CN107866148A - A kind of VOCs purification methods of petrochemical industry waste gas - Google Patents

A kind of VOCs purification methods of petrochemical industry waste gas Download PDF

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CN107866148A
CN107866148A CN201711270793.9A CN201711270793A CN107866148A CN 107866148 A CN107866148 A CN 107866148A CN 201711270793 A CN201711270793 A CN 201711270793A CN 107866148 A CN107866148 A CN 107866148A
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waste gas
vocs
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CN107866148B (en
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项敬来
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Suzhou fengerda Environmental Technology Co.,Ltd.
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/84—Biological processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/84—Biological processes
    • B01D53/85—Biological processes with gas-solid contact
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/02—Particle separators, e.g. dust precipitators, having hollow filters made of flexible material
    • B01D46/023—Pockets filters, i.e. multiple bag filters mounted on a common frame
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D50/00—Combinations of methods or devices for separating particles from gases or vapours
    • B01D50/60—Combinations of devices covered by groups B01D46/00 and B01D47/00
    • 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
    • B01D53/007—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 irradiation
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/38—Removing components of undefined structure
    • B01D53/44—Organic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75—Multi-step processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/95—Specific microorganisms
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
    • B01D2259/804—UV light
    • 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 discloses a kind of VOCs purification methods of petrochemical industry waste gas, creative make use of adaptability and its bioactivity degradation of the Verticillium lecanii KM9083 bacterial strains to higher concentration VOCs, and the VOCs compositions in waste gas are finally decomposed into H2O and CO2, its biodegradable efficiency to VOCs can meet industrial waste gas purified treatment requirement.Meanwhile the ultra-violet radiation resisting protective action combined using Benzophenone HMPA, the medicament is added in Verticillium lecanii KM9083 bacterial strains in advance, can effectively prevent ultraviolet from acting on the biological inhibition of above-mentioned bacterial strains.

Description

A kind of VOCs purification methods of petrochemical industry waste gas
Technical field
The present invention relates to a kind of VOCs purification methods of petrochemical industry waste gas, the exhaust-gas treatment neck belonged in environmental protection Domain.
Background technology
VOCs is VOC（volatile organic compounds）English abbreviation.Typically VOCs emission sources can be divided into anthropogenic discharge source（Including stationary source and moving source）With natural emission source（Including biological source with it is abiotic Source）Two classes, wherein taking human as based on emission source, mostly for the production process of petrochemical industry related industry, product consumption behavior with And motor-vehicle tail-gas causes.VOCs complicated component, the harm to human body is big, and possessed special odor can cause the kind of human body Kind sense of discomfort, and there is toxicity and excitant.Known many VOCs have neurotoxicity, kidney and hepatotoxicity, or even have Carcinogenesis, blood constituent and cardiovascular system can be damaged, cause gastrointestinal disturbance, induce immune system, internal system and Disease of hematopoietic system, cause metabolic deficiency.A variety of VOCs can act on human body simultaneously in air, produce cumulative effect, and it endangers Degree greatly increases.
Traditional VOCs control technologies are basically divided into two major classes：Recovery technology and destruction technology.Recovery technology is basis The properties of VOCs in itself, by physical method, under certain temperature and pressure, use absorption and sorption agent and selectively penetrating Film etc. realizes VOCs separation, mainly including absorption process, absorption method, condensation method and membrane separation process.And it is then to use to destroy technology Chemistry or biological method, make VOCs gas molecules be changed into the water and carbon dioxide of small molecule, mainly include combustion method and biology Method.
（1）Absorption process：The method of absorption process purifying VOCs is to utilize stripping liquid processing mixed gas, in mixed gas One or more of gas components be dissolved in liquid, or with absorbing liquid component occur selection chemical reaction, remove it The process of middle one or more of gases, so as to reach a kind of method of control atmosphere pollution.The method is suitable for atm number, medium The processing of the waste gas containing VOCs of concentration.
（3）Absorption method：Absorption method is to utilize gaseous mixture of the porous solid sorbent treatment containing VOCs, utilizes solid The unbalanced chemical bond force or molecular attraction on surface, make one or more components therein concentrate on the surface of solids, with up to To the purpose of separation.The active charcoal of conventional adsorbent, NACF, activated alumina, molecular sieve and zeolite etc..
（3）Combustion method：VOCs is converted into carbon dioxide, water and hydrogen chloride etc. is nontoxic or small toxicity by combustion method Inorganic matter process, the method for purification of referred to as burning, its chemical action be mainly under combustion oxidation and high temperature thermal decomposition effect.This Method is applied to administer pernicious gas that is flammable or can decomposing in the case of a high temperature.The advantages of combustion method be clearance compared with Height, typically more than 95%；Shortcoming is that direct combustion method is easily exploded, and wastes heat energy and is also easy to produce secondary pollution, heating power combustion Burning method operating cost is higher.
（4）Condensation method：Condensation method is that have different saturated vapor pressures under different temperature and pressures using VOCs, is led to Reduction temperature and increase pressure are crossed, condenses out the pollutant in steam condition, it is purified and is reclaimed.This method Advantage is that apparatus and process is simple, and energy consumption is low, recyclable useful component；Shortcoming is the organic gas for being not suitable for handling low concentration, right Entrance VOCs requirements are strict, and when chilling temperature is relatively low, power consumption is larger.
（5）Bioanalysis：Bioanalysis is under suitable environmental condition, using the vital movement of microorganism by VOCs gases Harmful substance be transformed into simple inorganic matter（CO2、H2O）And the process of cellular material etc..Common Biochemical method VOCS's Method has：Zinc cation method, biofiltration process and biological island.The advantages of bioanalysis is that clearance is high, small investment, equipment letter Single, operating cost is low, less formation secondary pollution, has a wide range of application；Shortcoming is that microorganism is higher to environmental requirement, crushing compared with Greatly, capacity of resisting impact load is poor, and equipment volume is big, is not suitable for the removal of high halogen compounds.
（6）Membrane separation process：Membrane separation process is utilized under the promotion of pressure differential, and the speed of air penetrating film is different, so as to The process that admixture of gas is separated.The advantages of membrane separation process is that selectivity is good, and strong adaptability, energy consumption is low, no phase-state change, can Reclaim useful component；Shortcoming is that investment is big, strong to the dependence of film；Higher is required to the granule surface contral of film, membrane separation device behaviour It is required height.
At present, the organic waste gas treatment method used both at home and abroad includes absorption and sorption, condensation, burning and biotechnology etc. Methods described above, but the shortcomings of investment is big, the cycle is long, operating cost is high all be present in it, and treatment effect is also difficult to meet Increasingly strict emission request.For this reason, it may be necessary to new method and approach are found to solve this problem.
The content of the invention
In order to solve problems present in prior art, the invention provides a kind of VOCs of petrochemical industry waste gas is net Change method, the petrochemical industry waste gas containing VOCs enter residual-heat exchanger by gas piping, made herein by heat exchange action The waste gas of overheat is cooled and stably, the outlet of residual-heat exchanger connects gas superheat protection device, gas by gas piping The outlet of body overtemperature protection system connects thermal type gas quality flow meter by gas piping, and thermal type gas quality flow meter goes out Mouth connects mixed gas flow regulating valve by gas piping, and the method by importing air adjusts the concentration of VOCs in waste gas, And accurate dilution cooling is carried out to waste gas, the outlet of mixed gas flow regulating valve connects cloth-sack-type dust removal by gas piping Device, the particulate pollutant in waste gas is removed at this, prevents from wearing or blocks back-end processing device, the outlet of fiber bag precipitator leads to Gas piping connection pulsed UV activation-microbial degradation reactor is crossed, pulsed UV activation-microbial degradation reactor goes out Mouthful gas fume washing purifying column is connected by gas piping, carry out further water washing cleaning and cold to the waste gas after processing at this But, the outlet of gas fume washing cooling tower connects air-introduced machine by gas piping, and the outlet of air-introduced machine is connected greatly by gas piping Compression ring border.
Wherein, it is installed in the bacterium solution groove of reactor head and stores Verticillium lecanii liquid and Benzophenone-hexamethyl phosphinylidyne The mixed solution of triamine mixture, meanwhile, porous catheter is filled with inside stainless steel hollow shaft, and be connected with bacterium solution groove, can Above-mentioned mixed solution is conducted to each pure cotton porous fibre bar by capillary conduction, reacts microbial degradation With lasting progress.
The working pressure range of its pulsed UV activation-microbial degradation reactor is 0.03 ~ 0.70MPa, operating temperature Scope is 20 ~ 42 DEG C, dischargeable capacity 260m3。
Its pulsed UV activation-microbial degradation reactor, the operating voltage of pulsed ultraviolet lamp is 25V, and power is 45W, its luminescent spectrum energy are focused primarily upon at 340nm wavelength, and average life was up to 2000 hours.
Its pulsed UV activation-microbial degradation reactor, pure cotton porous fibre strip adoption long-staple cotton are made, fibre length More than 33mm, line density is 7500 public branch or so, strongly more than 5.2cN.
Waste gas after being handled by the system, its VOCs removal efficiency is up to 99.8%.
The advantage of the invention is that：
（1）This method has broken away from existing industrial waste gas VOCs governance models, and creative make use of Verticillium lecanii to higher Concentration VOCs adaptability and its bioactivity degradation, under conditions of pulsed ultraviolet irradiation activation is used in combination, Above-mentioned bacterial strains can play highly efficient VOCs degradations, and its biodegradable efficiency to VOCs can meet industrial waste gas Purified treatment requirement.This method is that very targetedly processing method, its treatment effeciency can reach 98.8% to one kind.
（2）This method takes full advantage of Benzophenone and the ultra-violet radiation resisting protection of HMPA mix reagent is made With it is added in bacterial strain in advance, can effectively prevent ultraviolet from acting on the biological inhibitions of above-mentioned bacterial strains, thoroughly solve bacterium The technical barrier that quasi-microorganism can not survive under ultraviolet irradiation.
（3）This method employs pure cotton porous fibre as Strain Vector, on the one hand possesses good liquid conductive performance, Strain solution can be uniformly distributed；On the other hand, the generation of electrostatic is also prevented from, has fundamentally prevented to be cremated by electrostatic Caused by VOCs gas bursts danger.
（4）This method technology path is advanced, and occupation area of equipment is smaller, and treatment effect is good, operation expense It is very low, be advantageous to a wide range of popularization and application.
Brief description of the drawings
Fig. 1 is the equipment schematic diagram of the present invention.
In figure：1- residual-heat exchangers, 2- gas superheats protection device, 3- thermal type gas quality flow meters, 4- mixed gas Flow control valve, 5- fiber bag precipitators, 6- pulsed UVs activation-microbial degradation reactor, 7- gas fume washings purifying column, 8- Air-introduced machine
Fig. 2 is the schematic diagram of pulsed UV activation-microbial degradation reactor.
61- air intake valves, 62- pulsed ultraviolets lamp, 63- pure cotton porous fibres bar, 64- stainless steels hollow shaft, 65- are more Hole catheter, 66- bacterium solutions groove, 67- motors, 68- drain taps.
Embodiment
As shown in figure 1, the VOCs purification methods of petrochemical industry waste gas, the petrochemical industry waste gas containing VOCs passes through flue Road enters residual-heat exchanger 1, the waste gas of overheat is cooled and stably by heat exchange action herein, and obtained residue Heat is available for utilizing, and the outlet of residual-heat exchanger 1 connects gas superheat protection device 2 by gas piping, and it is when remaining that it, which is acted on, When the failure of heat exchanger 1 or the EGT after heat exchange remain unchanged too high, can temporarily disconnected gas circuit, play protection back-end processing The effect of device, the outlet of gas superheat protection device 2 connect thermal type gas quality flow meter 3 by gas piping, can be to useless The information such as throughput, flow velocity carry out real-time monitoring record, and the outlet of thermal type gas quality flow meter 3 is connected by gas piping to be mixed Gas flow regulating valve 4 is closed, the method by importing air adjusts the actual concentrations of VOCs in waste gas, and waste gas is carried out accurate Dilution cooling, the outlet of mixed gas flow regulating valve 4 connects fiber bag precipitator 5 by gas piping, removed herein useless Particulate pollutant in gas, prevent from wearing or block back-end processing device, the outlet of fiber bag precipitator 5 is connected by gas piping Pulsed UV activation-microbial degradation reactor 6 is connect, the outlet of pulsed UV activation-microbial degradation reactor 6 passes through gas Pipeline connection gas fume washing purifying column 7, further water washing cleaning and cooling, gas fume washing are carried out at this to the waste gas after processing The outlet of cooling tower 7 connects air-introduced machine 8 by gas piping, and the outlet of air-introduced machine 8 connects atmospheric environment by gas piping；Its In, pulsed UV activation-microbial degradation reactor 6 is made up of hard stainless steel, and its left upper portion is provided with air intake valve 61, right Side lower part is provided with drain tap 68, and 1 pulsed uviol lamp 62, reactor bottom are respectively provided with reactor arranged on left and right sides wall 1 motor 67 is installed, connects 1 set of stainless steel hollow shaft 64 thereon, the inside of stainless steel hollow shaft 64 is filled with more Hole catheter 65, porous catheter 65 are connected with the pure cotton porous fibre bar 63 being fixed on outside stainless steel hollow shaft 64, and And porous catheter 65 is also connected with being installed on the bacterium solution groove 66 of reactor head；Waste gas containing VOCs passes through positioned at pulse The air intake valve 61 of UV activation-upper left quarter of microbial degradation reactor 6 enters inside reactor, be now placed in reactor it is left, Pulsed ultraviolet lamp 62 on right two side is opened, can be intermittent to inside reactor spoke with the working method of pulsed Ultraviolet is penetrated, meanwhile, the motor 67 positioned at reactor bottom is opened, and drives the stainless steel quill shaft positioned at reactor center Body 64 starts to rotate with certain rotating speed, and some pure cotton porous fibre bars 63 being fixed on stainless steel hollow shaft 64 are in centrifugal force In the presence of got rid of, with inside reactor waste gas occur sufficiently contact, the lecanium wheel adhered on pure cotton porous fibre bar 63 Branch bacterium under the ultraviolet protection effect of pulsed ultraviolet irradiation activation and Benzophenone-HMPA mixture, Efficient biological respiration can occur, the VOCs compositions in waste gas are finally decomposed to H2O and CO2, by biodegradable net Waste gas after change processing by activated positioned at pulsed UV-drain tap 68 of the right lower quadrant of microbial degradation reactor 6 discharges instead Device is answered, into next treatment process；Wherein, it is installed in the bacterium solution groove 66 of reactor head and stores Verticillium lecanii liquid and benzene The mixed solution of ketone-HMPA mixture, meanwhile, the inside of stainless steel hollow shaft 64 is filled with porous catheter 65, and be connected with bacterium solution groove 66, above-mentioned mixed solution can be conducted to each pure cotton porous fibre by capillary conduction On bar 63, microbial degradation reaction is set to be able to continue progress；Wherein, the work of pulsed UV activation-microbial degradation reactor 6 Pressure limit is 0.03 ~ 0.70MPa, and operating temperature range is 20 ~ 42 DEG C, dischargeable capacity 260m3；Wherein, pulsed UV is lived Change-microbial degradation reactor 6, the operating voltage of its pulsed ultraviolet lamp 62 are 25V, power 45W, its luminescent spectrum energy Focus primarily upon at 340nm wavelength, average life was up to 2000 hours；Wherein, pulsed UV activation-microbial degradation is anti- Device 6 is answered, its pure cotton porous fibre bar 63 is made of long-staple cotton, and fibre length is more than 33mm, and line density is 7500 public branch or so, Strength is more than 5.2cN.
Waste gas after being handled by the system, its VOCs removal efficiency is up to 99.8%.

Claims (3)

1. a kind of VOCs purification methods of petrochemical industry waste gas, it is characterised in that the petrochemical industry waste gas containing VOCs passes through gas Body pipeline enters residual-heat exchanger, the waste gas of overheat is cooled and stably by heat exchange action herein, residual-heat exchanger Outlet by gas piping connect gas superheat protection device, the outlet of gas superheat protection device is connected by gas piping Thermal type gas quality flow meter, the outlet of thermal type gas quality flow meter connect mixed gas flow by gas piping and adjusted Valve, the method by importing air adjust the concentration of VOCs in waste gas, and accurate dilution cooling, mixed gas are carried out to waste gas The outlet of flow control valve connects fiber bag precipitator by gas piping, and the particulate pollutant in waste gas is removed at this, is prevented Abrasion or obstruction back-end processing device, the outlet of fiber bag precipitator connect pulsed UV activation-microorganism by gas piping Degradation reaction device, the waste gas containing VOCs is by activating-the intake valve of microbial degradation reactor upper left quarter positioned at pulsed UV Door enters inside reactor, and the pulsed ultraviolet lamp being now placed on reactor arranged on left and right sides wall is opened, can be with pulsed Working method, it is intermittent to radiate ultraviolet to inside reactor, while opened positioned at the motor of reactor bottom, drive Stainless steel hollow shaft positioned at reactor center starts to rotate with certain rotating speed, is fixed on some on stainless steel hollow shaft Pure cotton porous fibre bar has been got rid of under the influence of centrifugal force, occurs sufficiently to contact with inside reactor waste gas, pure cotton is porous The Verticillium lecanii adhered on ribbon is in pulsed ultraviolet irradiation activation and Benzophenone-HMPA mixture Ultraviolet protection effect under, it may occur that efficient biological respiration, the VOCs compositions in waste gas are finally decomposed to H2O And CO2, the waste gas after biodegradable purified treatment is by activating-microbial degradation reactor right lower quadrant positioned at pulsed UV Drain tap discharge reactor, gas fume washing purifying column is entered by gas piping, at this to the waste gas after processing enter traveling The water washing cleaning of one step and cooling, the outlet of gas fume washing cooling tower connect air-introduced machine, the outlet of air-introduced machine by gas piping Atmospheric environment is connected by gas piping；
Wherein, the working pressure range of pulsed UV activation-microbial degradation reactor is about 0.03 ~ 0.70MPa, operating temperature Scope is about 20 ~ 42 DEG C, dischargeable capacity 260m3；
The pure cotton porous fibre strip adoption long-staple cotton of pulsed UV activation-microbial degradation reactor is made, and fibre length is more than 33mm, line density is 7500 public branch or so, strongly more than 5.2cN.
2. the VOCs purification methods of petrochemical industry waste gas according to claim 1, it is characterised in that pulsed UV activation- The operating voltage of the pulsed ultraviolet lamp of microbial degradation reactor is 25V, power 45W, and its luminescent spectrum energy mainly collects In at 340nm wavelength, average life was up to 2000 hours.
3. the VOCs purification methods of petrochemical industry waste gas according to claim 1, it is characterised in that be installed on reactor top The mixed solution of Verticillium lecanii liquid and Benzophenone-HMPA mixture is stored in the bacterium solution groove in portion, meanwhile, it is stainless Porous catheter is filled with inside steel hollow shaft, and is connected with bacterium solution groove, by capillary conduction by above-mentioned mixed solution On conduction to each pure cotton porous fibre bar, microbial degradation reaction is set to be able to continue progress.
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