WO2020258924A1 - 一种甲醛降解装置及甲醛降解方法 - Google Patents

一种甲醛降解装置及甲醛降解方法 Download PDF

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WO2020258924A1
WO2020258924A1 PCT/CN2020/079328 CN2020079328W WO2020258924A1 WO 2020258924 A1 WO2020258924 A1 WO 2020258924A1 CN 2020079328 W CN2020079328 W CN 2020079328W WO 2020258924 A1 WO2020258924 A1 WO 2020258924A1
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formaldehyde
chamber
degradation device
reaction vessel
formaldehyde degradation
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English (en)
French (fr)
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徐爱玲
宋志文
李慧娟
乔凤禄
袁小懿
李英杰
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Qingdao University of Technology
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Qingdao University of Technology
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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
    • B01D53/46—Removing components of defined structure
    • B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
    • 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
    • B01D2258/00—Sources of waste gases
    • B01D2258/06—Polluted air
    • 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

Definitions

  • the invention belongs to the technical field of air purification equipment, and relates to a formaldehyde degradation device and a formaldehyde degradation method, in particular to a device and method for degrading harmful gas formaldehyde in indoor air based on a microbial method.
  • the commonly used methods of formaldehyde removal mainly include physical adsorption, chemical and microbiological methods: physical adsorption is mainly activated carbon adsorption. Although it can absorb formaldehyde, it also has defects. The passive adsorption of formaldehyde by activated carbon is limited and the efficiency is low.
  • Microbiological method is an emerging formaldehyde treatment method, which has the advantages of low operating cost and no secondary pollution, but it has the problems of low dissolved amount of formaldehyde in direct aeration, poor degradation efficiency, and long degradation time; for example: Chinese patent 201710677599.6 discloses A household formaldehyde removal device relates to the technical field of formaldehyde removal.
  • Formaldehyde absorption system formaldehyde removal system and auxiliary structure.
  • the formaldehyde absorption system includes air inlet, air inlet fan, absorption liquid nozzle, spray absorption cavity, air outlet, water-proof ventilation net, exhaust outlet, liquid collection hopper, formaldehyde
  • the removal system includes a microbial purification column, an absorption liquid tank, an absorption liquid circulation pump, a flow meter, and an absorption liquid emptying pipe.
  • the auxiliary structure includes a housing, a base and a switch.
  • the atomized absorption liquid is used to dissolve the formaldehyde and the immobilized microorganisms are used to degrade and remove the formaldehyde. Therefore, the development of a formaldehyde degradation device based on the microbial method can achieve high-efficiency dissolution and degradation of formaldehyde without causing any harm to the human body, which has high social significance and practical value.
  • the purpose of the present invention is to overcome the shortcomings of the prior art and design a formaldehyde degradation device to maximize degradation and dissolve formaldehyde in the air.
  • a formaldehyde degradation device which includes a main reaction unit, a liquid circulation unit and an air inlet unit.
  • the reaction unit includes a reaction vessel for degrading formaldehyde.
  • the reaction vessel includes at least two chambers.
  • the first chamber of the at least two chambers is provided with an ultrasonic generator, and the second chamber is provided with a microorganism carrier and attached to the microorganism carrier Formaldehyde-reducing bacteria biofilm on the upper;
  • the liquid circulation unit is used to connect the chambers of the reaction vessel to circulate the liquids in different chambers;
  • the air inlet unit transports the formaldehyde-containing gas to the first chamber.
  • the present invention also discloses a formaldehyde degradation method. Based on the above formaldehyde degradation device, optimized process conditions are provided. .
  • the formaldehyde degradation device of the present invention is equipped with an ultrasonic generator and uses low-intensity ultrasonic waves to smash water molecules to dissolve formaldehyde in the water and then be efficiently degraded by formaldehyde-reducing strains, so that the formaldehyde in the air can be dissolved in the liquid with maximum efficiency
  • maximize the dissolution of formaldehyde and use the formaldehyde-reducing strains that grow on the biofilm and use formaldehyde as the only carbon source and nitrogen source to degrade formaldehyde to maximize the degradation of formaldehyde;
  • the formaldehyde degradation device of the present invention has simple structure, convenient use, low cost, strong operability and practicability, can efficiently adsorb and degrade formaldehyde, improve the dissolution rate and degradation rate of formaldehyde, and at the same time purify other pollutants in the air, with the highest efficiency Degrading indoor formaldehyde and improving indoor air quality have very practical practical significance and practical value.
  • Figure 1 is a schematic diagram of the main structure of the present invention.
  • Fig. 2 is a schematic diagram of a cross-sectional view of the main structure of the present invention.
  • Fig. 3 is a linear graph of formaldehyde dissolution rate of ultrasonic generator aeration and direct aeration according to the present invention.
  • FIG. 4 is a schematic diagram of the linear relationship between the frequency of the ultrasonic generator and the inactivation rate of microorganisms according to the present invention.
  • the current microbial formaldehyde treatment method generally has the problems of low dissolved formaldehyde, poor degradation efficiency, and long degradation time in direct aeration.
  • the present invention specifically addresses the above problems and designs a formaldehyde Degradation device to maximize the degradation and dissolution of formaldehyde in the air.
  • the formaldehyde degradation device in this embodiment includes a main reaction unit, a liquid circulation unit, and an air inlet unit.
  • the main reaction unit includes a reaction vessel for degrading formaldehyde, and the reaction vessel includes At least two chambers.
  • the first chamber of the at least two chambers is provided with an ultrasonic generator, and the second chamber is provided with a microorganism carrier and a formaldehyde-reducing bacteria biofilm attached to the microorganism carrier;
  • the liquid circulation unit is used for communication
  • the chamber of the reaction vessel allows liquids in different chambers to circulate; the air inlet unit delivers formaldehyde-containing gas to the first chamber.
  • the air intake unit transports formaldehyde gas (such as indoor air after decoration) to the first chamber.
  • formaldehyde gas such as indoor air after decoration
  • the water molecules in the liquid in the chamber can be shattered. Formaldehyde and water molecules are large Area contact fusion increases the dissolution rate of formaldehyde, so that the liquid in the first chamber contains sufficient formaldehyde.
  • the liquid in the first chamber flows into the second chamber through the liquid circulation unit, so that the formaldehyde dissolved liquid enters the second chamber In the chamber, the formaldehyde stays on the microbial carrier and the biofilm and is degraded.
  • the liquid in the second chamber is transported to the first chamber through the liquid circulation unit to realize the circulation and reuse of the liquid.
  • the biofilm is composed of formaldehyde-degrading strains that use formaldehyde as the sole carbon source and nitrogen source; the present invention can use the formaldehyde-reducing bacteria reported in the prior art, such as methylotrophic bacteria, or some fungi and non-methylotrophic bacteria.
  • Formaldehyde bacteria the current methods of formaldehyde-reducing bacteria to degrade formaldehyde are mainly divided into two categories: assimilation and dissimilation. Assimilation includes serine pathway and ribulose monophosphate pathway (RuMP).
  • the serine pathway transfers the carbon molecules of formaldehyde to Tetrahydrofolate forms methylenetetrahydrofolate and then combines with glycine to form serine; another way of assimilation-RuMP pathway starts with the condensation reaction of formaldehyde and 5-phosphate ribulose (RuMP), and finally produces dihydroacetone phosphate (DHAP).
  • the dissimilation of formaldehyde generally refers to the oxidation pathway of formaldehyde. Formaldehyde is converted into formic acid by formaldehyde dehydrogenase, which then reacts to generate CO 2 and H 2 O.
  • Another formaldehyde oxidation pathway is the cyclization oxidation pathway, which forms formaldehyde and C 5 receptors. The molecules combine to form C 6 compounds into the metabolic cycle.
  • the liquid in the chamber of the reaction vessel is a liquid culture medium for maintaining the activity of formaldehyde-reducing bacteria, for example, a water-soluble liquid medium containing nitrogen sources, carbon sources, and trace elements necessary to maintain the activity of formaldehyde-reducing bacteria.
  • a liquid culture medium for maintaining the activity of formaldehyde-reducing bacteria for example, a water-soluble liquid medium containing nitrogen sources, carbon sources, and trace elements necessary to maintain the activity of formaldehyde-reducing bacteria.
  • the growth of bacteria provides the best nutritional environment and growth conditions.
  • the microbial carrier is set in the second chamber, and the microbial carrier can be selected from nutshell activated carbon, volcanic stone, medical stone, columnar activated carbon, quartz ball, bacterial ball, Nitri microbial fiber ring, ceramsite filter material, culture biological ball And one or more of coral bones.
  • the addition of microbial carriers usually does not increase the degradation ability of formaldehyde-degrading bacteria, but it will speed up the start-up rate and film hanging efficiency under dormant conditions.
  • the selected microbial carrier of the present invention has better effect, strong adhesion of formaldehyde bacteria, fast reproduction, high film-hanging efficiency, and adheres to the formaldehyde degrading bacteria group. Better degradation ability.
  • the position of the microbial carrier in the second chamber is optionally shown in Figure 1.
  • the microbial carrier 13 is arranged at 2/5 of the lower end of the second chamber 7. This position setting can better provide space for microbial film. The film hangs faster.
  • the reaction vessel for degrading formaldehyde may include two chambers or three or more chambers, and the third chamber or more chambers may be similar to the first chamber Or the second chamber works.
  • the third chamber is equipped with a microorganism carrier and a biofilm, and communicates with other chambers through a liquid circulation unit.
  • the chambers of the reaction vessel can be arranged side by side or up and down.
  • two chambers are arranged up and down, and the reaction vessel is divided into a first chamber 6 and a second chamber by a partition 4
  • the chamber 7 is set up and down, so that after the dissolved formaldehyde and air in the first chamber enter the second chamber, because the liquid pressure in the second chamber is greater, the formaldehyde and air are not easy to dissolve out of the water.
  • the formaldehyde-reducing bacteria biofilm degrades the formaldehyde, the liquid pressure decreases when it enters the first chamber through the liquid circulation unit, and the gas dissolved in the liquid after the formaldehyde is removed is easier to dissolve and release.
  • the ultrasonic generator is arranged in the first chamber, and its position can be distributed in the middle, bottom, and side positions of the first chamber, as long as it can promote gas dissolution.
  • the ultrasonic generator 12 is arranged at the bottom of the first chamber 6, and the air inlet unit delivers gas to a position close to the upper part of the ultrasonic generator, so as to promote gas dispersion and dissolution more efficiently.
  • the ultrasonic frequency that the ultrasonic generator can choose to use includes 20KHz, 25KHz, 28KHz, 30KHz, 35KHz, 40KHz, 60KHz, 80KHz, 100KHz, etc.
  • the ultrasonic generator In specific use, consider the ultrasonic generator's inactivation rate of formaldehyde reduction microorganisms and the degradation of formaldehyde in the entire device
  • the effect of the frequency is selected in the range of 30KHz-35KHz low-intensity ultrasonic, the effect is better.
  • the ultrasonic generator studio works in an intermittent mode to find the balance between gas dissolution and liquid circulation, and maximize the dissolution of formaldehyde.
  • the air inlet unit in the formaldehyde degradation device usually includes a pipe for conveying gas or an air inlet channel formed by a partition.
  • the air inlet unit may include an air pump 10, an air pump 10, and a ventilation pipe.
  • One end of the air duct 11 is connected, the other end of the air duct 11 communicates with the first chamber 6, and the other end of the air duct 11 is arranged at a position close to the upper part of the ultrasonic generator.
  • a porous aeration plate or similar structure can be further added to the other end of the aeration pipe 11 to cooperate with the function of the ultrasonic generator, so as to aerate more quickly and increase the dissolution rate of the formaldehyde-containing gas.
  • the liquid circulation unit in the formaldehyde degradation device is used to connect the chambers of the reaction vessel, so that the liquids in different chambers are circulated.
  • the liquid circulation unit can be connected to different chambers of the reaction vessel in a way that is not limited to pipes. There can be two or three pipes. One, four or more, meet the needs of different chamber liquids to achieve circulation.
  • a preferred embodiment of the present invention is shown in Fig. 1, for at least two chambers of the container, the liquid circulation unit includes at least two communicating pipes, and a second chamber is provided between the upper part of the first chamber 6 and the upper part of the second chamber 7.
  • a communicating pipe 16 the first communicating pipe 16 is located above the biofilm at the entrance of the second chamber 7, and a second communicating pipe 17 is provided between the lower part of the first chamber 6 and the lower part of the second chamber 7, so
  • the setting can make the liquid in the first chamber with sufficient amount of formaldehyde dissolved after ultrasound flow into the second chamber through the first pipe, the formaldehyde stays on the microbial carrier and the biofilm and is degraded, after passing through the microbial carrier and the biofilm
  • the formaldehyde-removing liquid is transported to the lower part of the first chamber through the second connecting pipe through the lower part of the second chamber to release the formaldehyde-removed gas dissolved in the liquid.
  • the liquid is again acted by the ultrasonic generator to dissolve the formaldehyde and realize the liquid Recycling and reuse.
  • the connecting pipes can be arranged on the same side of the reaction vessel, or on the opposite side, or arranged around the reaction vessel.
  • a screen should be set between the communication pipe and the chamber of the reaction vessel to prevent large particles in the air and liquid from entering the chamber.
  • the aperture of the screen is also suitable to prevent large particles of pollutants in the air and liquid from entering the chamber.
  • a screen 18 is provided between the first communication pipe 16 and the first chamber 6, and between the second communication pipe 17 and the first chamber 6.
  • the second communication pipe 17 is close to One end of the second chamber 7 is provided with a water pump 19, and the second communication pipe 17 is provided with a check valve 20, and the check valve 20 is above the water pump 19.
  • the water pump 19 provides power for the circulation of the liquid culture medium 15, and transports the liquid culture medium 15 flowing through the microorganism carrier 13 in the second chamber 7 to the first chamber 6 to complete the circulation of the liquid culture medium 15;
  • the check valve 20 is set At 1/10 of the lower end of the lower communicating pipe 17, it is used to prevent the liquid culture medium 15 in the second communicating pipe 17 from returning.
  • the main reaction unit of the formaldehyde degradation device also includes an activated carbon carrier
  • the top wall of the first chamber in the reaction vessel is provided with a second vent, (after the formaldehyde degradation reaction) the gas in the first chamber of the reaction vessel passes through the second After the vent, it is further adsorbed by the activated carbon carrier, thereby improving the removal rate of formaldehyde or other harmful gases in the air.
  • the reaction vessel 1 is divided into a first chamber 6 and a second chamber 7 by a partition 4 and a cover plate 5.
  • the cover plate 5 is fixedly connected to the reaction vessel 1 (the cover plate forms the first chamber).
  • the top wall of the chamber), the cover plate 5 is provided with a second vent 8, and the top side wall of the main reaction unit with an inner hollow structure is provided with a pair of first vents 2 arranged below the first vent 2
  • the first vent 2 and the second vent 8 provide outlets for the degraded and purified air; the activated carbon carrier 3 absorbs undegraded formaldehyde and other toxic gases in the air, which can increase formaldehyde and other toxic hazards in the air. Degradability of gas.
  • a baffle 9 can be provided below the second vent 8 to block the water waves that are shattered and oscillated by the ultrasonic generator 12 from passing through the second vent 8.
  • the reaction vessel 1 involved in this embodiment has a rectangular parallelepiped structure, and the side wall can also be provided with an opening and closing door for easy access to the inside of the reaction vessel 1 for inspection and maintenance, to increase the service life and aesthetics, and it is convenient to move.
  • the first chamber 6 and the second chamber 7 of the reaction vessel can also be provided with valves that facilitate the filling, renewal and discharge of the liquid culture medium 15, which is convenient for application.
  • reaction vessels can be provided, or multiple groups of main reaction units can be provided.
  • multiple formaldehyde degradation devices of the present invention under permitted conditions.
  • the formaldehyde degradation device of the present invention may also include a temperature control device for controlling the temperature of the liquid culture medium and promoting the occurrence of the formaldehyde degradation reaction.
  • the formaldehyde degradation device of this embodiment can be applied to various environments, and is particularly suitable for removing formaldehyde in an indoor environment.
  • the specific formaldehyde degradation device is shown in Figures 1 to 2.
  • the air pump 10 draws the indoor air containing formaldehyde into the first chamber 6 through the ventilation pipe 11, and the ultrasonic generator 12 Working intermittently, the water molecules in the first chamber 6 are shattered, and the formaldehyde and the water molecules come into contact and fuse in a large area, so that the liquid medium 15 in the first chamber 6 contains sufficient formaldehyde.
  • the liquid culture medium 15 in the medium flows into the second chamber 7 through the first connecting pipe 16, so that the formaldehyde enters the second chamber 7, and the formaldehyde stays on the microbial carrier 13 and the biofilm 14 and is degraded.
  • the liquid is transported to the first chamber 6 through the water pump 19 and the second connecting pipe 17, and the released gas is discharged into the room through the second vent 8, the activated carbon carrier 13, and the first vent 2 in sequence.
  • the undegraded gas enters the room after being adsorbed and degraded by the activated carbon carrier 13, which improves the degradation rate of formaldehyde or other harmful gases in the air.
  • the power provided by the water pump 19 passes through the second connecting pipe 17 to transfer the lower end of the second chamber 7
  • the liquid culture medium 15 is delivered to the first chamber 6 to realize the circulation and reuse of the liquid culture medium 15.
  • the indoor formaldehyde degradation device involved in this embodiment uses ultrasonic generator 12 for aeration and the prior art formaldehyde degradation device uses direct aeration to dissolve formaldehyde with a concentration of 3.0 mg/L, respectively, and formaldehyde dissolution measured by high performance liquid chromatography
  • the formaldehyde dissolution rate of ultrasonic generator 12 aeration is higher than that of direct aeration; when the frequency of ultrasonic generator 12 is 40KHz, the formaldehyde dissolution rate is the largest; ultrasonic generator 12 is effective against formaldehyde reducing bacteria It has inactivation effect.
  • formaldehyde degradation rate initial dissolution rate of formaldehyde-final dissolution rate of formaldehyde, when the reflux ratio is 100%, the degradation rate of formaldehyde is the highest and the rate of microbial inactivation is the lowest.
  • the frequency of the ultrasonic generator 12 and the reflux ratio of the first chamber 6 of the indoor formaldehyde degradation device involved in this embodiment have the greatest influence on the formaldehyde dissolution rate and the survival rate of microorganisms.
  • the power of the ultrasonic generator 12 in Example 3 is 38W
  • the survival rate of microorganisms is the highest
  • the reflux ratio in Example 4 is 100%
  • the degradation rate of formaldehyde is the highest and the microorganism inactivation rate is the lowest.
  • the inactivation rate of formaldehyde reducing bacteria is the lowest, the survival rate is the highest, and the microorganism inactivation rate in the circulating liquid is 42.6%.
  • the microorganism inactivation rate on the carrier is 9.2%.
  • the formaldehyde dissolution rate and degradation rate are both high, the formaldehyde dissolution rate is 81.0%, and the formaldehyde degradation rate is 77.5%.
  • the indoor formaldehyde degradation device involved in this embodiment can fully meet the requirements for degrading indoor formaldehyde.

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Abstract

一种室内甲醛降解装置及甲醛降解方法，基于微生物降解室内空气中的有害气体甲醛，设有超声波发生器（12），采用低强度超声波震碎水分子，使甲醛溶解于水中，继而被降甲醛菌株高效降解，最大效率让空气中甲醛溶于液体培养基中，实现甲醛溶解的最大化，利用生物膜上面生长的以甲醛为唯一碳源和氮源的降甲醛菌株来降解甲醛，实现甲醛降解的最大化。

Description

一种甲醛降解装置及甲醛降解方法 技术领域：
本发明属于空气净化设备技术领域，涉及一种甲醛降解装置及甲醛降解方法，尤其涉及一种基于微生物法降解室内空气中的有害气体甲醛的装置及方法。
背景技术：
室内空气污染对人体健康的威胁触目惊心，其中甲醛更成为健康的“隐形杀手”。中国消费者协会公布过一项调查结果：抽样检测新装修的住房中有七成含有有毒气体，新装修房子室内甲醛超标达75％以上，有些浓度甚至可达到3.0mg/L。在这样的新居中，人们往往出现头痛、头晕、过敏性疲劳和眼、鼻、喉刺痛等不适感，世界卫生组织(WHO)将此现象称为“病态建筑物综合征”。基于此，对室内空气甲醛的降解净化尤为重要，“健康呼吸”已成为迫切需要。
目前常用的甲醛去除方式主要有物理吸附法，化学法和微生物法：物理吸附法主要为活性炭吸附法，虽然可以吸收甲醛，但是也存在缺陷，活性炭对甲醛的被动吸附作用范围有限，效率低，若重复使用操作麻烦且仅仅是吸收甲醛并不能实现降解甲醛的目的；化学法降解甲醛的作用较快，但是药剂消耗量大，成本高，更换麻烦，存在产生其他更难降解的污染物的可能性；微生物法是新兴的甲醛处理方法，具有运行费用低，无二次污染的优点，但是存在直接曝气甲醛溶解量少，降解效率差，降解时间长等问题；例如：中国专利201710677599.6公开的一种家用除甲醛装置，涉及除甲醛技术领域。包括：壳体、进风口、出风口、紫外线灯、甲醛吸附网、活性炭吸附网和微生物净化柱、吸收液槽、固定板以及风机；甲醛吸附网上浸润有二氧化钛溶液；微生物净化柱内设有经过活化的固定化微生物小球；吸收液槽内装有三聚氰胺溶液；可通过紫外线灯照射甲醛吸附网上的二氧化钛溶液使其发生光催化反应，从而氧化分解空气中的甲醛；通过微生物净化柱内的固定化微生物小球降解甲醛；通过活性炭吸附网对室内空气进行净化；最后通过吸收液槽内的三聚氰胺溶液进一步吸收甲醛；中国专利201410607342.X公开的一种除甲醛空气净 化器，属于环保技术领域，由甲醛吸收系统、甲醛去除系统和附属结构组成，甲醛吸收系统包括进气口、进气风机、吸收液喷头、喷淋吸收腔、过风口、隔水透气网、排气口、集液斗，甲醛去除系统包括微生物净化柱、吸收液槽、吸收液循环泵、流量计、吸收液排空管，附属结构包括外壳、底座和开关，利用雾化吸收液溶解甲醛、利用固定化微生物降解去除甲醛。因此研发一种基于微生物法的甲醛降解装置，实现高效溶解降解甲醛、对人体不产生任何伤害，具有很高的社会意义及实用价值。
发明内容：
本发明的目的在于克服现有技术存在的缺点，设计一种甲醛降解装置，实现最大化降解和溶解空气中的甲醛。
为了解决目前降解甲醛过程中直接曝气甲醛溶解量少、降解效率差、降解时间长等的问题，本发明公开了一种甲醛降解装置，包括主反应单元、液体循环单元和进气单元，主反应单元包括用于降解甲醛的反应容器，反应容器包括至少两个腔室，至少两个腔室中的第一腔室内设置有超声波发生器，第二腔室内设置有微生物载体及附着于微生物载体上的降甲醛菌生物膜；液体循环单元用于连通反应容器的腔室，使得不同腔室内的液体循环；进气单元将含甲醛气体输送至第一腔室。
此外，为了更好利用甲醛降解装置，提升甲醛降解效率、提高降甲醛菌存活率、降低降甲醛菌损耗，本发明还公开了一种甲醛降解方法，基于上述甲醛降解装置，提供优化的工艺条件。
本发明的技术方案取得了以下有益效果：
本发明甲醛降解装置与现有技术相比，设有超声波发生器，采用低强度超声波震碎水分子，使甲醛溶解于水中，继而被降甲醛菌株高效降解，最大效率让空气中甲醛溶于液体培养基中，实现甲醛溶解的最大化，利用生物膜上面生长的以甲醛为唯一碳源和氮源的降甲醛菌株来降解甲醛，实现甲醛降解的最大化；
本发明甲醛降解装置结构简单、使用方便、成本低，操作性和实用性强，能够高效吸附和降解甲醛，提高甲醛的溶解率和降解率，同 时对空气中其他污染物也有净化作用，最高效率降解室内甲醛，提高室内空气质量，具有非常实用的现实意义和实用价值。
附图说明：
图1为本发明的主体结构原理示意图。
图2为本发明的主体结构剖视原理示意图。
图3为本发明涉及的超声波发生器曝气与直接曝气的甲醛溶解率线性图。
图4为本发明涉及的超声波发生器频率与微生物灭活率的线性关系示意图。
具体实施方式：
下面通过实施例并结合附图对本发明作进一步说明。应该指出，以下详细说明都是示例性的，旨在对本申请提供进一步的说明。除非另有指明，本发明使用的所有技术和科学术语具有与本申请所属技术领域的普通技术人员通常理解的相同含义。
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本申请的示例性实施方式。如在这里所使用的，除非本发明另外明确指出，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。
为了方便叙述，本发明中如果出现“上”、“下”、“左”“右”字样，仅表示与附图本身的上、下、左、右方向一致，并不对结构起限定作用,仅仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的设备或元件必须具有特定的方位，以特定的方位构造和操作，因此不能理解为对本发明的限制。
正如背景技术所介绍的，目前基于微生物法甲醛处理方法，普遍存在直接曝气甲醛溶解量少、降解效率差、降解时间长等问题，本发明有针对性的对于上述问题，设计了一种甲醛降解装置，实现最大化降解和溶解空气中的甲醛。
实施例1：
如图1-图2所作示例但不限于此，本实施方式中的甲醛降解装 置，包括主反应单元、液体循环单元和进气单元，主反应单元包括用于降解甲醛的反应容器，反应容器包括至少两个腔室，至少两个腔室中的第一腔室内设置有超声波发生器，第二腔室内设置有微生物载体及附着于微生物载体上的降甲醛菌生物膜；液体循环单元用于连通反应容器的腔室，使得不同腔室内的液体循环；进气单元将含甲醛气体输送至第一腔室。
进气单元将含有甲醛气体(如装修后的室内空气等)输送至第一腔室，第一腔室内的超声波发生器工作后可将腔室内的液体中水分子震碎，甲醛与水分子大面积接触融合，增加甲醛的溶解率，从而使得第一腔室的液体中含有足量甲醛，第一腔室中的液体通过液体循环单元流入第二腔室，使甲醛溶解的液体进入第二腔室，甲醛在微生物载体和生物膜上停留并被降解，同时，通过液体循环单元将第二腔室的液体输送到第一腔室，实现液体的循环和重复利用。
生物膜为以甲醛为唯一碳源和氮源的降解甲醛菌株组成；本发明可以采用现有技术中报道的降甲醛解菌，例如甲基营养型细菌，或一些真菌和非甲基营养菌降甲醛菌，目前降甲醛菌降解甲醛的方式主要分为同化作用和异化作用两大类途径，同化作用包括丝氨酸途径和核酮糖单磷酸途径(RuMP)，丝氨酸途径是将甲醛的碳分子转移到四氢叶酸上形成亚甲基四氢叶酸，然后与甘氨酸结合形成丝氨酸；同化的另一条途径-RuMP途径开始于甲醛和5-磷酸核酮糖(RuMP)的缩合反应，最终生成磷酸二氢丙酮(DHAP)。甲醛的异化作用一般指甲醛的氧化途径，通过甲醛脱氢酶将甲醛转化为甲酸，而后反应生成CO 2和H 2O，另一种甲醛氧化途径为环化氧化途径，甲醛与C 5受体分子结合形成C 6化合物进入代谢循环。
反应容器中腔室内的液体为用于维持降甲醛菌活性的液体培养基，例如包括维持降甲醛菌活性所必须的氮源、碳源、微量元素等的水溶性液体培养基，能够为降甲醛菌的生长提供最好的营养环境和生长条件。
微生物载体设置于第二腔室内，微生物载体可选的由果壳活性炭、火山石、麦饭石、柱状活性炭、石英球、细菌球、尼特利微生物 纤维环、陶粒滤料、培养生物球和珊瑚骨中的一种或几种组成。微生物载体的添加通常不会提高甲醛降解菌的降解能力，但会加快其在休眠条件下的启动速率和挂膜效率。相较于常见的碳酸钙和钙基膨润土等微生物载体材料，本发明所选的微生物载体效果更优，甲醛菌附着能力强，繁殖快、挂膜效率高，附着于其上甲醛降解菌群的降解能力更优。微生物载体在第二腔室的位置，可选的如图1所示，微生物载体13设置在第二腔室7下端的2/5处，该位置设置可以更好的为微生物挂膜提供空间，较快挂膜。
本发明其他实施例中，用于降解甲醛的反应容器，可以包括两个腔室，也可以包括三个或更多个腔室，第三腔室或更多个腔室可以如第一腔室或第二腔室发生作用，例如第三腔室中设置微生物载体和生物膜，并通过液体循环单元与其他腔室连通。
反应容器的腔室可以并排设置也可以上下设置，较佳的实施例子中例如图1所示，两个腔室上下设置，通过隔板4将反应容器间隔为第一腔室6和第二腔室7，通过上下方式设置，可以使得第一腔室中溶解的甲醛及空气进入第二腔室后，因第二腔室内液体压力更大，甲醛及空气不易从水中溶出，第二腔室的降甲醛菌生物膜降解甲醛后，通过液体循环单元进入第一腔室时液体压强减少，除甲醛后溶解在液体中的气体更容易溶出释放。
本实施例中超声波发生器设置于第一腔室中，其位置可以分布于第一腔室的中部、底部、侧边位置，只要能促进气体溶解发生即可。优选的方式中，如图1中，将超声波发生器12设置于第一腔室6的底部，进气单元输送气体至超声发生器的上部接近的位置，以便于更大效率的促进气体分散溶解。超声波发生器可以选择使用的超声波频率包括20KHz、25KHz、28KHz、30KHz、35KHz、40KHz、60KHz、80KHz、100KHz等，具体使用时，考虑到超声波发生器对于降甲醛微生物灭活率和整个装置甲醛降解率的影响，超声波频率选择在30KHz-35KHz范围内低强度超声波，效果更好。此外，超声波发生器工作室采用间歇模式工作，以寻求气体溶解和液体循环输送的平衡，实现甲醛溶解最大化。
甲醛降解装置中的进气单元通常包括输送气体的管道或隔板形成的进气通道等，较优的实施例子中，如图1所示，进气单元可以包括气泵10，气泵10与通气管道11的一端连接，通气管道11的另一端与第一腔室6连通，通气管道11的另一端设置于超声发生器的上部接近的位置。当然，在通气管道11的另一端可以进一步增加多孔的曝气盘或类似结构，以配合超声发生器的作用，从而可以更为快速的曝气、增加含甲醛气体溶解速率。
甲醛降解装置中的液体循环单元用于连通反应容器的腔室，使得不同腔室内的液体循环，液体循环单元可以采用不限于管道方式来连通反应容器的不同腔室，管道可以有2个、3个、4个或更多个，满足不同腔室液体实现循环即可。较优的实施例如本发明图1中，针对容器的至少两个腔室，液体循环单元包括至少两个连通管道，第一腔室6的上部与第二腔室7的上部之间设置有第一连通管道16，第一连通管道16在第二腔室7的入口位于生物膜的上方，第一腔室6的下部与第二腔室7的下部之间设置有第二连通管道17，这样设置，可以使得超声后溶解有足量甲醛的第一腔室中的液体，通过第一管道流入第二腔室，甲醛在微生物载体和生物膜上停留并被降解，经过微生物载体和生物膜后的去甲醛液体，通过第二腔室下部经第二联通管道输送到第一腔室下部，释放溶解在液体中的去除甲醛后气体，液体再次被超声发生器作用，用于溶解甲醛，实现液体的循环和重复利用。连通管道布设方式可以选择位于反应容器同侧，或异侧，或以环绕反应容器方式布设等。
进一步的，甲醛降解装置中，为维持装置的长时间运行稳定性，连通管道与反应容器的腔室之间应设置有筛网，用于阻挡空气和液体中的大颗粒污染物进入腔室，筛网的孔径也以阻挡空气和液体中的大颗粒污染物进入腔室为宜。例如，如图1所示，第一连通管道16与第一腔室6之间、第二连通管道17与第一腔室6之间均设置有筛网18，此外，第二连通管道17靠近第二腔室7的一端设置有水泵19，第二连通管道17设置有止回阀20，止回阀20在水泵19的上方。水泵19为液体培养基15的循环提供动力，将第二腔室7中流经微生物 载体13的液体培养基15输送到第一腔室6，以完成液体培养基15的循环；止回阀20设置于下连通管道17下端的1/10处，用于防止第二连通管道17中的液体培养基15回流。
进一步的，甲醛降解装置的主反应单元还包括活性炭载体，反应容器中的第一腔室顶壁开设有第二通风口，(甲醛降解反应后)反应容器第一腔室中的气体经第二通风口后通过活性炭载体进一步吸附，从而提高甲醛或空气中其他有害气体的去除率。具体的，可以如图1所示，反应容器1由隔板4和盖板5分隔成第一腔室6和第二腔室7，盖板5与反应容器1固定连接(盖板形成第一腔室的顶壁)，盖板5开设有第二通风口8，内空式结构的主反应单元的顶端侧壁开设有成对布置的第一通风口2，第一通风口2的下方设置有活性炭载体3。该方案中，第一通风口2和第二通风口8为降解净化后的空气提供出口；活性炭载体3吸收未降解的甲醛和空气中其他有毒害的气体，能够提高甲醛和空气中其他有毒害气体的降解能力。此外，在第二通风口8下方还可以设置挡板9，用于阻挡被超声波发生器12震碎而震荡起来的水波通过第二通风口8。
优选的方案中，本实施例涉及的反应容器1为长方体结构，在侧壁还可以设置有便于进入反应容器1内部进行检修和维护的开关门，以增加使用年限和美观程，移动方便，结构简单易操作；在反应容器的第一腔室6和第二腔室7还可以设置有便于液体培养基15灌装、更新和排出的阀门，方便应用。
为了更为快速和充分的去除一定空间内的甲醛，反应容器可以设置多个，抑或是主反应单元设置多组，当然使用多个本发明的甲醛降解装置在允许的条件下也是可行的。
此外，本发明的甲醛降解装置还可以包括温控装置，用于控制液体培养基的温度，促进甲醛降解反应的发生。
本实施例的甲醛降解装置可以应用于多种环境，尤其适用于室内环境去除甲醛。
实施例2：
如图1-图2所示具体的甲醛降解装置，本实施例涉及的室内甲醛降解装置使用时，气泵10通过通气管道11将含有甲醛的室内空气抽入第一腔室6，超声波发生器12间歇工作，将第一腔室6中的水分子震碎，甲醛与水分子大面积接触融合，使第一腔室6中的液体培养基15中含有足量甲醛，同时，第一腔室6中的液体培养基15通过第一连通管道16流入第二腔室7，使甲醛进入第二腔室7，甲醛在微生物载体13和生物膜14上停留并被降解，被降解的含溶解气体的液体通过水泵19和第二连通管道17被输送至第一腔室6，释放的气体依次经过第二通风口8、活性炭载体13和第一通风口2排入室内。其中，未被降解的气体通过由活性炭载体13吸附降解后进入室内，提高了甲醛或空气中其他有害气体的降解率，水泵19提供的动力通过第二连通管道17将第二腔室7下端的液体培养基15输送到第一腔室6，实现液体培养基15的循环和重复利用。
实施例3：
本实施例涉及的室内甲醛降解装置采用超声波发生器12曝气与现有技术中的甲醛降解装置采用直接曝气分别溶解浓度为3.0mg/L的甲醛，利用高效液相色谱法测定的甲醛溶解率如图3所示，超声波发生器12曝气的甲醛溶解率高于直接曝气的甲醛溶解率；超声波发生器12的频率为40KHz时，甲醛溶解率最大；超声波发生器12对降甲醛菌有灭活作用，不同超声条件下样品微生物灭活率(i)的计算公式为：i＝(1-Nt/N0)×100％，其中，Nt为超声处理后水样中微生物菌落数，cfu/mL；N0为超声处理前水样中微生物菌落数，cfu/mL；随着超声时间的增加，微生物灭菌率先呈上升趋势，后呈下降趋势，超声时间在20min时，微生物灭菌率达到最大，超声波发生器12在间歇工作20min后(间歇：工作＝8:2)，在不同超声波发生器12的频率下的微生物灭活率，如图4所示，超声波发生器12的功率为38W，频率为30KHz时，微生物存活率最高。
实施例4：
本实施例涉及的室内甲醛降解装置的上腔室6的不同回流比对 液体培养基15的停留时间、降甲醛菌灭活率和甲醛降解率的影响结果如下表：
Figure PCTCN2020079328-appb-000001
其中：甲醛降解率＝甲醛最初溶解率-甲醛最终溶解率，回流比为100％时，甲醛降解率最高，微生物灭活率最低。
实施例5：
本实施例涉及的室内甲醛降解装置的超声波发生器12的频率和第一腔室6的回流比对甲醛溶解率和微生物存活率影响最大。基于实施例3中超声波发生器12的功率为38W时，微生物存活率最高，以及实施例4中回流比为100％时，甲醛降解率最高，微生物灭活率最低的影响。设置最优频率和回流比如下表：
Figure PCTCN2020079328-appb-000002
通过控制变量法对频率和回流比的优化从而对微生物灭活率和甲醛降解率的影响如下表：
Figure PCTCN2020079328-appb-000003
Figure PCTCN2020079328-appb-000004
如上表结果所述在超声波发生器12的频率为35KHz，第一腔室6的回流比为100％时，降甲醛菌灭活率最低，存活率最高，循环液体内微生物灭活率为42.6％，载体上微生物灭活率为9.2％。且甲醛溶解率和降解率都较高，甲醛溶解率为81.0％，甲醛降解率为77.5％。此时本实施例涉及的室内甲醛降解装置完全可以满足降解室内甲醛的需求。

Claims (10)

  1. 一种甲醛降解装置，其特征在于，包括主反应单元、液体循环单元和进气单元，主反应单元包括用于降解甲醛的反应容器，反应容器包括至少两个腔室，至少两个腔室中的第一腔室内设置有超声波发生器，第二腔室内设置有微生物载体及附着于微生物载体上的降甲醛菌生物膜；液体循环单元用于连通反应容器的腔室，使得不同腔室内的液体循环；进气单元将含甲醛气体输送至第一腔室。
  2. 根据权利要求1所述的一种甲醛降解装置，其特征在于，微生物载体设置于第二腔室内，微生物载体可选的由果壳活性炭、火山石、麦饭石、柱状活性炭、石英球、细菌球、尼特利微生物纤维环、陶粒滤料、培养生物球和珊瑚骨中的一种或几种组成。
  3. 根据权利要求1所述的一种甲醛降解装置，其特征在于，超声波发生器设置于第一腔室的底部，进气单元输送气体至超声发生器的上部接近的位置。
  4. 根据权利要求1-3任一项所述的一种甲醛降解装置，其特征在于，进气单元包括气泵和通气管道，气泵与通气管道的一端连接，通气管道的另一端与第一腔室连通，通气管道的另一端设置于超声发生器的上部接近的位置。
  5. 根据权利要求1-3任一项所述的一种甲醛降解装置，其特征在于，液体循环单元包括至少两个连通管道，第一腔室的上部与第二腔室的上部之间设置有第一连通管道，第一连通管道在第二腔室的入口位于生物膜的上方，第一腔室的下部与第二腔室的下部之间设置有第二连通管道。
  6. 根据权利要求5所述的一种甲醛降解装置，其特征在于，第一连通管道与第一腔室之间、第二连通管道与第一腔室之间均设置有筛网，第二连通管道靠近第二腔室的一端设置有水泵，第二连通管道设置有止回阀，止回阀在水泵的上方。
  7. 根据权利要求1-3任一项所述的一种甲醛降解装置，其特征在于，反应容器由隔板和盖板分隔成第一腔室和第二腔室，盖板与反应容器固定连接，盖板开设有第二通风口，内空式结构的主反应单元的顶端侧壁开设有成对布置的第一通风口，第一通风口的下方设置有 活性炭载体，第二通风口下方设置挡板。
  8. 根据权利要求1-3任一项所述的一种甲醛降解装置，其特征在于，反应容器为长方体结构，在侧壁设置有便于进入反应容器内部进行检修和维护的开关门；在反应容器的第一腔室和第二腔室设置有便于液体培养基灌装、更新和排出的阀门。
  9. 根据权利要求1-3任一项所述的一种甲醛降解装置，其特征在于，甲醛降解装置还包括温控装置。
  10. 一种甲醛降解方法，其特征在于，使用如权利要求1-9任一项所述的甲醛降解装置，使用时超声波发生器的超声波频率选择在30KHz-35KHz范围内，超声波发生器工作室采用间歇模式，第一腔室的工作回流比为100％。
PCT/CN2020/079328 2019-06-27 2020-03-13 一种甲醛降解装置及甲醛降解方法 Ceased WO2020258924A1 (zh)

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