阅读说明：本技术 复合型填充材料的填充塔 (Filling tower of composite filling material ) 是由 林国清 许诗韩 穆钰棠 于 2020-04-22 设计创作，主要内容包括：本发明提供了一种复合型填充材料的填充塔。该复合型填充材料的填充塔包括至少一塔体及一复合型填充材料,所述塔体具有一过滤流体入口及一过滤流体出口；所述复合型填充材料,承载于塔体中,用以去除液相或气相中的氧化剂,所述复合型填充材料包括第一氧化剂去除催化剂用以处理氧化剂,以及催化剂再生剂用以活化所述第一氧化剂去除催化剂；当处理的氧化剂溶液pH为3-7时,所述第一氧化剂去除催化剂及所述催化剂再生剂的比例为2:1-8:1,且当处理的氧化剂溶液pH为7-12时,所述第一氧化剂去除催化剂及所述催化剂再生剂的比例为1:1-5.5:1,其中,第一氧化剂去除催化剂为氧化铝、石英砂、天然矿石、碳或其组合。(The invention provides a filling tower made of composite filling materials. The filling tower of the composite filling material comprises at least one tower body and the composite filling material, wherein the tower body is provided with a filtered fluid inlet and a filtered fluid outlet; the composite filling material is borne in the tower body and used for removing an oxidant in a liquid phase or a gas phase, the composite filling material comprises a first oxidant removing catalyst used for treating the oxidant, and a catalyst regenerant used for activating the first oxidant removing catalyst; the ratio of the first oxidant removal catalyst to the catalyst regenerant is from 2:1 to 8:1 when the pH of the treated oxidant solution is from 3 to 7, and from 1:1 to 5.5:1 when the pH of the treated oxidant solution is from 7 to 12, wherein the first oxidant removal catalyst is alumina, silica sand, natural ore, carbon, or a combination thereof.)

1. A packed tower of composite packing material, comprising:

at least one tower having a filtered fluid inlet and a filtered fluid outlet; and

a composite filling material at least loaded in the tower body for removing the oxidant in liquid phase or gas phase, wherein the composite filling material comprises:

a first oxidant removal catalyst for treating the oxidant; and

a catalyst regenerant for activating the first oxidant removal catalyst, wherein the ratio of the first oxidant removal catalyst to the catalyst regenerant is 2:1-8:1 when the pH of the treated oxidant solution is 3-7, and the ratio of the first oxidant removal catalyst to the catalyst regenerant is 1:1-5.5:1 when the pH of the treated oxidant solution is 7-12, wherein the first oxidant removal catalyst is alumina, silica sand, natural ore, carbon, or a combination thereof.

2. A packed column of composite packing material according to claim 1, wherein the first oxidant removal catalyst is configured to treat an oxidant having a concentration of 50ppm to 10000ppm, and the composite packing material further comprises a second oxidant removal catalyst configured to treat an oxidant having a concentration of 10ppm to 4000ppm and the catalyst regenerant is configured to reduce the first oxidant removal catalyst and the second oxidant removal catalyst.

3. The packed tower of composite packing material according to claim 2, wherein the first and second oxidant removing catalysts of the composite packing material are oxidant trapping or decomposing materials.

4. A packed tower of composite filler according to claim 2, wherein the first and second oxidant-removing catalysts are used to capture or decompose ozone, oxygen, hydrogen peroxide, chlorate, perchlorate, potassium dichromate, potassium permanganate, and peroxide.

5. A packed tower of composite packing material according to claim 1, wherein the at least one tower body is a plurality of tower bodies arranged in series with one another.

6. A packed tower of composite packing material according to claim 1, wherein the composite packing material comprises a single layer or a plurality of layers, and the layers are stacked in an orderly manner, randomly, hierarchically arranged according to different particle sizes, or mixed packing according to different particle sizes.

7. A packed column of composite packing material according to claim 2, wherein the second oxidant removing catalyst is selected from the group consisting of carbon, silica sand, silicon, alumina, natural ore, manganese, iron, platinum, palladium, ruthenium, vanadium, chromium, cobalt, copper and nickel, and the catalyst regenerant is selected from the group consisting of carbon, silica sand, silicon, alumina, natural ore, manganese, iron, platinum, palladium, ruthenium, vanadium, chromium, cobalt, copper and nickel, and a component containing manganese heptaoxide, potassium permanganate or iron oxide in the matrix.

8. The packed tower of composite packing material according to claim 1, wherein the composite packing material is granular or spherical and has a grain size or diameter of 0.5mm to 10cm, or the composite packing material is brick-shaped, plate-shaped or columnar and has a side length of 0.1mm to 100 cm.

9. A packed tower of composite packing material according to claim 1, wherein the composite packing material comprises two layers, in order from the inlet to the outlet, a first packing layer and a second packing layer, wherein the material size of the first packing layer is smaller than the material size of the second packing layer.

10. A packed tower of composite packing material according to claim 1, wherein the composite packing material comprises at least three layers, in order from the inlet to the outlet of the filtered fluid, of a first packing layer, a second packing layer and a third packing layer, wherein the material size of the first packing layer is smaller than the material size of the second packing layer, and the material size of the second packing layer is smaller than the material size of the third packing layer.

Technical Field

The present invention relates to a packed tower of composite packing material, and more particularly, to a packed tower of composite packing material including an oxidant removing catalyst and a catalyst regenerant.

Background

The packed tower is a mass transfer device commonly used in chemical production, mainly consists of a cylindrical tower body and packing materials arranged in the tower, and is commonly used for filtration, absorption, distillation, extraction and the like. However, in the chemical production process, an oxidant is often added for reaction, and after the reaction is completed, the residual oxidant is difficult to remove.

In addition, the oxides generated from the combustion of exhaust gas from a steam engine, plant exhaust gas, and chemical-containing fumes, and the chemical reaction of sunlight, generate environmental ozone pollutants which are also difficult to remove. The ozone has far stronger reaction activity than oxygen, belongs to a strong oxidant and is harmful to animals, plants and a plurality of structural materials such as plastics and rubber.

Therefore, it is a common effort objective of the related industries to develop a packed tower capable of effectively removing liquid or gas phase oxidant components, which can be applied in chemical production processes or living environments.

Disclosure of Invention

The invention relates to a filling tower of a composite filling material, which utilizes an oxidant to remove a catalyst treatment oxidant, and utilizes a catalyst regenerant to activate and regenerate the oxidant to remove the catalyst so as to effectively remove the oxidant. The present invention includes the following aspects:

according to an aspect of the present invention, there is provided a packed tower of composite packing material, the packed tower of composite packing material comprises at least a tower body and a composite packing material, the tower body has a filtered fluid inlet and a filtered fluid outlet, the composite packing material is carried in the tower body for removing an oxidant in a liquid phase or a gas phase; the composite filling material comprises a first oxidant removal catalyst for treating an oxidant and a catalyst regenerant for activating the first oxidant removal catalyst; the ratio of the first oxidant removal catalyst to the catalyst regenerant is from 2:1 to 8:1 when the pH of the treated oxidant solution is from 3 to 7, and from 1:1 to 5.5:1 when the pH of the treated oxidant solution is from 7 to 12, wherein the first oxidant removal catalyst is alumina, silica sand, natural ore, carbon, or a combination thereof.

In the packed tower of the composite packing material, preferably, the first oxidant removing catalyst is used for treating an oxidant with a concentration of 50ppm to 10000ppm, and the composite packing material further comprises a second oxidant removing catalyst which is used for treating an oxidant with a concentration of 10ppm to 4000ppm, and the catalyst regenerant is used for reducing the first oxidant removing catalyst and the second oxidant removing catalyst.

In the packed column of composite packing material described above, preferably, the first oxidant removal catalyst and the second oxidant removal catalyst of the composite packing material are oxidant trapping or decomposing materials.

In the packed tower of the composite packing material, preferably, the first and second oxidant removal catalysts are used to capture or decompose ozone, oxygen, hydrogen peroxide, chlorate, perchlorate, potassium dichromate, potassium permanganate, and peroxide.

In the above-mentioned packed tower of composite packing material, preferably, the at least one tower body is a plurality of tower bodies arranged in series with each other.

In the packed tower of the composite packing material, preferably, the composite packing material comprises a single layer or a plurality of layers, and the layers are stacked in a manner of orderly stacking, randomly stacking, layering according to different particle sizes or mixed packing according to different particle sizes.

In the packed column using the composite packing material, the second oxidant-removing catalyst is preferably selected from the group consisting of carbon, silica sand, silicon, alumina, natural ore, manganese, iron, platinum, palladium, ruthenium, vanadium, chromium, cobalt, copper, and nickel, and the catalyst regenerant is preferably selected from the group consisting of carbon, silica sand, silicon, alumina, natural ore, manganese, iron, platinum, palladium, ruthenium, vanadium, chromium, cobalt, copper, and nickel, and a component containing manganese heptaoxide, potassium permanganate, or iron oxide in the base material.

In the packed tower of the composite packing material, preferably, the composite packing material is granular or spherical and has a grain size or diameter of 0.5mm to 10cm, or the composite packing material is brick-shaped, plate-shaped or columnar and has a side length of 0.1mm to 100 cm.

In the packed column of composite packing material, preferably, the composite packing material includes two layers, namely, a first packing layer and a second packing layer in sequence from the filtered fluid inlet to the filtered fluid outlet, wherein the material size of the first packing layer is smaller than that of the second packing layer.

In the packed tower of composite packing material, preferably, the composite packing material includes at least three layers, which are a first packing layer, a second packing layer and a third packing layer in sequence from the filtered fluid inlet to the filtered fluid outlet, wherein the material size of the first packing layer is smaller than that of the second packing layer, and the material size of the second packing layer is smaller than that of the third packing layer.

Drawings

FIG. 1 is a schematic view of a single packed column according to an embodiment of the present invention.

Fig. 2 is a schematic view of a packed tower with two packed layers according to an embodiment of the invention.

FIG. 3 is a schematic view of a packed tower with three packed layers according to an embodiment of the present invention.

Description of the symbols

10. 20, 30: filling tower

100. 200 and 300: tower body

102: composite filling material

202. 302: first filling layer

204. 304: second filling layer

306: third filling layer

F: filtered fluid inlet

O: filtered fluid outlet

Detailed Description

Fig. 1 is a schematic view of a single packed-layer packed tower according to an embodiment of the invention. As shown in fig. 1, the packed tower 10 includes a tower body 100 and a composite packing material 102. The tower 100 has a filtered fluid inlet F and a filtered fluid outlet O. The composite filling material 102 is supported in the tower body 100 and is used for removing the oxidant in the liquid phase or the gas phase. The composite filling material 102 may be stacked in order, randomly, in layers with different particle sizes, or mixed with different particle sizes. The length to width ratio of the tower 100 may be 0.1-1.5 (diameter/height), preferably 1.0-1.5.

In one embodiment, the composite filler material 102 includes a first oxidant removal catalyst and a catalyst regenerant. The first oxidant removing catalyst is an oxidant trapping or decomposing material, and can be used for treating, for example, an oxidant having a high concentration, preliminarily removing impurities such as the oxidant by structural properties, and treating an oxidant having a concentration of, for example, 50ppm to 10000ppm at a reaction rate k (oxidant concentration) by chemical reactivityⁿ(catalyst concentration)^mAnd 5 is>n,m>0. Depending on the catalytic material used, there may be different reaction pathways which influence the order of the reaction rates and/or the value of the rate constant k. The reaction rate of the oxidant removed by the first oxidant removal catalyst is related to the material size of the oxidant removal catalyst and the pore size of the porous material. The first oxidant removal catalyst may be a single material or a combination of materials, has a reduced activation energy of the oxidant, and catalyzes the reaction to proceed. In particular, one or more reaction pathways may be catalyzed to achieve an increase in overall reaction rate. The chemical treatment is to remove the surface of the catalyst with the oxidant to adsorb or bind the oxidant, thereby providing different reaction paths for the oxidant, in this case, providing a low activation energy path to increase the decomposition rate of the oxidant. The activation and regeneration of the oxidant removal catalyst is by a catalyst regenerant or other regeneration or activation procedure such as heat treatment or addition of a reducing agent.

In one embodiment, the first oxidant removal catalyst can adsorb or decompose a compound selected from the group consisting of ozone, oxygen, hydrogen peroxide, chlorate, perchlorate, potassium dichromate, potassium permanganate, and peroxide, such as carbon (activated carbon, coconut carbon, charcoal, coal, and upgraded carbon) in a ratio of 5% to 99% or preferably 10% to 80% or most preferably 30% to 75%, silicon (in a ratio of 5% to 99%, 10% to 80%, or 15% to 60%), alumina (in a ratio of 5% to 99% or preferably 10% to 95% or most preferably 30% to 90%), natural minerals (e.g., zeolite), manganese, iron, platinum, palladium, ruthenium, vanadium, chromium, cobalt, copper, and nickel, wherein the metal content of manganese, iron, platinum, palladium, ruthenium, vanadium, chromium, cobalt, copper, and nickel is 0.5% to 80% or preferably 1% to 70% or most preferably 1% to 50% And includes the oxidized form thereof. The catalyst regenerant is, for example, a base material selected from the above-mentioned materials (carbon, quartz sand, silicon, alumina, natural ore (e.g., zeolite), manganese, iron, platinum, palladium, ruthenium, vanadium, chromium, cobalt, copper, and nickel), and contains a component having a high oxidation potential such as manganese heptaoxide, potassium permanganate, or iron oxide.

The proportion of the first oxidant removing catalyst and the catalyst regenerating agent can be adjusted according to the type and concentration of the oxidant to be removed, and the proportion is 0.1:1-99: 1. Further, when the oxidant to be removed is hydrogen peroxide, the interval of the first oxidant removing catalyst and the catalyst regenerating agent with the ratio of 1:1-99:1 has better reactivity, but when the ratio of the first oxidant removing catalyst and the catalyst regenerating agent is 4:1, the optimal use condition is provided. In another embodiment, when the pH of the treated oxidant solution is less than 7 and the concentration of hydrogen peroxide is 8000ppm, the ratio of the first oxidant to the catalyst removal agent and the catalyst regeneration agent is 1:1-9:1, and the optimal service life is achieved. When the pH value of the treated oxidant solution is more than 7 and the concentration of hydrogen peroxide is 8000ppm, the ratio of the first oxidant removal catalyst to the catalyst regenerant is 0.5:1-6:1, and the catalyst has the best service life. In another embodiment, the ratio of the first oxidant-removal catalyst to the catalyst regenerant is from 2:1 to 8:1 when the pH of the treated oxidant solution is from 3 to 7, and the ratio of the first oxidant-removal catalyst to the catalyst regenerant is from 1:1 to 5.5:1 when the pH of the treated oxidant solution is from 7 to 12, which is effective in removing fluoride ions and silica.

In a preferred embodiment, when the pH of the treated oxidant solution is 10, the first oxidant removal catalyst and the catalyst regenerant can reduce the silica content from 1000ppm at a ratio of 7:3 to 0.75-5ppm and the fluoride ion content from 500ppm at 150 to 10-40 ppm.

Experimental data for hydrogen peroxide removal efficiency when the height of the packed column was about 110 centimeters (cm) and the pH of the treated oxidant solution was between 4 and 10 are shown in table 1. The removal efficiency of the hydrogen peroxide solution in the embodiment a and the embodiment B reaches 99%, and the residue of the hydrogen peroxide solution cannot be detected. The hydrogen peroxide removal efficiency of the embodiment C reaches 95%, and it is obvious that the composite filling material provided by the embodiment of the invention has an excellent removal effect.

TABLE 1

Examples	Composite filling material	Concentration of hydrogen peroxide	Residence time	Outlet concentration	Removal efficiency
						A	Zeolite/alumina/iron/manganese	2000ppm	3.5 minutes	0ppm	99％
B	Zeolite/alumina/iron/manganese	4000ppm	3.5 minutes	0ppm	99％
						C	Zeolite/alumina/iron/manganese	8000ppm	3.5 minutes	<100ppm	95％

In one embodiment, the composite filler material 102 further comprises a second oxidizer removal catalyst for treating an oxidizer having a concentration of 10ppm to 4000ppm, wherein the reaction rate and the treatment concentration of the second oxidizer removal catalyst are related to the selected component ratios, pore sizes, and particle sizes. For example, the small particle size with larger pores can help to increase the contact of the oxidant with the surface of the material for adsorption and removal, and the reaction by-product such as oxygen stays in the interior of the voids for a shorter time, which is advantageous to increase the reaction per unit time, the reaction rate is k (oxidant concentration)^a(catalyst concentration)^bWherein 5 is>a,b>0. Depending on the catalytic material used, there may be different reaction pathways which influence the order of the reaction rates and/or the value of the rate constant k. The reaction rate of the second oxidant for removing the oxidant is related to the size of the material of the oxidant for removing the catalyst and the pore diameter of the porous material. The catalyst regenerant may be used to reduce (activate or regenerate) the first oxidant to remove the catalystThe agent and the second oxidant removing catalyst can recover the activity of the first and second oxidant removing catalysts by reduction of the regenerating agent when the first and second oxidant removing catalysts age or lose effectiveness due to repeated use, without taking out the first and second oxidant removing catalysts from the packed tower 10 or replacing them, thereby increasing the service life of the packed tower 10.

In one embodiment, both the first and second oxidizer removal catalysts react at any concentration of oxidizer, but the first and second oxidizer removal catalysts have different material designs (e.g., structural strength, pore size, etc.) and may exhibit different actual reaction rates at different concentrations. For example, the first oxidant removing catalyst (material a) may be selected from materials with hard structure suitable for directly contacting with high concentration oxidant, but the holes thereof reduce the overall reaction efficiency due to the occupation of by-products generated after the reaction, so that the treated oxidant is reduced from 10000ppm to 4000ppm, and at this time, the second oxidant removing catalyst may be selected from material B which has a structure weaker than that of material a but has a lighter weight or smaller particles, and the residual oxidant is continuously treated.

In one embodiment, the composite filler material 102 may include a first and second oxide removal catalyst selected from the group consisting of carbon, silica sand, silicon, alumina, natural minerals (e.g., zeolites), manganese, iron, platinum, palladium, ruthenium, vanadium, chromium, cobalt, copper, and nickel, which may be in any form of fine sand, granular, spherical, irregular, brick, plate, pillar, honeycomb, porous materials, or a combination of different forms. And the composite filling material 102 is granular or spherical and has a grain diameter or diameter of 0.5mm-10cm, or the composite filling material 102 is brick-shaped, plate-shaped or columnar and has a side length of 0.1mm-100 cm. The composite filler 102 may be used as a catalyst to treat an oxidizing agent, and may have a physical filtering effect, so that fine particles having a particle size of 1 μm or more can be removed depending on the size, particle diameter, or structure of the filler.

In an embodiment, the packed tower may include a plurality of tower bodies connected in series, the arrangement may be adjusted according to the type of the oxidant to be actually filtered, and the appropriate composition may be adjusted according to the concentration of the oxidant at the outlet of each packed tower, for example, if the concentration of hydrogen peroxide in the first packed tower is 8000ppm and the residue is less than 4000ppm after removal, the second packed tower may use the second oxidant removal catalyst with a high percentage ratio to remove hydrogen peroxide.

In one embodiment, the filling layer of the composite filling material 102 may also be formed by mixing and filling materials with different sizes and spacing according to the requirement.

Fig. 2-3 are schematic diagrams of a packed tower with two and three packed layers according to an embodiment of the invention. Referring to fig. 2, the packed tower 20 includes a tower body 200, a first packing layer 202, and a second packing layer 204 supported in the tower body 200 for removing the oxidant in liquid phase or gas phase. The tower 200 has a filtered fluid inlet F and a filtered fluid outlet O. The stacking mode of each layer comprises orderly stacking, random stacking, layered arrangement according to different particle sizes or mixed filling of different particle sizes. The material of the first filling-up layer 202 may be one or a mixture of the first oxide removal catalyst and the second oxide removal catalyst, and the material of the second filling-up layer 204 may be one or a mixture of the first oxide removal catalyst and the second oxide removal catalyst. The materials of the first filling layer 202 and the second filling layer 204 may be the same or different, and the materials of the first oxide removal catalyst and the second oxide removal catalyst are selected as described above, and will not be described herein again. In one embodiment, the material size of the first filling-up layer 202 is smaller than the material size of the second filling-up layer 204.

Referring to fig. 3, the packed tower 30 includes a tower body 300, a first packed layer 302, a second packed layer 304, and a third packed layer 306, which are supported in the tower body 300 for removing the oxidant in the liquid phase or the gas phase. The tower 300 has a filtered fluid inlet F and a filtered fluid outlet O. The stacking mode of each layer comprises orderly stacking, random stacking, layered arrangement according to different particle sizes or mixed filling of different particle sizes. The materials of the first filling layer 302, the second filling layer 304 and the third filling layer 306 may be any one or a mixture of a first oxide removal catalyst and a second oxide removal catalyst, and the materials of the first filling layer 302, the second filling layer 304 and the third filling layer 306 may be the same or different, and the materials of the first oxide removal catalyst and the second oxide removal catalyst are selected as described above, and will not be described again. In one embodiment, the material size of the first filling-up layer 302 is smaller than the material size of the second filling-up layer 304, and the material size of the second filling-up layer 304 is smaller than the material size of the third filling-up layer 306.

In one embodiment, the composite filler material 102 is porous, which increases the surface area and improves the efficiency of treating the oxidant. The sizes of the porous composite filling materials are arranged from small to large in the direction from the filtering fluid inlet F to the filtering fluid outlet O, so that the size of the porous composite filling material filled at the upper part of the tower body closer to the filtering fluid inlet F is smaller, for example, a first oxidant with the size of 0.6mm-1.5mm removes a catalyst, particles with the size of more than 3 microns can be preliminarily filtered, when the porous composite filling material reacts with the oxidant, the oxidant to be treated can permeate into pores of the porous material and be adsorbed or react inside, when the particle size is smaller, the path of gas generated by reaction escaping from the inside of the pores of the material is shortest, the residence time is also shorter, the reaction rate is fastest, and the material structure damage caused by the fact that the pores are opened by gas expansion can be reduced. The porous composite filling material filled at the lower part of the tower body, which is closer to the filtering fluid outlet O, has larger size, for example, the second oxidant with the size of 1mm-10mm removes the catalyst, the gas escape path is longer when reacting with the oxidant, and the reaction rate is slowest. Therefore, the high-concentration oxidant can be treated in the first stage, the concentration of the oxidant can be reduced, when the fluid enters the second stage and then enters the second stage to treat the low-concentration oxidant, namely when the filtered fluid enters the rear section of the tower body to remove the residual oxidant, the oxidant required to be treated is reduced, and the phenomenon that when medium and large particles directly treat the high-concentration oxidant, the oxidant enters the holes to react to generate gas and damage the structure of the porous composite filling material is avoided.

In addition, by reverse washing, that is, by reversing the tower body and washing the tower body with the cleaning liquid from the filtering fluid outlet O to the filtering fluid inlet F, small particles and blocked impurities can be washed away, thereby removing the dirt and prolonging the service life of the packed tower. In addition, when the packed column is used for a period of time, the composite packing materials 102 having various particle sizes can be directly supplied through the upper portion (region of the filtered fluid inlet F) of the column body, and then the composite packing materials 102 can be rearranged to obtain a small-to-large arrangement of the composite packing materials 102 in the direction from the filtered fluid inlet F to the filtered fluid outlet O by passing through the rapid reverse-flow lift bed. If the porous composite filling material is damaged and becomes small-size particles, the particles can be rearranged through backwashing, and the filling area of the middle and upper layers can be replenished to be used as the supplement of the small-size porous composite filling material. The above-described back washing embodiment is applicable to a structure in which the packed column has two or more packed layers.

In summary, the present invention provides a packed tower of composite packing material, which uses an oxidant to remove the catalyst treatment oxidant, and uses a catalyst regenerant to activate and regenerate the oxidant to remove the catalyst, so as to effectively remove the oxidant in a liquid phase or a gas phase, and also filter impurity particles, and the removal efficiency reaches 80% to 99%.