CN114618266A - Solubilization absorbent, preparation method thereof and organic waste gas treatment method - Google Patents
Solubilization absorbent, preparation method thereof and organic waste gas treatment method Download PDFInfo
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- CN114618266A CN114618266A CN202011461871.5A CN202011461871A CN114618266A CN 114618266 A CN114618266 A CN 114618266A CN 202011461871 A CN202011461871 A CN 202011461871A CN 114618266 A CN114618266 A CN 114618266A
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- 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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01D53/1493—Selection of liquid materials for use as absorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
- B01D2252/2056—Sulfur compounds, e.g. Sulfolane, thiols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/50—Combinations of absorbents
- B01D2252/504—Mixtures of two or more absorbents
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- B01D2257/702—Hydrocarbons
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- B01D2257/708—Volatile organic compounds V.O.C.'s
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Abstract
The invention discloses a solubilizing absorbent, which comprises the following components and contents thereof based on the total mass of the solubilizing absorbent: 1.0-5.0% of nonionic gemini surfactant, 20.0-45.0% of cyclodextrin and derivatives thereof, 18.0-65% of water, 10.0-40.0% of dimethyl sulfoxide, 1.0-5.0% of inorganic base and 0.5-2.0% of anionic surfactant. The invention also discloses a preparation method of the solubilizing absorbent and a treatment method of organic waste gas. The solubilizing absorbent and the hypergravity absorption method are suitable for treating high-concentration organic waste gas in an oil refining sewage farm, indexes such as non-methane total hydrocarbon, benzene, toluene, xylene and the like in the treated waste gas can meet the requirements of the emission Standard of pollutants for Petroleum refining industry (GB31570-2015), and stable standard emission is realized.
Description
Technical Field
The invention belongs to the technical field of organic waste gas treatment, and particularly relates to a solubilizing absorbent and a preparation method thereof, and a treatment method for treating organic waste gas by utilizing the solubilizing absorbent in a hypergravity field, in particular to a treatment method for high-concentration VOCs waste gas in an oil refining sewage field.
Background
In recent years, pollution problems and treatment measures of Volatile Organic Compounds (VOCs) and malodorous substances have been receiving increasing attention and importance from government, enterprise and social public. The sewage field of the refining enterprise is one of the main sources of Volatile Organic Compounds (VOCs) emission of each enterprise, and hydrocarbon-containing waste gas generated by the sewage field has wide source and complex gas composition and contains alkanes and benzene series (mainly C)2-C10) The organic gas and the gas have high concentration and large fluctuation, and the non-methane total hydrocarbon in the waste gas is generally 500-3000 mg/m3The amount of exhaust gas is about 1/3 of the total gas amount. Currently, the emission standard implemented by each enterprise is the national emission standard for malodorous pollutants (GB14554-93) issued in 1993, which sets emission limits for ammonia, trimethylamine, hydrogen sulfide, methyl mercaptan, methyl sulfide, dimethyldisulfide, carbon disulfide, and 8 species of malodorous pollutants styrene. On 16 days 4 months 4 in 2015, the national environmental protection department releases 'emission Standard for pollutants for the refining industry' (GB31570-2015) and 'emission Standard for pollutants for the petrochemical industry' (GB31571-2015), clear regulations on the emission limits of 64 volatile organic compounds are provided, and special emission limits are provided for indexes of four pollutants including non-methane total hydrocarbons, benzene, toluene and xylene generated by a wastewater treatment organic waste gas collection and treatment device (the non-methane total hydrocarbons are less than or equal to 120 mg/m)3Benzene is less than or equal to 4mg/m3Toluene is less than or equal to 15mg/m3Xylene is less than or equal to 20mg/m3). Therefore, it is an important research subject to develop a fast, efficient, economically applicable treatment technology for high-concentration hydrocarbon-containing waste gas generated by sewage plants of refinery enterprises.
At present, the treatment methods for the waste gas containing VOCs mainly include adsorption method, absorption method, catalytic combustion method, membrane separation method, isothermal plasma technology, photocatalytic oxidation, and the like. The organic waste gas of the oil refining sewage farm has complex components, contains VOCs, malodorous substances and water, and has large concentration fluctuation of the VOCs. Therefore, when the organic waste gas of the oil refining sewage field is treated by an adsorption method, the surface and the inner pore channels of the adsorption material can be covered by the moisture in the waste gas, so that the adsorption effect is influenced; when the catalytic combustion method is used, malodorous substances such as hydrogen sulfide in the waste gas can cause catalyst poisoning, and the treatment effect is seriously influenced; when the low-temperature plasma technology is used, the electrode plates are polluted by moisture, hydrogen sulfide and the like in the waste gas, so that the treatment effect is poor.
The absorption method has the advantages of strong adaptability to complex components in the waste gas, simple process, low investment and operation cost and the like, and is suitable for treating the organic waste gas in the oil refining sewage farm. The key to the liquid absorption process is the selection of the absorbent, and the types of absorbent commonly used at present are high boiling point organic solvent and water-based composite absorbent. Among them, the high boiling point organic solvent itself generates VOCs, and the absorption rate under high temperature conditions is lower, and secondary pollution may be caused. The water-based absorbent generally comprises water, mineral oil, water, a surfactant, an auxiliary agent and the like, and VOCs in the organic waste gas mainly comprise alkanes, aromatic hydrocarbons and the like, so that the solubility of the substances in water is low, the mass transfer efficiency in the gas-liquid absorption process is low, and the treatment effect is influenced.
The hypergravity technology is a novel chemical process strengthening technology developed in nearly two decades, under the condition of a hypergravity field (generally less than 1000g), the gas-liquid mass transfer efficiency can be greatly improved (1-3 orders of magnitude can be improved), meanwhile, the flooding gas speed can be effectively improved, the production efficiency and the capacity of the device can be improved while the scale of the treatment device is greatly reduced, and meanwhile, because the hypergravity device has the characteristics and the advantages of simplicity and convenience in operation, high starting speed, high adaptability and the like, good application effects are obtained in the aspects of flue gas desulfurization and dust removal, deoxidation in water, waste gas deamination and the like. Aiming at the problem of low gas-liquid mass transfer efficiency of insoluble gases such as alkane, aromatic hydrocarbon and the like in organic waste gas, the supergravity technology has good research and application prospects.
Disclosure of Invention
Aiming at the problems in the prior art and the technical problem of high treatment difficulty of organic waste gas, particularly high-concentration organic waste gas in an oil refining sewage field, the invention aims to provide a solubilizing absorbent and a preparation method thereof, and simultaneously, the solubilizing absorbent is utilized to effectively treat low-carbon alkane and benzene series in the high-concentration VOCs waste gas in the oil refining sewage field.
Therefore, the invention provides a solubilizing absorbent which comprises the following components and contents thereof based on the total mass of the solubilizing absorbent:
1.0 to 5.0% of a nonionic gemini surfactant,
20.0 to 45.0 percent of cyclodextrin and derivatives thereof,
18.0 to 65% of water,
10.0 to 40.0% of dimethyl sulfoxide,
1.0 to 5.0% of an inorganic base,
0.5 to 2.0% of an anionic surfactant.
According to the principle of absorbing organic gas, organic gas molecules firstly enter a liquid phase from a gas phase through gas-liquid mass transfer; the organic gas molecules entering the liquid phase and the absorbent are adsorbed by intermolecular force and exist stably, so that the purpose of solubilization and absorption is achieved. Therefore, the nonpolar lipophilic structure of the surfactant is selected to be matched with the molecular structure of the organic gas in the waste gas, so that the similar compatibility can be effectively realized. Specifically, on one hand, the nonionic gemini surfactant and the anionic surfactant can greatly reduce the oil-water interfacial tension and provide good mass transfer conditions for organic gas molecules entering a liquid phase from a gas phase; on the other hand, the nonionic gemini surfactant and the anionic surfactant can form stable micelles in the solution, and the lipophilic group of the nonionic gemini surfactant has alkyl and aryl, so that the nonionic gemini surfactant has good matching property with organic gas molecules in waste gas in structure, and the organic gas molecules can stably exist after entering the micelles; the cyclodextrin surfactant can be combined with organic matters entering a cavity in modes of intermolecular force, hydrogen bonds and the like due to a special nonpolar cavity structure, so that the cyclodextrin surfactant can exist stably; and the cyclodextrins with different polymerization degrees have nonpolar cavities with different diameters, and can adsorb alkane and arene with different structures and molecular weights, so that the cyclodextrin has the adjustability in the aspect of solubilization and absorption, and is favorable for solubilization and absorption of mixed gas. In addition, the synergistic effect exists among various surfactants, so that the structure of the interfacial film has more stability and elasticity in the absorption process, and the comprehensive absorption capacity of organic gas molecules is favorably improved.
The solubilizing absorbent of the present invention preferably comprises the following components and their contents, based on the total mass of the solubilizing absorbent:
1.5 to 3.5% of a nonionic gemini surfactant,
25.0-40.0% of cyclodextrin and its derivatives,
20.0 to 40% of water,
20.0 to 35.0% of dimethyl sulfoxide,
1.5 to 3.5% of an inorganic base,
0.8 to 1.8% of an anionic surfactant.
The solubilizing absorbent of the present invention, wherein preferably, the nonionic gemini surfactant has a structural formula shown in the following formula,
wherein, the terminal substituent R1An alkyl group having 2 to 10 carbon atoms or an alkylphenyl group having 8 to 18 carbon atoms, preferably an alkylphenyl group having 14 to 15 carbon atoms; intermediate linking group R2Is alkyl or aryl with 2-6 carbon atoms; the polymerization degree x of the oxyethylene is 6 to 30, preferably 5 to 35, and more preferably 12 to 25.
The solubilizing absorbent according to the present invention, wherein the cyclodextrin includes at least one of α -cyclodextrin, β -cyclodextrin, and γ -cyclodextrin.
The solubilizing absorbent according to the present invention, wherein the derivative group of the cyclodextrin derivative preferably includes a methyl substituent, an ethyl substituent, a hydroxypropyl substituent, a hydroxyethyl substituent, a hydroxymethyl substituent, a carboxyethyl substituent, an ethyl ether substituent, a monoglucose substituent, and a monomaltose substituent.
The solubilizing absorbent according to the present invention, wherein the cyclodextrin and its derivative is preferably α -cyclodextrin, β -cyclodextrin, γ -cyclodextrin, α -cyclodextrin methyl substituent derivative, α -cyclodextrin ethyl substituent derivative, α -cyclodextrin hydroxypropyl substituent derivative, α -cyclodextrin hydroxyethyl substituent derivative, α -cyclodextrin hydroxymethyl substituent derivative, α -cyclodextrin carboxyethyl substituent derivative, α -cyclodextrin ethyl ether substituent derivative, α -cyclodextrin monoglucose substituent derivative, α -cyclodextrin monomaltose substituent derivative, β -cyclodextrin methyl substituent derivative, β -cyclodextrin ethyl substituent derivative, β -cyclodextrin hydroxypropyl substituent derivative, β -cyclodextrin hydroxyethyl substituent derivative, β -cyclodextrin hydroxypropyl substituent derivative, β -cyclodextrin hydroxyethyl substituent derivative, or a mixture thereof, Two or three of beta-cyclodextrin hydroxymethyl substituent derivatives, beta-cyclodextrin carboxyethyl substituent derivatives, beta-cyclodextrin ethyl ether substituent derivatives, beta-cyclodextrin monoglucose substituent derivatives, beta-cyclodextrin monomaltose substituent derivatives, gamma-cyclodextrin methyl substituent derivatives, gamma-cyclodextrin ethyl substituent derivatives, gamma-cyclodextrin hydroxypropyl substituent derivatives, gamma-cyclodextrin hydroxyethyl substituent derivatives, gamma-cyclodextrin hydroxymethyl substituent derivatives, gamma-cyclodextrin carboxyethyl substituent derivatives, gamma-cyclodextrin ethyl ether substituent derivatives, gamma-cyclodextrin monoglucose substituent derivatives and gamma-cyclodextrin monomaltose substituent derivatives.
In the solubilizing absorbent according to the present invention, preferably, the inorganic base is one or both of sodium hydroxide and potassium hydroxide.
The solubilizing absorbent of the present invention, wherein the anionic surfactant is preferably one or both of sodium oleate and sodium citrate.
The water is water with common water quality, such as tap water, well water, distilled water and the like, or formation water with total mineralization degree not more than 3000 mg/L.
Therefore, the invention also provides a preparation method of the solubilizing absorbent, which is the preparation method of the solubilizing absorbent and comprises the following steps: under the stirring state, firstly, sequentially adding inorganic base, dimethyl sulfoxide, cyclodextrin and derivatives thereof into water, uniformly mixing, then sequentially adding a nonionic surfactant and an anionic surfactant into the water, and uniformly mixing to form the homogeneous solubilization absorbent.
The preparation method of the solubilizing absorbent provided by the invention is preferably that the stirring is low-speed stirring, the rotating speed is 120-180r/min, and the preparation method has the following conditions: the temperature is 10 to 35 ℃, and more preferably 20 to 30 ℃.
Therefore, the invention also provides a method for treating the organic waste gas, which comprises the following steps: firstly, organic waste gas is introduced from the middle lower part of the supergravity device through a fan, meanwhile, the solubilizing absorbent enters from a liquid inlet at the axial upper part of the supergravity device, the treated waste gas is discharged from a gas outlet through a gas channel at the axial upper part of the supergravity device, and the absorbent is recycled.
In the organic waste gas treatment method, the hypergravity factor of the hypergravity device is preferably 50-150, and the liquid-gas ratio is preferably 5-15L/m3。
The invention provides a method for absorbing and treating organic waste gas by utilizing a solubilizing absorbent, which specifically comprises the following steps: organic waste gas is firstly introduced from the middle lower part of the supergravity device through a fan, a solubilizing absorbent enters from a liquid inlet at the axial upper part of the supergravity device, absorption liquid is radially distributed on the surface of a filler along a rotating packed bed under the action of centrifugal force, the waste gas and the absorption liquid are in countercurrent contact on the surface of the filler for gas-liquid mass transfer, organic gas molecules in the waste gas enter a solubilizing absorbent micelle to be dissolved and absorbed, and the treated waste gas is discharged from a gas outlet through a gas channel at the axial direction of the supergravity device.
Preferably, regular packing is filled in the supergravity device, the material of the regular packing is stainless steel wire mesh or stainless steel corrugated plate, and the stainless steel wire mesh regular packing is further preferably selected; the specific surface area of the filler is 900-1400 m2/m3More preferably 1000 to 1300m2/m3。
The organic waste gas is high-concentration hydrocarbon-containing malodorous gas in an oil refining sewage plant, and the concentration of non-methane total hydrocarbons in the waste gas is generally 500-2500 mg/m3。
The principle of the method for absorbing and treating organic waste gas by using the solubilizing absorbent is as follows: the collected high-concentration organic waste gas enters the supergravity device through the fan, the solubilizing absorbent is dispersed into a liquid film, a liquid wire or liquid drops under the action of the packed bed rotating at a high speed, a huge interphase contact area is formed, and meanwhile, the updating rate of a phase interface is very high, so that the gas-liquid mass transfer efficiency can be greatly improved (the mass transfer efficiency is improved by 1-3 orders of magnitude compared with that under the conventional gravity condition), benzene series and other volatile organic matters in the waste gas enter micelles and a nonpolar cavity of the solubilizing absorbent through a gas phase, and the purpose of solubilizing absorption is achieved. The solubilizing absorbent can be recycled, and meanwhile, a certain proportion of fresh solubilizing absorbent is continuously supplemented to the absorption liquid storage tank by the metering pump, so that the solubilizing absorbent in the device has stable adsorption capacity and absorption effect.
In conclusion, the solubilizing absorbent and the hypergravity absorption method are suitable for treating high-concentration organic waste gas in an oil refining sewage field, indexes such as non-methane total hydrocarbon, benzene, toluene and xylene in the treated waste gas can meet the requirements of the emission standard of pollutants for petroleum refining industry (GB31570-2015), and stable standard emission is realized.
Drawings
FIG. 1 is a schematic structural diagram of a hypergravity apparatus in the organic waste gas treatment method of the present invention.
Wherein the content of the first and second substances,
1. the gas is introduced from the gas inlet, and the gas inlet is connected with the gas outlet,
2. a liquid inlet is arranged at the bottom of the shell,
3. a gas outlet is arranged at the bottom of the gas tank,
4. and a liquid outlet.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
Example 1
The preparation of a solubilizing absorbent comprises the following steps:
100kg of solubilizing absorbent is prepared, and the specific preparation process is as follows: adding 33.5kg of tap water into a liquid preparation tank, and adding 3.5kg of sodium hydroxide at a stirring speed of 120 r/min; after the sodium hydroxide is fully dissolved, sequentially adding 30.0kg of dimethyl sulfoxide, 10.0kg of hydroxypropyl-alpha-cyclodextrin and 20.0kg of hydroxypropyl-beta-cyclodextrin; after the substances are fully dissolved, 2.0kg of nonionic gemini surfactant (with the molecular weight of about 1200g/mol) and 1.0kg of sodium oleate are sequentially added, and finally, a stable and transparent homogeneous solubilization absorbent is formed for later use.
(II) organic waste gas treatment:
referring to fig. 1, the method for treating organic waste gas specifically includes the following steps: firstly, organic waste gas is introduced from a gas inlet 1 at the middle lower part of the supergravity device through a fan, meanwhile, the solubilizing absorbent enters from a liquid inlet 2 at the axial upper part of the supergravity device, the treated waste gas is discharged from a gas outlet 3 through an axial gas channel of the supergravity device, the solubilizing absorbent is discharged from a liquid outlet 4, and the solubilizing absorbent is recycled.
At the test site, the waste gas intake of the supergravity device is 100m3Per hour, the circulating amount of the absorption liquid is 1.2m3H, liquid-gas ratio 12L/m3The hypergravity factor is 50-100, the temperature is 25-30 ℃, the used packing is stainless steel corrugated plate regular packing, and the specific surface is 1000m2/m3. The device continuously operates, the inlet gas and the outlet gas are sampled according to the national standard HJ 732-2014, a non-methane total hydrocarbon analyzer and a gas chromatograph are used for analyzing the non-methane total hydrocarbon, benzene, toluene and xylene in the waste gas, and the treatment effects are as follows: the concentration of non-methane total hydrocarbon in the inlet gas is 489-625 mg/m3Benzene concentration of 9.8-16.7 mg/m3, toluene concentration of 12.9-23.6 mg/m3The concentration of xylene is 32.7-40.5 mg/m3The concentration of the export non-methane total hydrocarbon is 96-110 mg/m3The concentration of benzene is 2.6-3.5 mg/m3The concentration of toluene is 3.8-7.1 mg/m3The concentration of xylene is 9.8-12.2 mg/m3And the emission reaching the standard is realized.
Example 2
The preparation of a solubilizing absorbent comprises the following steps:
100kg of solubilizing absorbent is prepared, and the specific preparation process is as follows: adding 27.5kg of tap water into a liquid preparation tank, and adding 3.0kg of potassium hydroxide at a stirring speed of 130 r/min; after the potassium hydroxide is fully dissolved, sequentially adding 35.0kg of dimethyl sulfoxide, 20.0kg of hydroxypropyl-beta-cyclodextrin and 10.0kg of carboxyethyl-gamma-cyclodextrin; after the above materials are fully dissolved, 1.5kg of gemini nonionic surfactant (molecular weight is about 1350g/mol) and 1.5kg of sodium oleate are sequentially added, and finally, a stable and transparent homogeneous solubilization absorbent is formed for standby.
(II) the absorption process of the solubilizing absorbent comprises the following steps:
referring to fig. 1, the method for treating organic waste gas specifically includes the following steps: firstly, organic waste gas is introduced from a gas inlet 1 at the middle lower part of the supergravity device through a fan, meanwhile, the solubilizing absorbent enters from a liquid inlet 2 at the axial upper part of the supergravity device, the treated waste gas is discharged from a gas outlet 3 through an axial gas channel of the supergravity device, the solubilizing absorbent is discharged from a liquid outlet 4, and the solubilizing absorbent is recycled.
At the test site, the waste gas intake of the supergravity device is 100m3Per hour, the circulating amount of the absorption liquid is 1.0m3H, liquid-gas ratio 10L/m3The hypergravity factor is 60-110, the temperature is 20-30 ℃, the used filler is stainless steel wire mesh regular filler, and the specific surface is 1100m2/m3. The device continuously operates, the inlet gas and the outlet gas are sampled according to the national standard HJ 732-2014, a non-methane total hydrocarbon analyzer and a gas chromatograph are used for analyzing the non-methane total hydrocarbon, benzene, toluene and xylene in the waste gas, and the treatment effects are as follows: the concentration of non-methane total hydrocarbon in the inlet gas is 528-685 mg/m3The benzene concentration is 10.5-15.3 mg/m3The concentration of toluene is 13.6-25.8 mg/m3The concentration of xylene is 33.5-41.6 mg/m3The concentration of non-methane hydrocarbon at the outlet is 90-105 mg/m3The concentration of benzene is 2.7-3.4 mg/m3The concentration of toluene is 3.4-6.5 mg/m3And the concentration of dimethylbenzene is 8.4-10.8 mg/m3And the emission reaching the standard is realized.
Example 3
The preparation of a solubilizing absorbent comprises the following steps:
100kg of solubilizing absorbent is prepared, and the specific preparation process is as follows: adding 32.0kg of tap water into a liquid preparation tank, and adding 3.5kg of sodium hydroxide at a stirring speed of 110 r/min; after the sodium hydroxide is fully dissolved, adding 25.0kg of dimethyl sulfoxide, 10.0kg of methyl-alpha-cyclodextrin, 15.0kg of ethyl-beta-cyclodextrin and 10.0kg of hydroxypropyl-gamma-cyclodextrin in sequence; after the substances are fully dissolved, 3.0kg of gemini nonionic surfactant (with the molecular weight of about 1400g/mol) and 1.5kg of sodium citrate are sequentially added to form a stable and transparent homogeneous solubilization absorbent for later use.
(II) the absorption process of the solubilizing absorbent comprises the following steps:
referring to fig. 1, the method for treating organic waste gas specifically includes the following steps: firstly, organic waste gas is introduced from a gas inlet 1 at the middle lower part of the supergravity device through a fan, meanwhile, the solubilizing absorbent enters from a liquid inlet 2 at the axial upper part of the supergravity device, the treated waste gas is discharged from a gas outlet 3 through an axial gas channel of the supergravity device, the solubilizing absorbent is discharged from a liquid outlet 4, and the solubilizing absorbent is recycled.
On the test site, the exhaust gas air inflow of the supergravity device is 100m3Per hour, the circulating amount of the absorption liquid is 1.0m3H, liquid-gas ratio 10L/m3The hypergravity factor is 60-130 ℃, the temperature is 20-30 ℃, the used packing is stainless steel corrugated plate regular packing, and the specific surface is 1200m2/m3. The device continuously operates, the inlet gas and the outlet gas are sampled according to the national standard HJ 732-: the concentration of non-methane total hydrocarbon in the inlet gas is 536-678 mg/m3The benzene concentration is 9.5-13.6 mg/m3The concentration of toluene is 15.2-23.6 mg/m3The concentration of xylene is 31.7-38.9 mg/m3The concentration of non-methane hydrocarbon at the outlet is 91-100 mg/m3The concentration of benzene is 2.0-3.1 mg/m3The concentration of toluene is 3.2-6.0 mg/m3And the concentration of dimethylbenzene is 8.6-11.2 mg/m3And the emission reaching the standard is realized.
Example 4
The preparation of a solubilizing absorbent comprises the following steps:
100kg of solubilizing absorbent is prepared, and the specific preparation process is as follows: 30.0kg of tap water is taken and added into a liquid preparation tank, and 1.5kg of potassium hydroxide is added under the stirring speed of 130 r/min; after potassium hydroxide is fully dissolved, 28.0kg of dimethyl sulfoxide, 12.0kg of ethyl-alpha-cyclodextrin, 15.0kg of hydroxypropyl-beta-cyclodextrin and 13.0kg of carboxymethyl-gamma-cyclodextrin are sequentially added; after the substances are fully dissolved, 2.0kg of gemini nonionic surfactant (with the molecular weight of about 1500g/mol), 0.5kg of sodium citrate and 1.0kg of sodium oleate are sequentially added to form a stable and transparent homogeneous solubilization absorbent for later use.
(II) the absorption process of the solubilizing absorbent comprises the following steps:
referring to fig. 1, the method for treating organic waste gas specifically includes the following steps: firstly, organic waste gas is introduced from a gas inlet 1 at the middle lower part of the supergravity device through a fan, meanwhile, the solubilizing absorbent enters from a liquid inlet 2 at the axial upper part of the supergravity device, the treated waste gas is discharged from a gas outlet 3 through an axial gas channel of the supergravity device, the solubilizing absorbent is discharged from a liquid outlet 4, and the solubilizing absorbent is recycled.
At the test site, the waste gas intake of the supergravity device is 100m3H, circulation volume of absorption liquid is 0.8m3H, liquid-gas ratio 8L/m3The hypergravity factor is 70-130 ℃, the temperature is 25-30 ℃, the used filler is stainless steel wire mesh regular filler, and the specific surface area is 1300m2/m3. The device continuously operates, the inlet gas and the outlet gas are sampled according to the national standard HJ 732-2014, a non-methane total hydrocarbon analyzer and a gas chromatograph are used for analyzing the non-methane total hydrocarbon, benzene, toluene and xylene in the waste gas, and the treatment effects are as follows: the concentration of non-methane total hydrocarbon in the inlet gas is 554-716 mg/m3The concentration of benzene is 10.2-14.8 mg/m3The concentration of toluene is 16.5-25.9 mg/m3The concentration of xylene is 33.2-41.5 mg/m3The concentration of non-methane hydrocarbon at the outlet is 85-95 mg/m3The concentration of benzene is 2.3-3.2 mg/m3The concentration of toluene is 3.5-5.8 mg/m3The concentration of xylene is 9.2-12.5 mg/m3And the emission reaching the standard is realized.
Example 5
The preparation of a solubilizing absorbent comprises the following steps:
100kg of solubilizing absorbent is prepared, and the specific preparation process is as follows: taking 36.2kg of tap water, adding into a liquid preparation tank, and adding 2.5kg of potassium hydroxide at a stirring speed of 120 r/min; after potassium hydroxide is fully dissolved, sequentially adding 20.0kg of dimethyl sulfoxide, 8.0kg of hydroxypropyl-alpha-cyclodextrin, 15.0kg of hydroxypropyl-beta-cyclodextrin and 15.0kg of methyl-gamma-cyclodextrin; after the above materials are fully dissolved, 1.5kg of gemini nonionic surfactant (with the molecular weight of about 1650g/mol) and 1.8kg of sodium oleate are sequentially added, and finally, a stable and transparent homogeneous solubilization absorbent is formed for standby.
(II) the absorption process of the solubilizing absorbent comprises the following steps:
referring to fig. 1, the method for treating organic waste gas specifically includes the following steps: firstly, organic waste gas is introduced from a gas inlet 1 at the middle lower part of the supergravity device through a fan, meanwhile, the solubilizing absorbent enters from a liquid inlet 2 at the axial upper part of the supergravity device, the treated waste gas is discharged from a gas outlet 3 through an axial gas channel of the supergravity device, the solubilizing absorbent is discharged from a liquid outlet 4, and the solubilizing absorbent is recycled.
At the test site, the waste gas intake of the supergravity device is 100m3H, circulation volume of absorption liquid is 0.5m3H, liquid-gas ratio 5L/m3The hypergravity factor is 80-150 ℃, the temperature is 25-30 ℃, the used filler is stainless steel wire mesh regular filler, and the specific surface is 1200m2/m3. The device continuously operates, the inlet gas and the outlet gas are sampled according to the national standard HJ 732-2014, a non-methane total hydrocarbon analyzer and a gas chromatograph are used for analyzing the non-methane total hydrocarbon, benzene, toluene and xylene in the waste gas, and the treatment effects are as follows: the concentration of non-methane total hydrocarbon in the inlet gas is 528-735 mg/m3The benzene concentration is 11.5-15.2 mg/m3The concentration of toluene is 14.8-26.3 mg/m3And the concentration of dimethylbenzene is 35.6-43.8 mg/m3The concentration of non-methane hydrocarbon at the outlet is 80-90 mg/m3The concentration of benzene is 2.5-3.4 mg/m3The concentration of toluene is 3.8-6.2 mg/m3The concentration of xylene is 8.5-10.2 mg/m3And the emission reaching the standard is realized.
From the above examples, it can be seen that the present invention has good implementation effect on the absorption treatment of hydrocarbon-containing waste gas in sewage plants, and the reason analysis is performed from the following two aspects:
1. supergravity absorption process
Volatile organic compounds in hydrocarbon-containing waste gas of the refinery sewage plant are mainly low-carbon alkane and benzene series, and the physical properties of all the components are insoluble in water. Therefore, the contact mass transfer of the volatile organic compounds in the waste gas at the gas-liquid interface is one of the limiting steps. For the absorption method treatment, the treatment process adopted by the general invention patent is carried out in an absorption tower under the conventional gravity condition, and the mass transfer efficiency is lower; the invention is carried out under the condition of supergravity, and the solubilizing absorbent can form tiny liquid drops, liquid threads or liquid films on the surface of the filler rotating at high speed, thereby greatly increasing the contact area of mass transfer and simultaneously greatly improving the update frequency of the contact surface of mass transfer. Compared with the conventional gravity condition, the gas-liquid mass transfer efficiency under the conventional gravity condition can be improved by 1-3 orders of magnitude, so that good mass transfer and absorption effects are achieved.
In addition, the concentration fluctuation range of each component in the hydrocarbon-containing waste gas of the sewage plant is generally dozens of mg/m to dozens of mg/m3The components in the waste gas treated by each comparative patent are relatively single and the concentration fluctuation range is generally hundreds to thousands of mg/m3When the embodiment of the patent is used for treating the hydrocarbon-containing waste gas of the sewage field, the mass transfer driving force of each component is very small, and the mass transfer effect is poor; under the condition of supergravity, the driving force of the low-concentration components is well solved by greatly improving the mass transfer efficiency, and the absorption effect is good.
2. Solubilizing absorbent structure-performance relationship
The key of the solubilizing absorbent for absorbing and treating volatile organic compounds is that organic gas molecules can be quickly adsorbed and stably exist by the solubilizing absorbent micelle and the nonpolar cavity after entering a liquid phase, so that the surfactant lipophilic molecular structure for forming the solubilizing absorbent micelle needs to have good matching property with the organic gas molecular structure so as to realize the maximum adsorption and dissolution. The invention starts from the solubilization absorption principle, and carries out molecular design on the material composition and the structure of a solubilization absorbent: firstly, gemini surfactant, sodium oleate, sodium citrate and the like can greatly reduce the oil-water interfacial tension and provide good mass transfer conditions for organic gas molecules to enter a liquid phase from a gas phase; meanwhile, the gemini surfactant, the sodium oleate, the sodium citrate and the like can form stable micelles in the solution, and the lipophilic group of the gemini surfactant has alkyl and aryl, so that the gemini surfactant has good matching property with organic gas molecules in the waste gas in structure, and the organic gas molecules can stably exist after entering the micelles; the cyclodextrin surfactant can be combined with organic matters entering a cavity in modes of intermolecular force, hydrogen bonds and the like due to a special nonpolar cavity structure, so that the cyclodextrin surfactant can exist stably; and the cyclodextrins with different polymerization degrees have nonpolar cavities with different diameters, and can adsorb alkane and arene with different structures and molecular weights, so that the cyclodextrin has the adjustability in the aspect of solubilization and absorption, and is favorable for solubilization and absorption of mixed gas. In addition, the synergistic effect exists among various surfactants, so that the structure of the interfacial film has more stability and elasticity in the absorption process, and the comprehensive absorption capacity of organic gas molecules is favorably improved.
In conclusion, the solubilizing absorbent and the hypergravity absorption method are suitable for treating high-concentration organic waste gas in an oil refining sewage field, indexes such as non-methane total hydrocarbon, benzene, toluene and xylene in the treated waste gas can meet the requirements of the emission standard of pollutants for petroleum refining industry (GB31570-2015), and stable standard emission is realized.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (10)
1. The solubilizing absorbent is characterized by comprising the following components in percentage by mass based on the total mass of the solubilizing absorbent:
1.0 to 5.0% of a nonionic gemini surfactant,
20.0 to 45.0 percent of cyclodextrin and derivatives thereof,
18.0 to 65% of water,
10.0 to 40.0% of dimethyl sulfoxide,
1.0 to 5.0% of an inorganic base,
0.5 to 2.0% of an anionic surfactant.
2. The solubilizing absorbent according to claim 1, which comprises the following components and their contents based on the total mass of the solubilizing absorbent:
1.5 to 3.5% of a nonionic gemini surfactant,
25.0-40.0% of cyclodextrin and its derivatives,
20.0 to 40% of water,
20.0 to 35.0% of dimethyl sulfoxide,
1.5 to 3.5% of an inorganic base,
0.8-1.8% of anionic surfactant.
3. The solubilizing absorbent according to claim 1, wherein the nonionic gemini surfactant has a structural formula shown below,
wherein, the terminal substituent R1Is C2-10 alkyl or C8-18 alkylphenyl, preferably C14-15 alkylphenyl; intermediate linking group R2An alkyl group or an aryl group having 2 to 6 carbon atoms; the polymerization degree x of the ethylene oxide is 6 to 30, preferably 5 to 35, and more preferably 12 to 25.
4. The solubilizing absorbent of claim 1, wherein the cyclodextrin comprises at least one of a-cyclodextrin, β -cyclodextrin, γ -cyclodextrin.
5. The solubilizing absorbent of claim 1, wherein the derivative group of the cyclodextrin derivative comprises a methyl substituent, an ethyl substituent, a hydroxypropyl substituent, a hydroxyethyl substituent, a hydroxymethyl substituent, a carboxyethyl substituent, an ethyl ether substituent, a monoglucose substituent, a monomaltose substituent.
6. The solubilizing absorbent of claim 1, wherein the cyclodextrin and its derivative is α -cyclodextrin, β -cyclodextrin, γ -cyclodextrin, α -cyclodextrin methyl substituent derivative, α -cyclodextrin ethyl substituent derivative, α -cyclodextrin hydroxypropyl substituent derivative, α -cyclodextrin hydroxyethyl substituent derivative, α -cyclodextrin hydroxymethyl substituent derivative, α -cyclodextrin carboxyethyl substituent derivative, α -cyclodextrin ethyl ether substituent derivative, α -cyclodextrin monoglucose substituent derivative, α -cyclodextrin monomaltose substituent derivative, β -cyclodextrin methyl substituent derivative, β -cyclodextrin ethyl substituent derivative, β -cyclodextrin hydroxypropyl substituent derivative, Beta-cyclodextrin hydroxyethyl substituent derivatives, beta-cyclodextrin hydroxymethyl substituent derivatives, beta-cyclodextrin carboxyethyl substituent derivatives, beta-cyclodextrin ethyl ether substituent derivatives, beta-cyclodextrin monoglucose substituent derivatives, beta-cyclodextrin monomaltose substituent derivatives, gamma-cyclodextrin methyl substituent derivatives, gamma-cyclodextrin ethyl substituent derivatives, two or three of gamma-cyclodextrin hydroxypropyl substituent derivatives, gamma-cyclodextrin hydroxyethyl substituent derivatives, gamma-cyclodextrin hydroxymethyl substituent derivatives, gamma-cyclodextrin carboxyethyl substituent derivatives, gamma-cyclodextrin ethyl ether substituent derivatives, gamma-cyclodextrin monoglucose substituent derivatives and gamma-cyclodextrin monomaltose substituent derivatives.
7. The solubilizing absorbent according to claim 1, wherein the inorganic base is one or both of sodium hydroxide and potassium hydroxide.
8. The solubilizing absorbent according to claim 1, wherein the anionic surfactant is one or both of sodium oleate and sodium citrate.
9. A method for producing the solubilizing absorbent according to any one of claims 1 to 8, characterized by comprising the steps of: under the stirring state, sequentially adding inorganic base, dimethyl sulfoxide, cyclodextrin and derivatives thereof into water, uniformly mixing, then sequentially adding a nonionic gemini surfactant and an anionic surfactant into the water, and uniformly mixing to form a homogeneous solubilization absorbent;
preferably, the stirring is low-speed stirring, the rotating speed is 100-200r/min, and the conditions of the preparation method are as follows: the temperature is 10-35 ℃, preferably 20-30 ℃.
10. A method for treating organic waste gas is characterized by comprising the following steps: firstly, organic waste gas is introduced from the middle lower part of a supergravity device through a fan, the solubilizing absorbent as defined in any one of claims 1 to 8 enters from a liquid inlet at the axial upper part of the supergravity device, the treated waste gas is discharged from a gas outlet through a gas channel at the axial direction of the supergravity device, and the absorbent is recycled;
preferably, the hypergravity factor of the hypergravity device is 50-150, and the liquid-gas ratio is 5-15L/m3。
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