degradation reaction tank 1, and the light source 8 is a visible light source and can be an explosion-proof xenon lamp.
The glufosinate-ammonium waste salt in the embodiment of the application refers to sodium chloride waste salt obtained by separating glufosinate-ammonium byproduct mixed salt, and the organic phosphine impurity content is 200-300 ppm after the sodium chloride waste salt is prepared into a 25% solution.
The solid catalyst 4 of the embodiment of the present application uses alumina as a carrier, and uses zinc porphyrazine metal compound B and/or compound C as a catalytic active component, and the compound B and the compound C can be prepared by the following methods: dissolving 50g of 2, 3-dibutyl-sulfo-maleonitrile in 300ml of n-butyl alcohol under the protection of nitrogen, slowly dropwise adding the solution into 650ml of n-butyl alcohol solution containing 7.6g of magnesium n-butyl alcohol, adding small-particle iodine, continuously refluxing for 5 hours, after the reaction is finished, evaporating the n-butyl alcohol under reduced pressure to obtain 56g of tetraazaporphyrin magnesium complex, adding the magnesium complex into 500ml of trifluoroacetic acid, continuously stirring for 5 hours under dark conditions, pouring the mixture into ice water after the reaction is finished, extracting with 500ml of dichloromethane, washing an organic phase with saturated saline water, drying with anhydrous sodium sulfate, dissolving a product into 300ml of DMF after the dichloromethane is evaporated under reduced pressure, adding 12g of zinc acetate dihydrate, heating to 120 ℃ under the protection of nitrogen, stirring for 4 hours to stop the reaction, pouring the reaction product into the ice water, separating out a solid, performing suction filtration, washing with water, drying to obtain a crude product, and using ethyl acetate for the mixture: petroleum ether =1 (volume ratio) to perform column chromatography, thereby obtaining 6.5g of compound B and 6.8g of compound C, respectively.
The solid catalyst 4 of the present embodiment can be prepared by the following method: 3g of the compound B or the compound C and 9g of 300 mesh neutral alumina were stirred in 300ml of ethanol for 1 hour, and then the ethanol was distilled off and vacuum-dried for 2 hours to obtain a supported solid catalyst.
The device of organic phosphine among photocatalysis degradation treatment glufosinate-ammonium waste salt of this application embodiment is at the during operation, provide light energy for the reaction through light source 8, provide oxygen for the reaction through aeration pipe 5, under the rotation of (mixing) shaft 2, the waste salt brine of glufosinate-ammonium that treats the degradation of splendid attire stirs in the photocatalysis degradation retort 1 for stirring paddle 3, and promote solid catalyst 4 and the waste salt brine of glufosinate-ammonium that the intussuseption of stirring paddle 3 intussuseption and fully contact, and then realize high-efficient ground photocatalysis degradation reaction.
The device of organic phosphine among the useless salt of a photocatalytic degradation processing glufosinate-ammonium of this application embodiment is through designing into hollow out construction with stirring paddle 3, and it has solid catalyst 4 to fill in stirring paddle 3, can realize stirring paddle 3 and drive solid catalyst 4 and rotate in the photocatalytic degradation retort 1 in step when the pivoted like this, the purpose of stirring has not only been reached, pivoted solid catalyst 4 can also promote the abundant contact of glufosinate-ammonium waste salt aqueous solution and solid catalyst 4 and take place the photocatalytic degradation reaction, the realization is to the high-efficient degradation of organic phosphine in the glufosinate-ammonium waste salt aqueous solution, and the device structure of organic phosphine among the useless salt of a photocatalytic degradation processing glufosinate-ammonium of this application is simple relatively, and convenient for assembly, and can reduce the cost of manufacture.
Further, the device for treating organic phosphine in the glufosinate-ammonium waste salt through photocatalytic degradation in the embodiment of the application further comprises a dissolving tank 9, wherein the dissolving tank 9 is used for containing a dissolved glufosinate-ammonium waste salt water solution; a first stirrer 10 is arranged in the dissolving tank 9, and a discharge port of the dissolving tank 9 is communicated with the photocatalytic degradation reaction tank 1 through a first discharge pipe 11.
Furthermore, a filter screen 12 is arranged at the discharge port of the dissolving tank 9. Insoluble impurities in the glufosinate ammonium waste salt water solution are filtered through a filter screen 12, and the filtered glufosinate ammonium waste salt water solution enters the photocatalytic degradation reaction tank 1 through a first discharge pipe 11.
Furthermore, a slag discharge port 13 is arranged at the bottom of the dissolving tank 9, and insoluble impurities filtered off are discharged through the slag discharge port 13.
Further, aeration pipe 5 is the helical structure, is equipped with a plurality of ventholes 501 on aeration pipe 5, and aeration pipe 5 locates the bottom of photocatalytic degradation retort 1. The aeration pipe 5 is structured as shown in fig. 3, and the spiral structure can make the air coming out from the air outlet 501 more uniformly distributed in the photocatalytic degradation reaction tank 1, promote the photocatalytic degradation reaction and provide the photocatalytic degradation efficiency.
Further, a plurality of stirring blades 3 are provided on the stirring shaft 2. A plurality of stirring paddle 3 evenly arranges along its direction of height in photocatalytic degradation retort 1, can further promote the contact of solid catalyst 4 and the useless salt solution of glufosinate-ammonium like this, promotes photocatalytic degradation efficiency.
Further, the light source 8 is provided in plurality, and the plurality of light sources 8 are uniformly arranged on the inner wall of the photocatalytic degradation reaction tank 1. Further, the light source 8 is disposed along the height direction of the photocatalytic degradation reaction tank 1. Compare in the arrangement mode with light source 8 setting at 1 top of photocatalytic degradation retort, the arrangement mode of this application embodiment can provide surrounding type illumination for the useless salt solution of glufosinate ammonium in the photocatalytic degradation retort 1, promotes going on of photocatalytic degradation reaction, promotes photocatalytic degradation efficiency.
Further, the device for treating organic phosphine in glufosinate-ammonium waste salt through photocatalytic degradation in the embodiment of the application further comprises an inorganic phosphorus removal reaction tank 14, wherein the inorganic phosphorus removal reaction tank 14 is communicated with the photocatalytic degradation reaction tank 1 through a second discharge pipe 15; the inorganic phosphorus removal reaction tank 14 is filled with a solid phosphorus removal agent 16. Further, a second stirrer 17 is provided in the reaction tank 14 except for inorganic phosphorus. After the photocatalytic degradation reaction is completed, the organic phosphine in the glufosinate ammonium waste salt water solution is converted into inorganic phosphorus, the glufosinate ammonium waste salt water solution after the photocatalytic degradation reaction is discharged into the inorganic phosphorus removing reaction tank 14 from the photocatalytic degradation reaction tank 1 through the second discharge pipe 15, and the operation of removing the inorganic phosphorus is further completed under the action of the solid phosphorus removing agent 16. The solid phosphorus removal agent 16 of the embodiment of the present application may use hydrated lime, and remove inorganic phosphorus by using a precipitation reaction between the hydrated lime and the inorganic phosphorus; further, the solid phosphorus removing agent 16 further comprises an auxiliary adsorptive phosphorus removing material, such as attapulgite clay, etc., and impurities such as inorganic calcium phosphate salt, etc., which are not fully precipitated in the waste saline solution, are adsorbed on the solid adsorption material by adsorption to be removed.
The above examples only express several embodiments of the present application, and the description thereof is more specific and detailed, but not to be construed as limiting the scope of the present application. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent application shall be subject to the appended claims.
Claims (10)
1. The utility model provides a device of organic phosphine in useless salt of photocatalytic degradation processing glufosinate-ammonium which characterized in that includes:
the photocatalytic degradation reaction tank is filled with a glufosinate-ammonium waste salt solution to be degraded;
the stirring shaft is arranged in the photocatalytic degradation reaction tank;
the stirring paddle is fixed on the stirring shaft; the stirring blade is in a hollow structure, and a solid catalyst is filled in the stirring blade;
the aeration pipe is arranged in the photocatalytic degradation reaction tank and used for providing oxygen for photocatalytic degradation reaction; one end of the aeration pipe is communicated with aeration equipment through an air inlet pipe; and
and the light source is fixed in the photocatalytic degradation reaction tank.
2. The apparatus for photocatalytic degradation treatment of organophosphines in glufosinate waste salt according to claim 1, further comprising a dissolving tank for containing dissolved glufosinate waste salt water solution; the dissolving tank is internally provided with a first stirrer, and a discharge port of the dissolving tank is communicated with the photocatalytic degradation reaction tank through a first discharge pipe.
3. The apparatus for treating organophosphines in glufosinate-ammonium waste salt through photocatalytic degradation according to claim 2, wherein a filter screen is arranged at the discharge port of the dissolving tank.
4. The apparatus for treating organophosphines in glufosinate waste salt through photocatalytic degradation according to claim 2, wherein a slag discharge port is arranged at the bottom of the dissolving tank.
5. The apparatus according to claim 1, wherein the aerator pipe is in a spiral structure, and a plurality of air outlets are formed in the aerator pipe, and the aerator pipe is disposed at the bottom of the photocatalytic degradation reaction tank.
6. The apparatus for treating organophosphines in glufosinate-ammonium waste salt through photocatalytic degradation according to claim 1, wherein a plurality of stirring blades are arranged on the stirring shaft.
7. The apparatus for treating organophosphines in glufosinate-ammonium waste salt through photocatalytic degradation according to claim 1, wherein a plurality of light sources are provided, and the plurality of light sources are uniformly arranged on the inner wall of the photocatalytic degradation reaction tank.
8. The apparatus for treating organophosphines in glufosinate-ammonium waste salt through photocatalytic degradation according to claim 7, wherein the light source is arranged along the height direction of the photocatalytic degradation reaction tank.
9. The apparatus for treating organophosphines in glufosinate-ammonium waste salt through photocatalytic degradation according to any one of claims 1 to 8, further comprising an inorganic phosphorus removal reaction tank, wherein the inorganic phosphorus removal reaction tank is communicated with the photocatalytic degradation reaction tank through a second discharge pipe; and the inorganic phosphorus removal reaction tank is filled with a solid phosphorus removal agent.
10. The apparatus for treating organophosphines in glufosinate-ammonium waste salt through photocatalytic degradation according to claim 9, wherein a second stirrer is arranged in the inorganic phosphorus removal reaction tank.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202222641142.9U CN218232020U (en) | 2022-09-30 | 2022-09-30 | Device for treating organic phosphine in glufosinate-ammonium waste salt through photocatalytic degradation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202222641142.9U CN218232020U (en) | 2022-09-30 | 2022-09-30 | Device for treating organic phosphine in glufosinate-ammonium waste salt through photocatalytic degradation |
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| CN218232020U true CN218232020U (en) | 2023-01-06 |
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| CN202222641142.9U Active CN218232020U (en) | 2022-09-30 | 2022-09-30 | Device for treating organic phosphine in glufosinate-ammonium waste salt through photocatalytic degradation |
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