CN108745328A - A kind of New Regenerated method of volatile organic contaminant adsorbent - Google Patents

A kind of New Regenerated method of volatile organic contaminant adsorbent Download PDF

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Publication number
CN108745328A
CN108745328A CN201810519310.2A CN201810519310A CN108745328A CN 108745328 A CN108745328 A CN 108745328A CN 201810519310 A CN201810519310 A CN 201810519310A CN 108745328 A CN108745328 A CN 108745328A
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adsorbent
vocs
regeneration
gas
volatile organic
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CN108745328B (en
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张佳
殷瑞
黄文忠
花慧
张伟业
周吉峙
钱光人
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University of Shanghai for Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3408—Regenerating or reactivating of aluminosilicate molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3416—Regenerating or reactivating of sorbents or filter aids comprising free carbon, e.g. activated carbon
    • 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
    • B01D2253/102—Carbon
    • 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
    • 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
    • B01D2253/11—Clays
    • 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
    • B01D2259/40—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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Treating Waste Gases (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

A kind of volatile organic contaminant（VOCs）The New Regenerated method of adsorbent belongs to atmosphere pollution control new technical field.Industrial waste gas of the present invention to contain NOx, SOx and CO makes the adsorbent that absorption VOCs reaches saturation complete to regenerate at a lower temperature for regeneration gas.Its reaction mechanism is VOCs absorption on the sorbent, so that the functional group content of adsorbent surface is promoted 50%-200%, while increasing its reduction effect, is then passed through regeneration gas again, and carrying out reaction makes VOCs mineralisings be CO2, to achieve the purpose that adsorbent reactivation, and the regeneration gas can recycle the regeneration in adsorbent.By the regenerated adsorbent of this method, its specific surface area loss amount is less than 0.05；Average pore size reduction amount is less than 0.3%；Adsorbent mass loss amount is less than 0.1%, and the industrial waste gas being discharged also has reached standard in green emissions, which is a kind of novel, simple, highly efficient regeneration VOCs adsorbents method.

Description

A kind of New Regenerated method of volatile organic contaminant adsorbent
Technical field
The present invention relates to a kind of volatile organic contaminants（VOCs）The New Regenerated method of adsorbent, belongs to atmosphere pollution Object controls new technical field.
Background technology
Volatile organic matter（VOCs）Be it is a kind of at normal atmospheric pressure, fusing point is less than 50-260 DEG C less than room temperature, boiling point Organic compound general name, include mainly alkanes, hydro carbons, esters, alcohols, benzene homologues etc..It is photochemical fog and PM2.5 One of important presoma.Haze event takes place frequently in recent years so that VOCs is monitored and administered to be paid attention to by the whole nation.For VOCs The great demand of improvement, various technologies are constantly born, including absorption method, condensation method, bioanalysis, plasma method and combustion method. But as the industrial source for accounting for artificial VOCs emission sources 55.5%, having VOCs, inorganization is volatilized in the production line, through in a organized way The characteristics of collecting after discharging, forming large-wind-volume low-concentration organic exhaust gas.If directly above method is used to handle, equipment body can be caused Product is excessively huge, and fuel consumption is excessively high, less economical.Therefore, combustion technology often makes ingeniously, to pass through with Adsorption Concentration technical tie-up Adsorbent adsorbs the VOCs components in exhaust gas, then is desorbed and to form small air quantity high-concentration waste gas, into combustion system mineralizing and degrading.Root It is put into effect in May, 2013 according to national government《Volatile organic matter（VOCs）Pollution prevention technique policy》, for low concentration VOCs exhaust gas, non-recovery value is appropriate to the occasion to be handled using Adsorption Concentration-combustion technology.
On the one hand, common combustion technology has heating power burning, heat accumulating type flame combustion in Adsorption Concentration-combustion method（RTO） It burns with catalysis（RCO）.Wherein RCO technologies reaction temperature（300-400°C）Far below flame combustion（760 °C or more）, can pole The big consumption for reducing auxiliary fuel.Catalyst is RCO technological cores, and primarily serving reduces reaction activity and enrichment reactant point The effect of son, the good and bad of performance have extreme influence to VOCs remineralization efficacies and processing energy consumption.Catalyst for catalytic combustion can divide For two class of noble metal and base metal.Noble metal catalyst have higher low-temperature catalytic activity and excellent selectivity, with Pd, Pt be active component loaded catalyst oneself through widely applying in the industry, exist for the initiation temperature of phenyl ring class VOCs 270 °C or so, but its production cost is high, and every cubic metre of price is at 100,000 yuans or more, and anti-toxicity can be poor.Your non-gold The cost of material relative moderate such as metal catalyst, such as Ce, Co, Cu, Mn, has attracted the concern of numerous researchers, still in recent years It is often higher than 300 °C for the initiation temperature of phenyl ring class VOCs.To sum up consider, for qualified discharge and reduces the fortune such as energy consumption Row expense, industrially still tendency uses noble metal catalyst RCO technologies.
And it is activated carbon to apply more adsorbent in a further aspect, in Adsorption Concentration-combustion technology.Activated carbon Raw material sources are extensive, and have many advantages, such as that large specific surface area, hole are flourishing, chemical property is stable, regenerating easily, can Effective absorption VOCs.One big advantage of Adsorption Concentration-combustion method is exactly activated carbon can take certain skill after usage Art carries out desorption and is regenerated, and reduces the cost for administering volatile organic matter to recycle, and save natural resources.It is living The regeneration of property charcoal has the conventional methods such as hot recycling, bio-regeneration and wet air regeneration, but these methods more or less have Regenerated carbon loss is big, and the adsorption effect after regeneration is continuously decreased with increasing for regeneration times.Industrially, acticarbon It is generally possible to adsorption-desorption to use 12 times, will be scrapped later because of the decline of adsorption capacity.Waste active carbon and useless VOCs Catalyst is the same, belongs to hazardous waste, and processing increases the production cost of enterprise.
Therefore, it is badly in need of finding a kind of new technical means, to solve multiple contradictions in current concentration-combustion method technique, packet Include noble metal initiation temperature it is low-price contradiction, high-cheap contradiction of transition-metal catalyst initiation temperature, using catalysis Agent reduces reaction temperature-increase operating cost contradiction, acticarbon is easy to scrap-high the contradiction of waste processing cost.
Invention content
In order to solve many contradictions in current VOCs removals technique, simplifies VOCs Adsorption Concentrations burning process, lowers VOCs removes operating cost, and the present invention provides a kind of brand-new technologies of VOCs adsorbent reactivations so that VOCs adsorbents It is regenerated on the basis of ensureing absorption property, to realize the recycling of adsorption-regeneration-absorption.In the art, using more The queen post reaction tower of the traditional common of layer active carbon layer is processing unit, and the adsorbent of saturation is reached for absorbing VOCs, is adopted It is being matched with a kind of specific group, its regenerated gas can be made, while make the volatile organic contaminant adsorbed on adsorbent decompose, from And realize the regeneration of adsorbent；The gas that a kind of specific group is matched, component and its content (volume %) are: O2（1~ 10%）,NOx（0.5~10%）,SOx(0.5~10%),CO（0.5~10%）,CO2（0.5~10%）And N2（50%~97%）.The spy The gas very assembled, it is 200 ~ 300 DEG C to operate required temperature；Its air speed is 20000h-1；It is 2 ~ 3 hours to need the reaction time. The adsorbent is preferably activated carbon, activated carbon fibre, can also be zeolite molecular sieve, active carbon-supported catalyst, clay Base adsorbent or organic adsorbent.Concrete technology is as described below：
Step 1：The adsorbent for adsorbing VOCs saturations is placed in regeneration reactor.
Step 2：Regeneration reactor is heated to 200-300oC, or with attemperator, will regenerate Gas preheater is to 200-300oC；
Step 3：It is passed through regeneration gas.In addition, the industrial waste gas with similar components can also be used after by components do match In adsorbent reactivation；
Step 4：Gained gas, is passed through carry out adsorbent reactivation, the purpose of recycling is reached, when it again after reaction In after various gases reach discharge standard, discharged.In the process, VOCs mineralisings are CO2, mineralization rate is more than 99%.
The present invention compared with prior art, has obvious prominent substantive distinguishing features and remarkable advantage：
（1）Compared to the reaction temperature 800 of general RTO techniquesoC, this technological reaction temperature are relatively low；
（2）Compared to general RCO techniques 270-300oC, this technological reaction temperature is proximate to it, but this technique does not use price Expensive noble metal catalyst, therefore reduce enterprise operation cost；
（3）Compared to the feature that absorption-catalysis in general activated carbon concentration-RCO techniques is separately reacted, this technology is using absorption- Catalyzing integrated design, reduces equipment input cost；
（4）Noble metal/heavy metal waste is easy tod produce compared to general VOCs absorption or Catalytic processes and activated carbon danger is useless The feature of object, this technology do not generate these solid waste, reduce later stage cost of disposal；
（5）For the gas after regenerative response, can recycle in adsorbent reactivation, when wherein various gases reach discharge mark After standard, green safe discharge may be implemented.
It can be seen that this technique has breakthrough advantage, the operating cost of enterprise and advantageous can be greatly reduced In circular economy and solid waste management and disposition.
Description of the drawings
Fig. 1 is VOCs adsorbent reactivations installation drawing of the present invention.
Specific implementation mode
Details are as follows for the embodiment of the present invention：
Referring to Fig. 1, in the present embodiment, use twin columns tower reactor arranged side by side (A and B) for adsorbent reactivation device, and Laying acticarbon in tower.For using a kind of industrial smoke as regeneration gas, the regeneration gas scale of construction is 3000-7000 m3/ h；Regeneration gas passes through dust-extraction unit；Temperature is 280-300 DEG C after dedusting, comprising 5000 ppm NOx in regeneration gas, 5000 Ppm CO and 5000 ppm SOx etc..The method and step of VOCs adsorbent reactivations is as follows：
A. valve 1 is opened, VOCs is passed through into the tower A for having been loaded into adsorbent, and open valve 5, gas is made to be discharged.Wait for tower After A reaches adsorption saturation, valve 1 and 5 is closed, valve 7 is then opened and is passed through regeneration gas into tower A, and open heater to make Adsorbent temperature is maintained between 200-300 DEG C, opens simultaneously valve 3, and gas after completion of the reaction is made to be discharged, to be regenerated to finish Afterwards, it is again turned on valve 1,5 and is passed through VOCs thereto and adsorbed, achieve the purpose that adsorption-regeneration cycles.
B. when tower A absorption, which finishes, to be regenerated, valve 2 and 6 is opened, VOCs is passed through into tower B and carries out adsorption reaction, is waited for When its absorption reaches saturation, adsorbent is nearly completed regeneration in tower A；At this point, opening valve 4 and 8, regeneration gas is passed through into tower B Body is reacted, and after adsorbent in tower A completes regeneration, is opened valve 1 and 5, is passed through VOCs and is adsorbed.So successively interlock It is reacted, the cycle of the continual adsorption-regeneration of whole system is completed with this.
C. pass through one month follow-on test, the absorption index of adsorbent replys 98% or more, including iodine number and butane value； Specific surface area loss amount is less than 0.05；Average pore size reduction amount is less than 0.3%；Adsorbent mass loss amount is less than 0.1%；After regeneration Adsorbent surface functional group content promotes 50%-200%；And the gas of reaction generation reaches the requirement of discharge standard.

Claims (3)

1. a kind of New Regenerated method of volatile organic contaminant adsorbent, which is characterized in that a kind of by the organic dirt of volatility The adsorbent that object absorbs saturation is contaminated, it is being matched using a kind of specific group, its regenerated gas can be made, while making to adsorb on adsorbent Volatile organic contaminant decomposes, to realize the regeneration of adsorbent；The gas that a kind of specific group is matched, component and its Content (volume %) is: O2（1~10%）,NOx（0.5~10%）,SOx(0.5~10%),CO（0.5~10%）,CO2（0.5~10%）With And N2（50%~97%）, the adsorbent is preferably activated carbon, activated carbon fibre；The gas that the specific group is matched, running Required temperature is 200 ~ 300 DEG C；Its air speed is 20000h-1；It is 2 ~ 3 hours to need the reaction time.
2. a kind of New Regenerated method of volatile organic contaminant adsorbent according to claim 1, it is characterised in that The adsorbent can also be zeolite molecular sieve, active carbon-supported catalyst, clay base adsorbent or organic adsorbent.
3. processing unit used in a kind of volatile organic contaminant adsorbent New Regenerated method, more to be internally provided with The queen post reaction tower of the traditional common of layer active carbon layer.
CN201810519310.2A 2018-05-28 2018-05-28 Regeneration method of volatile organic pollutant adsorbent Active CN108745328B (en)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN110935281A (en) * 2019-04-11 2020-03-31 北京诺维新材科技有限公司 Adsorption and regeneration device and method for solid adsorbent for adsorbing volatile organic compounds
CN113262757A (en) * 2021-06-01 2021-08-17 上海市固体废物处置有限公司 Method for preparing furfural while regenerating waste activated carbon

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110935281A (en) * 2019-04-11 2020-03-31 北京诺维新材科技有限公司 Adsorption and regeneration device and method for solid adsorbent for adsorbing volatile organic compounds
CN110935281B (en) * 2019-04-11 2022-04-15 北京诺维新材科技有限公司 Adsorption and regeneration device and method for solid adsorbent for adsorbing volatile organic compounds
CN113262757A (en) * 2021-06-01 2021-08-17 上海市固体废物处置有限公司 Method for preparing furfural while regenerating waste activated carbon
CN113262757B (en) * 2021-06-01 2022-07-26 上海市固体废物处置有限公司 Method for preparing furfural simultaneously by regenerating waste activated carbon

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