CN111068462A - Treatment method of styrene waste gas - Google Patents
Treatment method of styrene waste gas Download PDFInfo
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- CN111068462A CN111068462A CN201811230831.2A CN201811230831A CN111068462A CN 111068462 A CN111068462 A CN 111068462A CN 201811230831 A CN201811230831 A CN 201811230831A CN 111068462 A CN111068462 A CN 111068462A
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- styrene
- separation membrane
- membrane
- gas
- potassium permanganate
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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
- B01D53/14—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 by absorption
- B01D53/1431—Pretreatment by other processes
- B01D53/1443—Pretreatment by diffusion
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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
- B01D53/14—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 by absorption
- B01D53/1487—Removing organic compounds
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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
- B01D53/22—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 by diffusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
Abstract
The invention provides a treatment method of styrene waste gas, which comprises the following steps: providing a separation membrane assembly comprising a hydrophobic separation membrane, and enabling the potassium permanganate solution to be arranged on one side of the separation membrane; and enabling the styrene waste gas to be positioned at the other side of the separation membrane and to be in contact with the potassium permanganate aqueous solution through the separation membrane. The treatment method provided by the invention can avoid the occurrence of a large amount of fog drops, entrainment of gas and liquid and other undesirable phenomena caused by the mixing of gas phase and liquid phase, and can remove the styrene more thoroughly.
Description
Technical Field
The invention relates to the field of petroleum refining, in particular to a treatment method of styrene waste gas.
Background
Styrene is an important chemical raw material and is widely applied in the rubber field and the synthesis field. Styrene can undergo self-polymerization, and therefore, it is common to store it under low temperature conditions and add a polymerization inhibitor thereto. However, once the styrene volatilizes during the storage and transportation process, the volatilized styrene is easy to block pipelines due to severe self-polymerization reaction caused by the rise of the temperature when entering a common oil gas recovery or waste gas treatment device, and is very easy to pollute and block key equipment for waste gas treatment such as an adsorbent, a separation membrane, a catalytic reactor and the like.
At present, few methods for treating styrene waste gas are available, and only reports are that potassium permanganate aqueous solution absorption method, modified sepiolite adsorption method and condensation method are adopted to liquefy waste gas. However, since the absorption effect of the aqueous potassium permanganate solution and styrene is not satisfactory, absorption is required many times, and the absorbent for pollution after absorption is not easy to handle. Sepiolite has the problem of complex preparation, and has certain potential safety hazard due to high desorption temperature. The condensation method only has good removal rate on the high-concentration styrene waste gas, but the tail gas index is difficult to reach 50 mg/m/2015 required by the current national standard (GB 31570-3And the condensing method has large energy consumption and difficult maintenance, needs long-time cold insulation and precooling and cannot be started and stopped at any time.
In addition to the above-disclosed styrene off-gas treatment method, an adsorption method is frequently used. However, the adsorption method for treating styrene sheets has a series of problems, such as easy polymerization of styrene, and significant polymerization heat effect and adsorption heat effect, so that deactivation of the adsorbent easily occurs and the risk of fire is high.
Disclosure of Invention
In view of the problems in the prior art, an object of the present invention is to provide a method for treating styrene waste gas, in which styrene waste gas is treated by a separation membrane module including a hydrophobic separation membrane, potassium permanganate aqueous solution is disposed on one side of the separation membrane, styrene waste gas is disposed on the other side of the separation membrane, and the separation membrane is in contact with the potassium permanganate aqueous solution, so that undesirable phenomena such as entrainment of gas and liquid and a large amount of mist due to mixing of gas and liquid phases can be avoided, and styrene in styrene waste gas can be removed more thoroughly.
One aspect of the present invention provides a method for treating styrene waste gas, comprising:
providing a separation membrane module comprising a hydrophobic separation membrane;
placing an aqueous potassium permanganate solution on one side of the separation membrane;
and enabling the styrene waste gas to be positioned at the other side of the separation membrane and to be in contact with the potassium permanganate aqueous solution through the separation membrane.
The inventor of the present application has found through research that by locating the hydrophilic potassium permanganate aqueous solution on one side of the hydrophobic separation membrane and locating the hydrophobic styrene waste gas on the other side of the hydrophobic separation membrane, it can be ensured that the hydrophilic potassium permanganate aqueous solution does not flow only on one side through the hydrophobic separation membrane, and styrene molecules in the styrene waste gas on the other side of the separation membrane can contact with the potassium permanganate aqueous solution on one side of the separation membrane through the membrane pores, and thus can be absorbed by the potassium permanganate aqueous solution. Therefore, in the absorption process, the potassium permanganate aqueous solution flows only on one side of the separation membrane, the flow process is very stable, and the undesirable phenomena of a large amount of fog drops, gas-liquid entrainment and the like caused by mixing with the styrene waste gas can be avoided.
In addition, the separation membrane in the separation membrane component has a large specific surface area, and the surface of the membrane is the gas-liquid contact area, so that the gas-liquid contact area is large, and the absorption efficiency of styrene is high. Moreover, the separation membrane module also has the characteristic of uniform flow channel distribution, so that the problem of low absorption efficiency caused by nonuniform gas-liquid contact, excessively high local gas flow speed and the like inherent in absorption units such as absorption towers and the like can be solved.
In a preferred embodiment of the present invention, the separation membrane is at least one selected from the group consisting of a cellulose derivative-based polymer organic membrane, a polysulfone-based polymer organic membrane, a polyamide-based polymer organic membrane, a polyimide-based polymer organic membrane, a polyester-based polymer organic membrane, and a polyolefin-based polymer organic membrane, preferably a polyolefin-based polymer organic membrane, and more preferably a silicone-modified polyolefin-based polymer organic membrane; the pore diameter of the membrane pores of the separation membrane is 5nm to 1000nm, preferably 20nm to 100 nm.
According to the present invention, when the pore diameter of the membrane pores of the separation membrane is within the above range, it is advantageous for styrene in the styrene off-gas to pass through the separation membrane to contact the absorbent, and thus styrene in the gas phase can be efficiently absorbed.
According to the present invention, the above-mentioned separation membranes are preferable in the present application from the viewpoint of obtaining a better styrene removal efficiency, as long as the separation membranes having hydrophobicity are suitable for the present invention.
In a preferred embodiment of the present invention, the separation membrane module is in the form of a hollow fiber membrane module or a wound membrane module or a disc-type membrane module.
In a preferred embodiment of the present invention, the packing density of the separation membrane in the separation membrane module is 50m2/m3～1000m2/m3Preferably 100m2/m3～300m2/m3。
According to the present invention, when the packing density is within the above range, it is advantageous to minimize the volume of the membrane separation module while efficiently removing styrene, so that the miniaturization of the apparatus and the modular design are possible.
According to the present invention, 2 or more than 2 separation membrane modules may be used in series and/or in parallel.
In a preferred embodiment of the invention, the concentration of the potassium permanganate solution is 0.001g/L to 10 g/L; the temperature of the absorbent is-5 ℃ to 55 ℃, preferably 5 ℃ to 20 ℃.
According to the present invention, when the concentration of the aqueous potassium permanganate solution is within the above range, efficient absorption of styrene is facilitated.
According to the invention, the aqueous potassium permanganate solution is preferably subjected to a cooling treatment or a heating treatment before it is used. Specifically, the cooling treatment temperature is-5-20 ℃, and the potassium permanganate aqueous solution is cooled to the temperature range, which is favorable for reducing and even avoiding the absorbed styrene to generate auto-polymerization; the heating treatment temperature is 20-50 ℃, and the potassium permanganate aqueous solution is heated to the temperature range, which is favorable for improving the absorption efficiency of the styrene which is difficult to absorb.
In a preferred embodiment of the invention, the flow rate of the aqueous potassium permanganate solution is between 0.01m/s and 5.0 m/s; the residence time of the potassium permanganate aqueous solution in the separation membrane assembly is 1 s-1000 s, preferably 5 s-100 s.
According to the present invention, when the flow rate of the aqueous potassium permanganate solution or the residence time of the aqueous potassium permanganate solution in the separation membrane module is within the above range, it is advantageous to improve the absorption efficiency of styrene in styrene off-gas.
In a preferred embodiment of the invention, a polymerization inhibitor is added to the aqueous potassium permanganate solution; the polymerization inhibitor is preferably at least one of nitrobenzene, benzenediol, sodium sulfate, sodium sulfide and ammonium thiocyanate.
According to the invention, the use of the above-mentioned specific polymerization inhibitors advantageously reduces or even avoids the auto-polymerization of the absorbed styrene.
In a preferred embodiment of the present invention, the flow velocity of the styrene off-gas is 0.1 to 10m/s, preferably 0.2 to 5m/s, and more preferably 0.5 to 2 m/s.
According to the present invention, when the flow rate of the styrene off-gas is within the above-specified range, it is advantageous to remove styrene with high efficiency in a shorter time frame.
In a preferred embodiment of the present invention, after the styrene off-gas is introduced, a pressure of 0.0001MPa to 10MPa, preferably 0.01MPa to 0.1MPa, is applied to the separation membrane module.
According to the present invention, the rapid permeation and penetration of styrene through the membrane pores of the separation membrane are facilitated by the above operation, while further reducing the possibility of the absorbent permeating through the membrane pores.
In a preferred embodiment of the present invention, the concentration of styrene in the styrene off-gas is 1mg/m3～50000mg/m3。
According to the invention, the styrene waste gas can be treated by adopting one absorbent, and the styrene waste gas can also be treated by adopting more than two absorbents in sequence.
The treatment method provided by the invention has the advantages of wide application range, high removal rate of styrene up to more than 85%, small floor area and wide industrial application prospect.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
In the following examples 1-2 and comparative example 1, the removal rate was calculated by the formula (1):
removal rate (inlet gas concentration-exhaust gas concentration)/inlet gas concentration formula (1)
Example 1
The styrene waste gas treated in this example mainly comprises styrene and a small amount of benzene-series pollutants, wherein the concentration of styrene is 960-4880mg/m3The concentration of other benzene series pollutants is not higher than 100mg/m in total3。
The polyethylene hydrophobic microporous membrane prepared by a melt-draw method is used as a separation membrane (average pore diameter is 0.1 mu m, porosity is 38%) to prepare a separation membrane component, the separation membrane component is provided with an air inlet, an air outlet, a liquid inlet and a liquid outlet, the external dimension is phi 150 multiplied by 1080mm, and the filling density of the polyethylene hydrophobic microporous membrane is 200m2/m3。
The prepared 1 separation membrane component is used independently;
and (2) introducing a potassium permanganate solution with the concentration of 0.01g/L and the temperature of 25 ℃ into a liquid inlet of the separation membrane component at the flow speed of 0.1m/s so as to enable the potassium permanganate solution to be positioned at one side of the separation membrane, and staying in the separation membrane component for 100 s. Introducing the styrene waste gas into an air inlet of a separation membrane component at the flow speed of 0.6m/s to enable the styrene waste gas to be positioned at the other side of the separation membrane, and contacting the styrene waste gas with an absorbent through the separation membrane so as to treat the styrene waste gas;
obtaining treated styrene waste gas at the gas outlet;
wherein the styrene content in the styrene off-gas before treatment was measured and taken as the intake gas concentration, the styrene content in the styrene off-gas after treatment was measured and taken as the off-gas concentration, and the styrene removal rate was calculated, the results of which are shown in table 1.
TABLE 1
As can be seen from Table 1, the styrene contents in the treated styrene waste gases were all 50mg/m3The removal rate of styrene was not less than 97%.
Example 2
In this example, the styrene waste gas generated from the styrene loading station was treated, and the concentration of styrene was 4890-3Left and right.
Preparing a separation membrane assembly by using a Polytetrafluoroethylene (PTFE) hollow fiber microporous membrane (the aperture of a membrane hole is 10nm) prepared by a melt spinning-stretching method, wherein the separation membrane assembly is provided with an air inlet, an air outlet, a liquid inlet and a liquid outlet, the external dimension is phi 280 x 1080mm, and the filling density of the PTFE hollow fiber microporous membrane is 500m2/m3。
The prepared 1 separation membrane component is used independently;
and (3) introducing a potassium permanganate aqueous solution with the concentration of 5g/L into a liquid inlet of the separation membrane module at the flow rate of 2.0m/s so as to enable the potassium permanganate aqueous solution to be positioned at one side of the separation membrane, and staying for 1000s in the separation membrane module. Introducing the styrene waste gas into an air inlet of a separation membrane component at the flow rates of 0.6m/s, 1.0m/s, 1.4m/s, 1.8m/s, 2.2m/s and 2.6m/s respectively to enable the styrene waste gas to be positioned at the other side of the separation membrane, and contacting the styrene waste gas with a potassium permanganate aqueous solution through the separation membrane so as to treat the styrene waste gas;
obtaining treated styrene waste gas at the gas outlet;
wherein the content of styrene in the styrene off-gas before treatment was measured and taken as the intake gas concentration, the content of styrene in the styrene off-gas after treatment was measured and taken as the off-gas concentration, and the styrene removal rate was calculated, and the results are shown in table 2.
TABLE 2
As can be seen from Table 2, the flow rate of the styrene off-gas can greatly affect the removal rate of styrene, especially when the flow rate is 0.6m/s, the content of styrene in the treated styrene off-gas reaches 20mg/m3About, and the removal rate reaches 99.9%.
Comparative example 1
The styrene off-gas treated in this comparative example mainly contained styrene and a small amount of benzene-based contaminants, wherein the concentration of styrene was 2856-3The concentration of other benzene series pollutants is not higher than 100mg/m in total3。
The absorption tower is filled with the packing (the absorption tower adopts corrugated plate packing, the number of the tower plates is 18, and the base area of the packing is 500m2And the size of the absorption tower was Φ 5600 × 1680mm), the remaining conditions of the temperature, flow rate, total flow rate, and the like of the styrene off-gas were the same as in example 1. The content of non-methane total hydrocarbons in the styrene off-gas before treatment was measured and taken as the intake gas concentration, the content of non-methane total hydrocarbons in the styrene off-gas after treatment was measured and taken as the off-gas concentration, and the removal rate of non-methane total hydrocarbons was calculated, with the results shown in table 3.
TABLE 3
As can be seen from Table 3, the styrene content in the styrene off-gas before treatment was 3000mg/m3About 600mg/m, the content of styrene in the treated styrene waste gas3The styrene removal rate was about 80%.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A method for treating styrene waste gas comprises the following steps:
providing a separation membrane module comprising a hydrophobic separation membrane;
placing an aqueous potassium permanganate solution on one side of the separation membrane;
and enabling the styrene waste gas to be positioned at the other side of the separation membrane and to be in contact with the potassium permanganate aqueous solution through the separation membrane.
2. The treatment method according to claim 1, wherein the separation membrane is at least one selected from the group consisting of a cellulose derivative-based polymer organic membrane, a polysulfone-based polymer organic membrane, a polyamide-based polymer organic membrane, a polyimide-based polymer organic membrane, a polyester-based polymer organic membrane, and a polyolefin-based polymer organic membrane, preferably a polyolefin-based polymer organic membrane, and more preferably a silicone-modified polyolefin-based polymer organic membrane; the pore diameter of the membrane pores of the separation membrane is 5nm to 1000nm, preferably 20nm to 100 nm.
3. The process according to claim 1 or 2, wherein the separation membrane module is in the form of a hollow fiber membrane module or a wound membrane module or a disc-type membrane module.
4. The process according to any one of claims 1 to 3, wherein the packing density of the separation membrane in the separation membrane module is 50m2/m3～1000m2/m3Preferably 100m2/m3～300m2/m3。
5. The treatment method according to any one of claims 1 to 4, wherein the concentration of the aqueous potassium permanganate solution is 0.001 to 10 g/L; the temperature of the absorbent is-5 ℃ to 55 ℃, preferably 5 ℃ to 20 ℃.
6. The process according to any one of claims 1 to 5, characterized in that the flow rate of the aqueous potassium permanganate solution is between 0.01 and 5.0 m/s; the residence time of the potassium permanganate aqueous solution in the separation membrane assembly is 1 s-1000 s, preferably 5 s-100 s.
7. The process according to any one of claims 1 to 6, wherein a polymerization inhibitor is added to the aqueous potassium permanganate solution; the polymerization inhibitor is preferably at least one of nitrobenzene, benzenediol, sodium sulfate, sodium sulfide and ammonium thiocyanate.
8. The treatment method according to any one of claims 1 to 7, wherein the flow velocity of the styrene off-gas is 0.1 to 10m/s, preferably 0.2 to 5m/s, more preferably 0.5 to 2 m/s.
9. The treatment method according to any one of claims 1 to 8, wherein a pressure of 0.0001MPa to 10MPa, preferably 0.01MPa to 0.1MPa, is applied to the separation membrane module after the styrene off-gas is introduced.
10. The treatment method according to any one of claims 1 to 9, wherein the concentration of styrene in the styrene off-gas is 1mg/m3～50000mg/m3。
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| CN201811230831.2A CN111068462A (en) | 2018-10-22 | 2018-10-22 | Treatment method of styrene waste gas |
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| CN201811230831.2A CN111068462A (en) | 2018-10-22 | 2018-10-22 | Treatment method of styrene waste gas |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5198000A (en) * | 1990-09-10 | 1993-03-30 | The University Of Connecticut | Method and apparatus for removing gas phase organic contaminants |
| CN1203537A (en) * | 1995-12-06 | 1998-12-30 | 宇宙工程公司 | Method of treating or recovering gaseous hydrocarbon contained in waste gas |
| CN101362044A (en) * | 2008-09-08 | 2009-02-11 | 江南大学 | Formaldehyde exhaust-gas efficient film absorption technique |
-
2018
- 2018-10-22 CN CN201811230831.2A patent/CN111068462A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5198000A (en) * | 1990-09-10 | 1993-03-30 | The University Of Connecticut | Method and apparatus for removing gas phase organic contaminants |
| CN1203537A (en) * | 1995-12-06 | 1998-12-30 | 宇宙工程公司 | Method of treating or recovering gaseous hydrocarbon contained in waste gas |
| CN101362044A (en) * | 2008-09-08 | 2009-02-11 | 江南大学 | Formaldehyde exhaust-gas efficient film absorption technique |
Non-Patent Citations (3)
| Title |
|---|
| 刘家祺 主编: "《分离过程与技术》", 31 December 2001, 天津大学出版社 * |
| 宫中昊: "高锰酸钾溶液处理苯乙烯废气中试", 《环境工程》 * |
| 杨座国 编著: "《膜科学技术过程与原理》", 31 August 2009, 华东理工大学出版社 * |
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