CN112295386B - Activating agent for manganese dioxide generated in styrene waste gas treatment and application thereof - Google Patents
Activating agent for manganese dioxide generated in styrene waste gas treatment and application thereof Download PDFInfo
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- CN112295386B CN112295386B CN201910712808.5A CN201910712808A CN112295386B CN 112295386 B CN112295386 B CN 112295386B CN 201910712808 A CN201910712808 A CN 201910712808A CN 112295386 B CN112295386 B CN 112295386B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
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- B01D2251/10—Oxidants
Abstract
The invention discloses an activating agent for manganese dioxide generated in styrene waste gas treatment and application thereof, belonging to the technical field of styrene waste gas treatment. The technical scheme is as follows: the activating agent comprises A, B two components, wherein the component A is inorganic acid, the component B is inorganic acid salt or organic acid salt, and the mixture ratio of the component A to the component B is 100 parts of the component A and 5-40 parts of the component B in parts by mass; manganese dioxide in potassium permanganate oxidation solution is filtered out, and the activating agent is added for activation. The method takes the potassium permanganate as the oxidant, activates the manganese dioxide generated after the styrene waste gas is oxidized, improves the oxidation performance of the manganese dioxide, returns the manganese dioxide to be used as the oxidant together with the potassium permanganate, generates the synergistic effect of the activated manganese dioxide and the potassium permanganate, changes waste into valuable, and avoids the generation of solid slag.
Description
Technical Field
The invention relates to the technical field of styrene waste gas treatment, in particular to an activating agent for manganese dioxide generated in styrene waste gas treatment and application thereof.
Background
The styrene monomer is active in chemical property, is an important polymerized monomer, can be polymerized by itself or with other monomers, and is widely applied to the fields of synthetic high polymer materials, coatings, medicines and the like. Styrene can undergo a slow thermally-activated polymerization at ambient temperature. In the exhaust gas treatment, styrene belongs to volatile organic compounds and malodorous gases. Volatile Organic Compounds (VOCs) are a large class of organic waste gases, usually referred to as ambient temperatureOrganic compound with saturated vapor pressure higher than 70Pa and boiling point lower than 260 deg.C under normal pressure. Mainly comprises hydrocarbons, benzene and derivatives thereof, phenol and derivatives thereof, alcohols, aldehydes, ketones and the like. Styrene belongs to typical monocyclic aromatic VOCs, and generates toxicity and carcinogenicity to human mucosa, liver, kidney, lung and nervous system through respiration. The emission standard GB 31571-2015 of the pollutants for the petrochemical industry, which is implemented from 7.1.2017, clearly limits that the emission concentration of the styrene does not exceed 50mg/m3。
In the processes of production, storage and loading of styrene, along with the rise of the liquid level of a product storage tank, the volume of a gas space is gradually reduced, oil gas is gradually discharged, factors such as process equipment and the like are added, the condition of external leakage of waste gas also exists in actual operation, the content of styrene in the tail gas of loading and the direct exhaust of a production device can not reach the discharge standard specified by the state, the styrene needs to be recycled, and the problem of environment pollution caused by waste gas is fundamentally solved.
The common treatment methods for volatile organic compounds include absorption, adsorption, oxidation, condensation, combustion, and membrane separation, and the methods for recovering valuable organic compounds from waste gas generally employ condensation, adsorption, oxidation, membrane separation, or their combination methods. Because of the difficult problem of easy polymerization in the styrene waste gas treatment process, most of the styrene waste gas generated in the styrene storage and transportation process of the existing refinery enterprises is directly discharged without treatment, pollutes the environment and has huge hidden troubles.
CN201510770073.3 discloses a styrene waste gas treatment method, in which styrene waste gas and an alkaline solution of potassium permanganate are in countercurrent contact in an absorption tower provided with a packing layer, during the contact process, styrene and the alkaline solution of potassium permanganate undergo an oxidation reaction, and after the reaction is completed, the waste gas which consumes styrene is discharged into the atmosphere. In the patent, the styrene waste gas is oxidized by using the alkaline solution of potassium permanganate, and a by-product manganese dioxide generated in the oxidation process has no treatment method, so that pipelines are easy to block, waste residues are generated, and secondary pollution is caused.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an activating agent for manganese dioxide generated in the treatment of styrene waste gas and the application thereof in the treatment of styrene waste gas, potassium permanganate is taken as an oxidizing agent, the manganese dioxide generated after the styrene waste gas is oxidized is activated, the oxidation performance of the manganese dioxide is improved, and then the activated manganese dioxide and the potassium permanganate are returned to be used as the oxidizing agent together, so that the activated manganese dioxide and the potassium permanganate generate a synergistic effect, the waste is changed into valuable, the generation of solid slag is avoided, the consumption of the potassium permanganate is effectively reduced, the problems of low oxidizing capability and secondary pollution of the manganese dioxide in the treatment of the styrene waste gas by the conventional potassium permanganate are solved, the process steps are few, and the process is economical and feasible.
The technical scheme of the invention is as follows:
the activator for manganese dioxide generated in styrene waste gas treatment comprises A, B two components, wherein the component A is inorganic acid, the component B is inorganic acid salt or organic acid salt, and the mixture ratio of the component A to the component B is 100 parts of the component A and 5-40 parts of the component B in parts by mass.
Further, the component A is one or a mixture of more of phosphoric acid, nitric acid and sulfuric acid, and the component B is one of phosphate, triphenylphosphine and diphenylphosphine.
Further, the component A is phosphoric acid.
Further, the paint also comprises 1-35 parts of a component C, wherein the component C is an alkoxy phenol compound.
Further, the component C is one or a mixture of more of 3-tert-butyl-4-hydroxymethoxyphenol, 3-tert-butyl-4-hydroxyethoxyphenol, 2, 6-di-tert-butyl-4-methoxyphenol and p-tert-butylcatechol.
Further, the component A is nitric acid, the component B is triphenylphosphine, and the component C is p-tert-butyl catechol.
Further, the component A is phosphoric acid, the component B is potassium phosphate, and the component C is 3-tert-butyl-4-hydroxyethoxyphenol.
Further, the proportion of the component A, the component B and the component C is 100 parts of the component A, 5-30 parts of the component B and 5-25 parts of the component C.
Further, the solvent and the dispersant are polyhydric alcohols, alcohol ether compounds or alkylbenzene compounds, such as ethylene glycol, propylene glycol, glycerol, ethylene glycol monobutyl ether, toluene and ethylbenzene.
The invention also provides an activation method of manganese dioxide generated in styrene waste gas treatment, which comprises the following steps: firstly, filtering manganese dioxide in potassium permanganate oxidation solution, adding an activating agent comprising A, B components for activation, wherein the component A is inorganic acid, the component B is inorganic acid salt or organic acid salt, the mixture ratio of the component A and the component B is 100 parts of the component A and 5-40 parts of the component B in parts by mass, and the weight ratio of the adding amount of the activating agent to the manganese dioxide is (1-10): 1, the activation temperature is 40-90 ℃, and the activation time is 10-60 min.
Further, the weight ratio of the addition amount of the activating agent to the manganese dioxide is (1-5): 1.
further, after activation, 1-35 parts of component C is added and fully and uniformly mixed, wherein the component C is an alkoxy phenol compound.
Further, the component C is one or a mixture of more of 3-tert-butyl-4-hydroxymethoxyphenol, 3-tert-butyl-4-hydroxyethoxyphenol, 2, 6-di-tert-butyl-4-methoxyphenol and p-tert-butylcatechol.
Or adding small amount of polyhydric alcohol or alcohol ether compound such as ethylene glycol monobutyl ether to play a role of solvent and dispersion, wherein the adding amount is not more than 30% of the total amount of the three components A, B, C, and adding the mixture into the potassium permanganate solution after mixing.
The component A is a main activator, the component B is an auxiliary activator, impurities in manganese dioxide are removed under the synergistic effect of the component A, B, the refining effect is achieved, the oxidation effect of the manganese dioxide is enhanced, the manganese dioxide can be used as an oxidant, waste is changed into valuable, solid slag is avoided, the oxidation reaction forms closed loop, and the environment-friendly treatment process is realized. The component C is used as an auxiliary oxidant and is compounded with activated manganese dioxide and potassium permanganate, so that the oxidation efficiency can be effectively improved.
In addition, the invention also provides a treatment method of the styrene waste gas, which comprises the following steps:
(1) the styrene waste gas enters an oxidation reaction system comprising an oxidation reaction tower, a liquid storage tank, a filter press, an activator and a water washing tower, a glass fractionating column is used as the oxidation reaction tower, and a flask is used as the liquid storage tank; the upper end of the oxidation reaction tower is provided with an air outlet, an oxidation liquid feeding port and a circulating liquid feeding port, the lower end of the oxidation reaction tower is provided with an air inlet and a discharging port, and the discharging port is connected with a liquid storage tank; styrene waste gas enters from a gas inlet at the lower end of the oxidation reaction tower and is in countercurrent contact with potassium permanganate oxidizing solution entering from the upper end to complete the oxidation reaction, and the reacted styrene waste gas is discharged from a gas outlet at the upper end; the reacted potassium permanganate solution enters a liquid storage tank from a discharge hole at the lower end, part of the potassium permanganate solution in the liquid storage tank is discharged, and part of the potassium permanganate solution is circulated to a circulating liquid feed hole at the upper end of an oxidation reaction tower through a mechanical diaphragm pump and is in countercurrent contact with styrene waste gas entering from the lower end of the oxidation reaction tower again to complete oxidation reaction, so that the oxidation efficiency is improved, and the consumption of the potassium permanganate is reduced;
(2) and pumping half of the potassium permanganate solution from the liquid storage tank every 24 hours, filtering the potassium permanganate solution by using a filter press to obtain filtrate and filter residue manganese dioxide, introducing the manganese dioxide into an activator, activating the manganese dioxide according to the activation method, introducing the activated manganese dioxide into the liquid storage tank to be mixed with the filtrate, then adding the component C to be fully and uniformly mixed, and merging the mixed filtrate into an external circulation line to enter an oxidation reaction tower through a circulation liquid feed inlet.
(3) The styrene waste gas discharged from the upper end of the oxidation reaction tower enters the water washing tower from the lower inlet through the pipeline, water enters from the top upper inlet, is in countercurrent contact with the styrene waste gas, is subjected to external circulation, further removes the styrene waste gas and entrained little high-potassium permanganate solution, avoids secondary pollution, and the styrene waste gas after the reaction is finished is discharged from the gas outlet at the top of the water washing tower, so that the standard discharge can be realized.
In the oxidation reaction process, the potassium permanganate solution is contacted with the styrene waste gas, most of the styrene waste gas is firstly dissolved or attached in the solution to become liquid-phase styrene, and then the liquid-phase styrene is oxidized; adding the component C, oxidizing the hydrogen of the phenolic hydroxyl group into a more stable semiquinone type free radical, and quenching a more active free radical; further oxidized to more stable quinones, which in turn quench a more reactive radical. That is, the polymerization of the styrene is free radical polymerization, and after the component C is added, the active free radical is quenched, so that the purpose of inhibiting the free radical polymerization can be achieved, and the polymerization inhibition effect is achieved, so that the styrene is oxidized before the polymerization, the polymerization loss is reduced, and the oxidation efficiency is improved.
Furthermore, in the step (1), the ratio of the circulation amount to the discharge amount of the potassium permanganate solution is (0.5-10): 1, the length-diameter ratio of the oxidation reaction tower is (10-30): 1, the concentration of the potassium permanganate solution is 6% -15%, the oxidation reaction temperature is 20 ℃ -50 ℃, and the volume ratio of the styrene waste gas to the potassium permanganate solution is (10-100): 1.
Further, in the step (1), the length-diameter ratio of the oxidation reaction tower is (10-15): 1, the concentration of the potassium permanganate solution is 7% -10%, the oxidation reaction temperature is 25 ℃ -50 ℃, and the volume ratio of the styrene waste gas to the potassium permanganate solution is (20-70): 1.
Further, in the step (3), the length-diameter ratio of the water washing tower is (5-10): 1, the water washing temperature is 20-60 ℃, and the volume ratio of the water circulation amount to the styrene waste gas is (1-50): 1.
Furthermore, in the step (3), the washing temperature is 25-45 ℃, and the volume ratio of the water circulation amount to the styrene waste gas is (1-30): 1.
Furthermore, in the step (3), the volume ratio of the water circulation volume to the styrene waste gas is (5-20): 1.
Further, in the step (1), a distributor is arranged in the oxidation reaction tower every 2-20 cm in height, small holes with the diameter of 1-3 cm are fully distributed in the distributor, and the small holes are arranged in a diamond shape, so that gas and liquid are fully contacted, and the oxidation efficiency is improved; in the step (3), 2-6 baffles are arranged in the water washing tower, so that water and gas in the water washing tower can be uniformly distributed, and the water washing effect is improved.
The invention has the beneficial effects that:
(1) according to the activator, the component A is a main activator, the component B is an auxiliary activator, under the synergistic effect of the component A, B, the oxidation effect of manganese dioxide is enhanced, the manganese dioxide can be used as an oxidant together with a potassium permanganate solution, waste is turned into wealth, solid slag is avoided, the consumption of potassium permanganate is effectively reduced, a closed loop is formed by an oxidation reaction, and a green and environment-friendly treatment process is realized. In addition, the component C is taken as an auxiliary oxidant and is compounded with activated manganese dioxide and potassium permanganate, so that the oxidation efficiency is effectively improved, and the consumption of potassium permanganate is further reduced.
(2) The invention arranges the distributor in the oxidation reactor, and the distributor is distributed with small holes in a diamond arrangement, so that gas and liquid are fully contacted, and the oxidation efficiency is improved. The potassium permanganate oxidizing solution is recycled, so that the potassium permanganate consumption is effectively reduced. In addition, the invention adds a water washing process, further removes a small amount of styrene waste gas in the exhaust gas, effectively prevents potassium permanganate from being entrained in the gas phase, avoids secondary pollution of the gas and ensures that the treated waste gas reaches the national emission standard. Therefore, the treatment process has the characteristics of high oxidation efficiency, safety and reliability, and realizes the safe removal of the easily polymerized styrene waste gas.
Drawings
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is a schematic view showing the connection of an oxidation reaction system in the present invention.
In the figure, a 1-oxidation reaction tower, a 2-liquid storage tank, a 3-filter press, a 4-activator, a 5-water washing tower, a 6-mechanical diaphragm pump, a 7-stainless steel reactor and an 8-mixer are arranged.
Detailed Description
The present invention is further illustrated by the following examples, but the present invention is not limited to these examples. The examples are given to fully understand the spirit and scope of the present invention and to further understand the features of the preparation method of the present invention.
EXAMPLES 1 to 10 preparation of styrene waste gas
700ml of styrene is added into a1 liter stainless steel reactor 7 with stirring, the electric heating temperature is 20-60 ℃, nitrogen is blown into the stainless steel reactor 7, and styrene-containing gas is generated and used as a styrene waste gas source. The generated styrene waste gas, compressed air and nitrogen are respectively introduced into a mixer 8 filled with phi 6 multiplied by 6 ceramic filler through a pipeline, and the styrene gas and the compressed air are uniformly mixed in the mixer 8. Wherein, nitrogen and compressed air are respectively measured by a gas rotameter, and different concentrations of the styrene waste gas can be obtained by adjusting the heating temperature and different gas pressures and flows. Wherein the electric heating temperature is preferably 25-45 ℃, the ratio of nitrogen to compressed air is (0.25-5): 1, preferably (0.5-3): 1, and the content of styrene gas in the mixed gas obtained in the range is 2000-8500 mg/m3The range is adjustable.
The styrene gas content of the mixed gas produced under different conditions is shown in table 1:
TABLE 1
Therefore, the styrene waste gas with different contents can be obtained by adjusting the heating temperature, the nitrogen and the compressed air flow, and various test requirements are met.
EXAMPLES 11 to 19 styrene waste gas treatment with different activators, oxidizing conditions and washing conditions
The method of examples 1 to 10 was used to prepare waste gases containing different amounts of styrene, which were then introduced into an oxidation reaction system. The oxidation reaction system comprises an oxidation reaction tower 1, a liquid storage tank 2, a filter press 3, an activator 4 and a water washing tower 5, wherein a glass fractionating column is used as the oxidation reaction tower 1, and a flask is used as the liquid storage tank 2. The upper end of the oxidation reaction tower 1 is provided with an air outlet, an oxidation liquid feeding port and a circulating liquid feeding port, the lower end is provided with an air inlet and a discharging port, and the discharging port is connected with a liquid storage tank 2; styrene waste gas enters from a gas inlet at the lower end of the oxidation reaction tower 1 and is in countercurrent contact with potassium permanganate oxidizing solution entering from the upper end to complete the oxidation reaction, and the reacted styrene waste gas is discharged from a gas outlet at the upper end; the reacted potassium permanganate solution enters the liquid storage tank 2 from the discharge hole at the lower end. And (3) discharging a part of the potassium permanganate solution in the liquid storage tank 2, circulating a part of the potassium permanganate solution to a circulating solution feeding hole at the upper end of the oxidation reaction tower 1 through a mechanical diaphragm pump 6, and performing countercurrent contact on the potassium permanganate solution and the styrene waste gas entering from the lower end of the oxidation reaction tower 1 again to complete the oxidation reaction.
And (3) pumping half of the potassium permanganate solution from the liquid storage tank 2 every 24 hours, filtering the potassium permanganate solution by using a filter press 3 to obtain filtrate and filter residue manganese dioxide, introducing the manganese dioxide into an activator 4, adding an activating agent in the table 2 to activate the manganese dioxide, adding the activated manganese dioxide into the liquid storage tank 2 to mix with the filtrate, then adding the component C to mix uniformly, merging the mixed filtrate into an external circulation line, and introducing the mixed filtrate into an oxidation reaction tower 1 through a feed inlet.
Styrene waste gas discharged from the upper end of the oxidation reaction tower 1 enters the water washing tower 5 from a lower inlet through a pipeline, water enters from an upper inlet at the top, is in countercurrent contact with the styrene waste gas, and is subjected to external circulation, so that the styrene waste gas and a small amount of high potassium permanganate solution carried by the styrene waste gas are further removed, and secondary pollution is avoided.
The results of the styrene off-gas treatment under different activators, oxidation conditions and water wash conditions are shown in table 2:
in table 2, a1 represents phosphoric acid, a2 represents nitric acid, and A3 represents sulfuric acid; a1Na and A1K respectively represent sodium and potassium salts of phosphoric acid; b2 represents triphenylphosphine; b3 represents diphenylphosphine; c1 represents 3-tert-butyl-4-hydroxymethoxyphenol, C2 represents 3-tert-butyl-4-hydroxyethoxyphenol, C3 represents 2, 6-di-tert-butyl-4-methoxyphenol, and C4 represents p-tert-butylcatechol.
TABLE 2
As can be seen from each example and comparative example 4 in Table 2, the activator and the styrene off-gas treatment method of the present invention were used even when the styrene content in the off-gas reached 8500mg/m3The content of the finally discharged styrene gas can still meet 50mg/m3National emission standard of (2).
In addition, as can be seen from example 14 and comparative example 1, after the component C is added in example 14, the concentration of the outlet styrene exhaust gas is greatly reduced, which indicates that the component C can be compounded with activated manganese dioxide and potassium permanganate as a co-oxidant, and the oxidation efficiency is effectively improved. Meanwhile, as can be seen from the example 14 and the comparative examples 2 and 3, one of the components A and B is absent, the activation effect of the manganese dioxide is not ideal, when the activated manganese dioxide and the potassium permanganate solution are used as the oxidizing agent together, the oxidation effect is poor, and the concentration of the outlet styrene waste gas is high, which fully indicates that the components A and B can play a synergistic effect when used as the activating agent together, so that the oxidation effect of the manganese dioxide is enhanced, and the components A and B can be used as the oxidizing agent together with the potassium permanganate solution, thereby changing waste into valuable and avoiding the generation of solid slag.
From the above analysis, when the A, B, C three components are all added, the styrene removal rate is higher than that of the component with less addition, which shows that the synergistic effect of the components is remarkable, and the styrene removal rate reaches more than 98.3%.
The test was conducted under the process conditions as described in example 14, and the continuous operation was continued for 5 days and 5 nights for 120 hours, and the concentration of the styrene off-gas at the inlet of the oxidation reaction tower 1 was 5000mg/m3Under the conditions of (1), the concentration of discharged styrene off-gas was kept at 50mg/m3Hereinafter, a potassium permanganate solution needs to be supplemented. The consumption of the potassium permanganate solution with and without the addition of the activator was comparatively examined, and the results are shown in table 3:
TABLE 3
| Number of times of potassium permanganate addition | Potassium permanganate additive amount% | |
| Example 14 | 1 | 5 |
| Comparative example 5 | 5 | 35 |
Therefore, under the condition of using the activator, the potassium permanganate solution is supplemented by 30% less, the potassium permanganate consumption is obviously reduced, the production cost is greatly reduced, and the generation of solid manganese dioxide slag is radically reduced.
EXAMPLES 20 to 27 styrene gas treatment in different distributors and Water scrubber 5
At the inlet concentration of styrene of 6000mg/m3Under the conditions, the length of an oxidation reactor is 60cm, the inner diameter of the oxidation reactor is 30mm, the concentration of a permanganate aqueous solution is 10%, the oxidation reaction temperature is 35 ℃, the gas-liquid ratio is 50:1, the ratio of the circulation amount to the discharge amount of the potassium permanganate solution is 8:1, and the activator ratio is as follows: a1: A1K: C2: 100:30:25, the weight ratio of the activating agent to the manganese dioxide is 6:1, the activation temperature is 50 ℃, the length of a water washing tower 5 is 60cm, the inner diameter is 100mm, the water washing temperature is 40 ℃, and the ratio of the water circulation amount to the styrene waste gas is 20: 1. The results of treating styrene gas with different distributors and water scrubber 5 configurations are shown in Table 4, wherein the inlet concentrations of styrene off-gas of comparative examples 7 and 8 are 2000mg/m3、3000mg/m3：
TABLE 4
As can be seen from examples 20 to 27 and comparative examples 6 to 8, under the same conditions, when the oxidation reaction tower 1 is provided with the distributor, the discharged styrene gas concentration is significantly lower than that without the distributor, and the discharge requirement is met, which indicates that the addition of the distributor effectively improves the oxidation efficiency.
As can be seen from example 23 and comparative example 9, when the water washing process was performed, the concentration of the discharged styrene gas was reduced, and when the water washing tower 5 was not installed, potassium permanganate was detected at the outlet, and a pale pink color was observed in the discharged styrene gas, indicating that the water washing process was used to avoid secondary pollution caused by potassium permanganate entrained in the styrene gas.
Claims (18)
1. The activating agent for manganese dioxide generated in styrene waste gas treatment is characterized by comprising A, B components, wherein the component A is one or a mixture of more of phosphoric acid, nitric acid and sulfuric acid, the component B is one of phosphate, triphenylphosphine and diphenylphosphine, and the ratio of the component A to the component B is 100 parts by mass and 5-40 parts by mass; the adhesive also comprises 1-35 parts of a component C, wherein the component C is one or a mixture of more of 3-tert-butyl-4-hydroxymethoxyphenol, 3-tert-butyl-4-hydroxyethoxyphenol, 2, 6-di-tert-butyl-4-methoxyphenol and p-tert-butylcatechol.
2. The activator for manganese dioxide generated in the treatment of styrene off-gas according to claim 1, wherein said a component is phosphoric acid.
3. The activator for manganese dioxide generated in the treatment of styrene off-gas according to claim 1, wherein said A component is nitric acid, B component is triphenylphosphine, and C component is p-tert-butylcatechol, or said A component is phosphoric acid, B component is potassium phosphate, and C component is 3-tert-butyl-4-hydroxyethoxyphenol.
4. The activator for manganese dioxide generated in the treatment of styrene off-gas according to claim 1, wherein the ratio of the component A, the component B and the component C is 100 parts of the component A, 5 to 30 parts of the component B and 5 to 25 parts of the component C.
5. The activator for manganese dioxide generated in the treatment of styrene off-gas according to claim 1 or 2, further comprising a solvent and a dispersant, wherein the solvent and the dispersant are polyhydric alcohols, alcohol ether type compounds or alkylbenzene type compounds.
6. The method for activating manganese dioxide generated in styrene waste gas treatment is characterized in that manganese dioxide in potassium permanganate oxidizing solution is filtered out, A, B components in the activator in claim 1 are added for activation, and the weight ratio of the added amount of the activator to the weight of the manganese dioxide is (1-10): 1, the activation temperature is 40-90 ℃, and the activation time is 10-60 min.
7. The method for activating manganese dioxide generated in the treatment of styrene off-gas according to claim 6, wherein the weight ratio of the added amount of the activating agent to manganese dioxide is (1-5): 1.
8. the method for activating manganese dioxide generated in the styrene waste gas treatment according to claim 6 or 7, wherein 1-35 parts of component C is added after activation and is fully and uniformly mixed, wherein the component C is one or a mixture of 3-tert-butyl-4-hydroxymethoxyphenol, 3-tert-butyl-4-hydroxyethoxyphenol, 2, 6-di-tert-butyl-4-methoxyphenol and p-tert-butylcatechol.
9. The method for treating the styrene waste gas is characterized by comprising the following steps of:
(1) the styrene waste gas enters an oxidation reaction system comprising an oxidation reaction tower (1), a liquid storage tank (2), a filter press (3), an activator (4) and a water washing tower (5); the upper end of the oxidation reaction tower (1) is provided with an air outlet, an oxidation liquid feeding hole and a circulating liquid feeding hole, the lower end is provided with an air inlet and a discharging hole, and the discharging hole is connected with the liquid storage tank (2); styrene waste gas enters from a gas inlet at the lower end of the oxidation reaction tower (1), and is in countercurrent contact with potassium permanganate oxidizing solution entering from the upper end to complete the oxidation reaction, and the reacted styrene waste gas is discharged from a gas outlet at the upper end; the reacted potassium permanganate solution enters the liquid storage tank (2) from a discharge hole at the lower end, part of the potassium permanganate solution in the liquid storage tank (2) is discharged, and part of the potassium permanganate solution is circulated to a circulating liquid feed hole at the upper end of the oxidation reaction tower (1) through a mechanical diaphragm pump (6) and is in countercurrent contact with the styrene waste gas entering from the lower end of the oxidation reaction tower (1) again to complete the oxidation reaction;
(2) pumping half of the potassium permanganate solution from the liquid storage tank (2) every 24 hours, filtering the potassium permanganate solution by using a filter press (3) to obtain filtrate and filter residue manganese dioxide, introducing the manganese dioxide into an activator (4), activating the manganese dioxide according to the activation method of claim 6, introducing the activated manganese dioxide into the liquid storage tank (2), mixing the activated manganese dioxide with the filtrate, then adding the component C, fully and uniformly mixing, and introducing the mixed filtrate into an oxidation reaction tower (1) from a circulating liquid feeding hole;
(3) styrene waste gas discharged from the upper end of the oxidation reaction tower (1) enters the water washing tower (5) from a lower inlet through a pipeline, water enters from an upper inlet at the top, is in countercurrent contact with the styrene waste gas, is subjected to external circulation, is further removed from the styrene waste gas and entrained little amount of potassium permanganate solution, and the treated waste gas is discharged from an air outlet at the top of the water washing tower (5).
10. The method of treating styrene off-gas according to claim 9,
in the step (1), the ratio of the circulating amount to the discharged amount of the potassium permanganate solution is (0.5-10): 1, the length-diameter ratio of an oxidation reaction tower (1) is (10-30): 1, the concentration of the potassium permanganate solution is 6% -15%, the oxidation reaction temperature is 20 ℃ -50 ℃, and the volume ratio of the styrene waste gas to the potassium permanganate solution is (10-100): 1;
in the step (3), the length-diameter ratio of the water washing tower (5) is (5-10): 1, the water washing temperature is 20-60 ℃, and the volume ratio of the water circulation volume to the styrene waste gas is (1-50): 1.
11. The method for treating the styrene waste gas according to claim 10, wherein in the step (1), the length-diameter ratio of the oxidation reaction tower (1) is (10-15): 1.
12. The method for treating styrene off-gas according to claim 10, wherein in the step (1), the concentration of the potassium permanganate solution is 7 to 10%.
13. The method according to claim 10, wherein the oxidation reaction temperature in the step (1) is 25 to 50 ℃.
14. The method for treating the styrene waste gas according to claim 10, wherein in the step (1), the volume ratio of the styrene waste gas to the potassium permanganate solution is (20-70): 1.
15. The method according to claim 10, wherein the washing temperature in the step (3) is 25 to 45 ℃.
16. The method according to claim 10, wherein in the step (3), the ratio of the water circulation amount to the volume of the styrene off-gas is (1-30): 1.
17. The method for treating styrene waste gas according to claim 16, wherein in the step (3), the volume ratio of the water circulation amount to the styrene waste gas is (5-20): 1.
18. The styrene waste gas treatment method according to claim 9, wherein in the step (1), distributors are arranged in the oxidation reaction tower (1) at intervals of 2-20 cm in height, and are fully distributed with small holes with the diameter of 1-3 cm, and the small holes are arranged in a diamond shape; in the step (3), 2-6 baffles are arranged in the water washing tower (5).
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| DE3727635A1 (en) * | 1987-08-19 | 1989-03-02 | Magdeburg Spezialbau | Method for removing styrene from the exhaust air |
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