CN112624244A - Method for efficiently removing volatile organic compounds in petrochemical wastewater - Google Patents
Method for efficiently removing volatile organic compounds in petrochemical wastewater Download PDFInfo
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- CN112624244A CN112624244A CN202110022485.4A CN202110022485A CN112624244A CN 112624244 A CN112624244 A CN 112624244A CN 202110022485 A CN202110022485 A CN 202110022485A CN 112624244 A CN112624244 A CN 112624244A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
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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
- B01D53/02—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 adsorption, e.g. preparative gas chromatography
- B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
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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
- B01D53/02—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 adsorption, e.g. preparative gas chromatography
- B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0454—Controlling adsorption
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/06—Arrangements of devices for treating smoke or fumes of coolers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
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- 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
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/40—Further details for adsorption processes and devices
- B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
- B01D2259/40088—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating
- B01D2259/4009—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating using hot gas
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention provides a method for efficiently removing volatile organic compounds in petrochemical wastewater, and belongs to the technical field of atmospheric environmental pollution treatment. The method comprises the steps of sealing and isolating waste gas containing volatile organic compounds dissipated by waste water, collecting the waste gas in a sealed environment by micro negative pressure, and then sending the waste gas into a pretreatment unit to remove particle impurities in the waste gas; the waste gas with the particle impurities removed is sent into an adsorption unit to adsorb volatile organic compounds in the waste gas, and the adsorption reaches the standardDirectly discharging gas, desorbing and regenerating after saturated adsorption, and oxidizing and combusting desorbed gas in a combustion unit to completely decompose organic components in the waste gas into CO2And H2And O. The method has low operation cost, small investment and quick effect, can completely realize automatic control, has the Volatile Organic Compounds (VOCs) removal efficiency of 95 to 99 percent after being treated by the method, and can meet the emission limit requirements of the discharge concentration and the discharge rate of the VOCs in China and places when exhausting.
Description
Technical Field
The invention belongs to the technical field of atmospheric environmental pollution treatment, and particularly relates to a method for efficiently removing volatile organic compounds in petrochemical wastewater.
Background
The petrochemical wastewater comprises wastewater generated in petroleum refining and wastewater generated in petrochemical devices, and the liquid-phase media contain a large amount of Volatile Organic Compounds (VOCs) which mainly comprise benzene, toluene, xylene, styrene, sulfide, acetone, ethyl acetate, methanol, ethanol, propanol, butanol and the like. A large amount of VOCs contained in petrochemical wastewater are volatile to the atmospheric environment, and the waste gas to be treated is intensively collected, so that the waste gas to be treated is characterized by large gas amount, multiple types of organic pollutants, complex composition and low concentration.
The existing process technology for treating Volatile Organic Compounds (VOCs) in petrochemical wastewater has the problems that: 1) the odor is mostly removed by adopting a biological treatment technical method, but the removal effect on Volatile Organic Compounds (VOCs) in the petrochemical wastewater is not good, and the requirement on the discharge concentration of the VOCs in China and places cannot be met. 2) The heat accumulating type organic waste gas incineration technology is adopted to remove Volatile Organic Compounds (VOCs) in petrochemical wastewater, and the waste gas has the main characteristics of large gas amount, low concentration of the Volatile Organic Compounds (VOCs), multiple types of organic pollutants, complex composition, large equipment investment, high energy consumption, high operation cost, low removal efficiency and the like. 3) Volatile Organic Compounds (VOCs) in the petrochemical wastewater contain sulfides, styrene and the like, and the catalyst is easily poisoned and loses activity by catalytic combustion; 4) volatile Organic Compounds (VOCs) in the petrochemical wastewater also contain organic compounds such as styrene and the like, and the method is characterized in that the volatile organic compounds are easy to self-polymerize, a zeolite molecular sieve adsorption method is used, the styrene is easy to self-polymerize, so that adsorbent cavities are blocked, a common regeneration method is difficult to remove, the adsorbent loses adsorption capacity, and the treatment effect is not obvious by using a conventional adsorption-desorption regeneration technology; 5) the activated carbon is adopted for adsorption, the regeneration is difficult, the regeneration temperature cannot be too high by hot air, potential safety hazards exist when the temperature exceeds 120 ℃, the regeneration temperature is low, organic matters with higher boiling points cannot be desorbed, a set of steam regeneration system is needed independently, the investment is large, and the operation cost is high.
Disclosure of Invention
The invention aims to provide a method for efficiently removing volatile organic compounds in petrochemical wastewater, which has the advantages of low operation cost, small investment, quick response and capability of completely realizing automatic control, and exhaust gas meets the requirements of discharge limit values in discharge concentration and discharge rate of national and local VOCs.
The purpose of the invention is realized by the following technical scheme:
a method for efficiently removing volatile organic compounds in petrochemical wastewater comprises the steps of sealing and isolating waste gas containing the volatile organic compounds dissipated by the wastewater, collecting the waste gas in a closed environment by micro negative pressure, and sending the collected waste gas into a pretreatment unit to remove particle impurities in the waste gas; the waste gas of getting rid of particle impurity is sent into the absorption unit, adsorbs the volatile organic compounds in the waste gas, adsorbs gas up to standard and directly discharges, carries out desorption regeneration after adsorbing saturation, and the gas that the desorption was come out gets into the combustion unit and carries out the oxidation combustion, makes the volatile organic compounds in the waste gas thoroughly decompose into CO2And H2O。
Furthermore, the adsorption unit adopts a zeolite molecular sieve adsorber, and after the zeolite molecular sieve is desorbed and regenerated by hot air, cold air is introduced for cooling, so that the adsorption efficiency is ensured.
Further, the temperature of the regenerated hot air is 200-220 ℃; the air volume of the regenerated hot air is controlled to be 1/10-1/15 of the air volume of the treated organic waste gas.
Furthermore, combustion tail gas generated by the combustion unit enters the heat exchanger to recover heat and then is discharged.
Further, the cold air enters the zeolite molecular sieve adsorber through the air blower, then enters the heat exchanger to exchange heat with the combustion tail gas, and returns to the zeolite molecular sieve adsorber as hot air after being heated and warmed for desorption and regeneration.
Further, the control of desorption regeneration of high-boiling-point organic matters and the self-polymers is realized by periodically adopting a program-controlled heating mode to desorb the zeolite molecular sieve adsorber, and the desorption temperature is sequentially operated for a period of time at 230 ℃, 260 ℃, 280 ℃ and 300 ℃ so as to remove the self-polymers. When the zeolite molecular sieve adsorbs organic waste gas, some high-boiling-point substances and styrene and other self-polymers adsorbed in the zeolite molecular sieve are adsorbed in cavities of the molecular sieve, after adsorption saturation, when the adsorbent is desorbed, some high-boiling-point substances are not completely desorbed and styrene and other self-polymers are not desorbed, the adsorption cavities of the adsorbent are blocked, after the operation is carried out for a period of time, the concentration is accumulated, the adsorption capacity of the adsorbent is influenced, a program-controlled heating mode is periodically adopted, the desorption temperature is sequentially carried out at 230 ℃, 260 ℃, 280 ℃ and 300 ℃ for a period of time, the high-boiling-point substances and styrene and other self-polymers accumulated in the adsorbent are thoroughly removed, and the adsorption capacity of the adsorbent is recovered.
Further, the combustion unit is a regenerative type oxidation furnace, the temperature of the oxidation combustion reaction is 800-820 ℃, and the residence time of the oxidation chamber is more than or equal to 1 second.
Furthermore, the concentration of volatile organic compounds in the desorbed gas is more than 10 times of that of the volatile organic compounds in the waste gas.
Further, the pretreatment unit adopts a polymer filter fiber material to remove particle impurities in the exhaust gas. The adsorption method has strict requirements on particles such as dust in the waste gas, prevents the particles from entering an adsorption layer to block micropores of the adsorbent and influence the purification effect, and the particles in the gas must be filtered and intercepted before the waste gas enters the adsorber, and the waste gas is collected and then sent to the pretreatment unit. The skilled person can select the type of the existing polymer filter fiber material according to the use requirement, as long as the effect of removing the particulate impurities in the exhaust gas can be achieved.
Compared with the prior art, the invention has the following beneficial effects:
the invention relates to a treatment method for efficiently removing Volatile Organic Compounds (VOCs) in petrochemical wastewater, which comprises the steps of sending waste gas subjected to pretreatment and particle impurity removal into an adsorption unit (zeolite molecular sieve adsorber), adsorbing the volatile organic compounds in the waste gas, and directly discharging the gas reaching the standard through adsorption; and (3) desorbing and regenerating Volatile Organic Compounds (VOCs) in the waste gas by using hot air after the molecular sieve is adsorbed and saturated, desorbing the Volatile Organic Compounds (VOCs) from the adsorber, and concentrating the concentration of the desorbed Volatile Organic Compounds (VOCs). In the desorption process, the organic waste gas is concentrated, the concentration is improved by ten to fifteen times compared with the original concentration, and the concentration of Volatile Organic Compounds (VOCs) contained in the waste gas is about 200-900 mg/Nm before concentration3After concentration, the concentration of Volatile Organic Compounds (VOCs) reaches more than 2000ppm, and the concentrated waste gas is sent to a combustion unit (regenerative oxidation furnace) and finally decomposed into CO2And H2And discharging the O. The concentration of Volatile Organic Compounds (VOCs) reaches more than 2000ppm, and the combustion unit (regenerative oxidation furnace) can maintain spontaneous combustion without external heating. The desorption regeneration of zeolite molecular sieve adsorber does not use steam, utilizes the heat that the burning unit (regenerative oxidation furnace) burning produced to be available for desorption, so energy resource consumption is low, and this scheme has not only saved the consumption of energy greatly, and because the throughput of burning unit (regenerative oxidation furnace) only needs 1/10 ~ 1/15 of former waste gas treatment capacity in addition, so also reduced the equipment investment simultaneously.
The method for efficiently removing the Volatile Organic Compounds (VOCs) in the petrochemical production wastewater has the advantages of low operation cost, small investment, quick response and complete realization of automatic control, and the Volatile Organic Compounds (VOCs) can reach 95-99% removal efficiency after being treated by the method, and exhaust gas meets the requirements of discharge concentration and discharge rate middle discharge limit value of national and local VOCs.
Drawings
FIG. 1 is a schematic view of the process for efficiently removing Volatile Organic Compounds (VOCs) from petrochemical wastewater in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The specific process for efficiently removing Volatile Organic Compounds (VOCs) in the petrochemical wastewater is as follows:
the method comprises the steps of sealing and isolating waste water and waste gas containing volatile organic compounds dissipated by waste residues in structures such as an oil removal tank, a neutralization tank, an air flotation tank, a regulating tank and a biochemical tank in the petrochemical sewage treatment device, collecting the waste gas in a sealed environment by micro-negative pressure, and then sending the collected waste gas into a pretreatment unit to remove particle impurities in the waste gas through a polymer filter fiber material; the concentration of Volatile Organic Compounds (VOCs) in the waste gas after removing the particle impurities is about 200-900 mg/Nm3。
The waste gas after removing the particle impurities enters a zeolite molecular sieve adsorber, the temperature is controlled below 40 ℃, the zeolite molecular sieve adsorbs Volatile Organic Compounds (VOCs) in the waste gas, and the gas up to the standard is directly discharged after adsorption; after the molecular sieve is adsorbed and saturated, the zeolite molecular sieve is purged by using a certain amount of hot air (200-220 ℃), the concentration ratio is controlled, the air volume of the regenerated hot air is controlled to be 1/10-1/15 of the air volume of the organic waste gas to be treated, organic matters are desorbed from the zeolite molecular sieve, the zeolite molecular sieve is regenerated, and the concentration of the desorbed Volatile Organic Compounds (VOCs) is concentrated to reach more than 2000ppm of the Volatile Organic Compounds (VOCs); the desorbed waste gas containing organic matters is sent into a heat accumulating type oxidation furnace through a fan for oxidation combustion (the oxidation reaction temperature is 800-8℃)The residence time of the oxidation chamber is more than or equal to 1 second at the temperature of 20 ℃) to ensure that Volatile Organic Compounds (VOCs) are thoroughly decomposed into CO2And H2O。
In order to ensure the adsorption efficiency of the regenerated zeolite molecular sieve, cold air is introduced by an air blower for cooling, the cold air enters a heat exchanger after coming out of a zeolite molecular sieve adsorber, and the cold air serving as hot air after absorbing heat from combustion tail gas and raising the temperature returns to the zeolite molecular sieve adsorber again to desorb and regenerate the zeolite molecular sieve with saturated adsorption.
The continuous cycle process of adsorption, desorption, concentration and cooling leads the organic waste gas with large air quantity and low concentration to be concentrated into waste gas with small air quantity and high concentration, and the concentrated waste gas enters a regenerative oxidation furnace for combustion and purification.
And (4) desorption regeneration of high-boiling-point organic matters and control of the self-polymerization. When the zeolite molecular sieve adsorber is used for adsorbing organic waste gas, some high-boiling-point substances and styrene and other self-polymers adsorbed in the zeolite molecular sieve are adsorbed in cavities of the molecular sieve, after adsorption saturation, when the adsorber is desorbed, some high-boiling-point substances are not completely desorbed and styrene and other self-polymers are not desorbed, the adsorption cavities of the adsorber are blocked, after a certain time of operation, the concentration is accumulated to influence the adsorption capacity of the adsorber, a program-controlled heating mode is periodically adopted, the desorption temperature is sequentially controlled at 230 ℃, 260 ℃, 280 ℃ and 300 ℃ for a period of time, so that the high-boiling-point substances and styrene and other self-polymers accumulated in the adsorber are thoroughly removed, and the adsorption capacity of the adsorber is recovered.
And (2) feeding the waste gas into a zeolite molecular sieve adsorber to adsorb volatile organic compounds in the waste gas, desorbing and regenerating the Volatile Organic Compounds (VOCs) in the waste gas by using a certain amount of hot air after the molecular sieve is adsorbed and saturated, desorbing the Volatile Organic Compounds (VOCs) from an adsorber, and concentrating the concentration of the desorbed Volatile Organic Compounds (VOCs). In the desorption process, the organic waste gas is concentrated, the concentration is improved by ten to fifteen times compared with the original concentration, and the concentration of Volatile Organic Compounds (VOCs) contained in the waste gas is 200-900 mg/Nm before concentration3Reaching the concentration of Volatile Organic Compounds (VOCs) above 2000ppm, sending the concentrated waste gas to a regenerative oxidation furnace device, and finally obtaining the finished productIs CO2And H2O is discharged, the concentration of Volatile Organic Compounds (VOCs) reaches more than 2000ppm, and spontaneous combustion can be maintained in the regenerative oxidation furnace without external heating. The desorption regeneration of molecular sieve adsorber does not use steam, utilizes the heat that regenerative oxidation furnace burning produced to be available for desorption, so energy resource consumption is low, and this embodiment has not only saved the consumption of energy greatly, because regenerative oxidation furnace's throughput only needs 1/10 ~ 1/15 of former exhaust gas treatment capacity moreover, so also reduced the equipment investment simultaneously.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. A method for efficiently removing volatile organic compounds in petrochemical wastewater is characterized in that waste gas containing volatile organic compounds dissipated by the wastewater is sealed and isolated, and the waste gas in a sealed environment is collected by micro negative pressure and then sent to a pretreatment unit to remove particle impurities in the waste gas; the waste gas of getting rid of particle impurity is sent into the absorption unit, adsorbs the volatile organic compounds in the waste gas, adsorbs gas up to standard and directly discharges, carries out desorption regeneration after adsorbing saturation, and the gas that the desorption was come out gets into the combustion unit and carries out the oxidation combustion, makes the volatile organic compounds in the waste gas thoroughly decompose into CO2And H2O。
2. The method for efficiently removing volatile organic compounds in petrochemical wastewater as claimed in claim 1, wherein the adsorption unit is a zeolite molecular sieve adsorber, and the zeolite molecular sieve is desorbed and regenerated by hot air and then cooled by introducing cold air to ensure the adsorption efficiency.
3. The method for efficiently removing volatile organic compounds in petrochemical wastewater according to claim 2, wherein the temperature of the regenerated hot air is 200-220 ℃; the air volume of the regenerated hot air is controlled to be 1/10-1/15 of the air volume of the treated organic waste gas.
4. The method for efficiently removing the volatile organic compounds in the petrochemical wastewater as claimed in claim 2, wherein the combustion tail gas generated by the combustion unit enters the heat exchanger to recover heat and then is discharged.
5. The method for efficiently removing the volatile organic compounds in the petrochemical wastewater as claimed in claim 2, wherein the cold air enters the zeolite molecular sieve adsorber through a blower, then enters the heat exchanger to exchange heat with the combustion exhaust gas, and returns to the zeolite molecular sieve adsorber as hot air after heating and temperature rise for desorption and regeneration.
6. The method as claimed in claim 2, wherein the desorption regeneration of high boiling point organic matter and the control of the self-polymerization are carried out by periodically using a programmed temperature raising method to desorb the zeolite molecular sieve adsorber, and the desorption temperature is sequentially operated at 230 ℃, 260 ℃, 280 ℃ and 300 ℃ for a period of time to remove the self-polymerization.
7. The method for efficiently removing volatile organic compounds in petrochemical wastewater as claimed in claim 1, wherein the combustion unit is a regenerative oxidation furnace, the temperature of the oxidation combustion reaction is 800-820 ℃, and the residence time of the oxidation chamber is not less than 1 second.
8. The method for efficiently removing volatile organic compounds in petrochemical wastewater according to claim 1, wherein the concentration of volatile organic compounds in the desorbed gas is more than 10 times of the concentration of volatile organic compounds in the exhaust gas.
9. The method for efficiently removing volatile organic compounds from petrochemical wastewater according to claim 1, wherein the pretreatment unit uses a polymer filter fiber material to remove particulate impurities from the exhaust gas.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114345074A (en) * | 2021-12-27 | 2022-04-15 | 东方电气自动控制工程有限公司 | Centralized treatment method of combustible waste gas |
| CN114849418A (en) * | 2022-04-29 | 2022-08-05 | 浙江天地环保科技股份有限公司 | Coking wastewater dissipation VOCs treatment system and method |
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