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沸石转轮中VOCs残留的处理
来源:/ 发布时间:2024-01-05

国内外对VOC的末端治理方法有:冷凝、吸附、氧化、生物处理、吸收、等离子体净化等。以沸石材料为载体的吸附浓缩法处理VOC废气(沸石转轮)得到了较为广泛的应用。全国对VOCs污染物防治的要求和力度逐渐加强,低浓度废气治理的沸石转轮吸附浓缩法成为了很多企业的优选治理方案。

The end treatment methods for VOC at home and abroad include condensation, adsorption, oxidation, biological treatment, absorption, plasma purification, etc. The adsorption concentration method using zeolite materials as carriers has been widely used in the treatment of VOC waste gas (zeolite wheels). The national requirements and efforts for the prevention and control of VOCs pollutants are gradually strengthening, and the zeolite rotary adsorption concentration method for low concentration waste gas treatment has become the preferred treatment plan for many enterprises.

在使用的过程中,因为VOCs在转轮内部的残留,会导致沸石转轮劣化,处理效率降低,要如何避免和应对这样的情况呢?

During use, the residue of VOCs inside the impeller can lead to the deterioration of the zeolite impeller and a decrease in treatment efficiency. How can we avoid and respond to such situations?

降低沸石转轮设备内部VOCs残留主要从改善VOCs废气的进气质量和加强脱附效率两方面入手。

Reducing the residual VOCs inside the zeolite rotary equipment mainly starts from improving the intake quality of VOCs waste gas and strengthening the desorption efficiency.

01.废气预处理

01. Waste gas pretreatment

废气预处理措施通常有除尘、除湿、除雾、除高沸物等。针对要处理的VOCs废气实际情况,需选取适当的废气预处理措施。比如,半导体生产制造过程对生产场所的颗粒物有严格的要求,生产场所通常为洁净车间。因此,有机废气中的颗粒物含量极少,通常无需进行除尘预处理。

The pre-treatment measures for exhaust gas usually include dust removal, dehumidification, defogging, and removal of high boiling substances. According to the actual situation of VOCs waste gas to be treated, appropriate waste gas pretreatment measures need to be selected. For example, the semiconductor manufacturing process has strict requirements for particulate matter in the production site, which is usually a clean workshop. Therefore, the particulate matter content in organic waste gas is extremely low and usually does not require dust removal pretreatment.

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比如,芯片制造业生产过程中使用的主要有机原料通常具有低沸点、易挥发的特点,但仍不排除少量高沸点物质,如剥离液的主要成分二甘醇胺(沸程218~224℃)等。可在高沸点物质的处理工序中增设冷凝、前道活性炭吸附等预处理装置,以避免VOCs废气中难脱附的高沸点物质进入沸石转轮。

For example, the main organic raw materials used in the production process of chip manufacturing usually have the characteristics of low boiling point and easy volatility, but a small amount of high boiling point substances cannot be ruled out, such as the main component of the stripping solution, diethylene glycol amine (boiling range 218-224 ℃). Pre treatment devices such as condensation and front activated carbon adsorption can be added in the treatment process of high boiling point substances to prevent high boiling point substances that are difficult to desorb from VOCs waste gas from entering the zeolite runner.

高沸点VOCs进入废气管道后容易凝结,从而使废气湿度增大。当进入沸石转轮系统的有机废气湿度大于80%时,将对疏水性沸石分子筛产生较为严重的影响。因此,建议对高湿度废气增设干燥除湿预处理装置,使得进入废水转轮系统的废气湿度保持在稳定、可控的范围内。

High boiling point VOCs are prone to condensation after entering the exhaust gas pipeline, thereby increasing the humidity of the exhaust gas. When the humidity of the organic waste gas entering the zeolite rotary system exceeds 80%, it will have a serious impact on the hydrophobic zeolite molecular sieve. Therefore, it is recommended to install a drying and dehumidification pre-treatment device for high humidity exhaust gas, so as to maintain the humidity of the exhaust gas entering the wastewater rotary system within a stable and controllable range.

02.高温再生

02. High temperature regeneration

根据对国内芯片企业开展的调研可知,芯片制造业常用的有机物质有异丙醇(沸点为82.45℃)、丙二醇单甲醚乙酸酯(沸点为146℃);同时还含有少量的高沸点物质,例如二甘醇胺(沸程218~224℃)。

According to research conducted on domestic chip companies, the commonly used organic substances in the chip manufacturing industry include isopropanol (boiling point of 82.45 ℃) and propylene glycol monomethyl ether acetate (boiling point of 146 ℃); It also contains a small amount of high boiling substances, such as diethylene glycol amine (boiling range 218-224 ℃).

通常芯片制造业沸石转轮的再生温度为180-200℃,在此再生温度下,高沸点的二甘醇胺等物质将无法从沸石转轮上有效脱附,从而逐渐积聚在转轮内部。

The regeneration temperature of zeolite wheels in the chip manufacturing industry is usually 180-200 ℃. At this regeneration temperature, high boiling substances such as diethylene glycol amine cannot be effectively desorbed from the zeolite wheels, gradually accumulating inside the wheels.

经过对沸石转轮系统的高沸点物质聚集情况开展的研究,可知当沸石转轮系统运行1个月后,转轮内部确实有较大量的有机物积聚,其有机物积聚量即达6wt%。进行有效的高温脱附之后,其内部的有机物积聚量可降低约40%~60%。因此,高温脱附可较为有效地去除沸石转轮内部积聚的高沸点有机物质。

After conducting research on the aggregation of high boiling substances in the zeolite rotary system, it is known that after one month of operation, there is indeed a large amount of organic matter accumulation inside the rotary system, with an organic matter accumulation amount of 6wt%. After effective high-temperature desorption, the accumulation of organic matter inside can be reduced by about 40% to 60%. Therefore, high-temperature desorption can effectively remove high boiling organic matter accumulated inside the zeolite impeller.

企业应根据废气的实际产生情况,分析废气组成分布,分析高沸点物质占比情况,以及废气的产生总量等内容,从而确定高温再生频次。较为适宜的高温再生频次为2~3个月一次。

Enterprises should analyze the distribution of exhaust gas composition, the proportion of high boiling substances, and the total amount of exhaust gas generated based on the actual generation of exhaust gas, in order to determine the frequency of high-temperature regeneration. The more suitable frequency for high-temperature regeneration is once every 2-3 months.

高温再生的温度也会影响高温脱附效果。若高温脱附温度选取过低,则高沸点物质仍无法有效脱除;若高温脱附温度选取过高,将对沸石分子筛的骨架结构产生一定的影响,从而降低其使用寿命。高温脱附温度宜选取300℃左右,并且,相应的沸石转轮内部配件均需采用可耐300℃高温的密封配件。

The temperature of high-temperature regeneration can also affect the high-temperature desorption effect. If the high-temperature desorption temperature is selected too low, the high boiling point substance cannot be effectively removed; If the high temperature desorption temperature is selected too high, it will have a certain impact on the skeleton structure of zeolite molecular sieve, thereby reducing its service life. The high-temperature desorption temperature should be around 300 ℃, and the corresponding internal components of the zeolite impeller should use sealing components that can withstand high temperatures of 300 ℃.

03.水洗再生

03. Water washing regeneration

芯片制造业常用的有机物质(如异丙醇、丙二醇单甲醚乙酸酯等)通常具有较好的水溶性,可采用水洗再生的方式去除沸石转轮内部聚集的高沸点物质。

Organic substances commonly used in the chip manufacturing industry, such as isopropanol, propylene glycol monomethyl ether acetate, etc., usually have good water solubility and can be removed by water washing regeneration to remove high boiling substances accumulated inside the zeolite impeller.

水洗再生可有效提高沸石转轮系统的治理效率,对于工厂,当水洗再生次数达到4~6次/年时,沸石转轮系统的治理效率可达95%~99%。因此,适当增加定期水洗再生频次,可有效防止高沸点物质在沸石转轮内部的聚集,保持高治理效率。

Water washing regeneration can effectively improve the treatment efficiency of zeolite rotary system. For factories, when the water washing regeneration frequency reaches 4-6 times per year, the treatment efficiency of zeolite rotary system can reach 95% to 99%. Therefore, increasing the frequency of regular water washing regeneration can effectively prevent the aggregation of high boiling substances inside the zeolite impeller and maintain high treatment efficiency.

由于沸石转轮通常采用无机粘合剂将分子筛涂覆在陶瓷纤维纸表面制造而成,故水洗时不仅转轮不会发生龟裂形变,也不会发生由于分子筛脱落所导致的性能劣化、使用寿命缩短等问题。

Due to the fact that zeolite wheels are usually manufactured by coating molecular sieves on the surface of ceramic fiber paper using inorganic adhesives, not only will the wheels not undergo cracking deformation during water washing, but also there will be no problems such as performance degradation and shortened service life caused by molecular sieve detachment.

但是,水洗时需要注意水质状况,若其中大量含有钙、镁等离子,将可能在沸石内部形成碳酸盐,阻塞沸石转轮的蜂窝状孔道;水中所含微量重金属物质、氯等也会毒化沸石。

However, attention should be paid to the water quality during washing. If a large amount of calcium and magnesium ions are present, carbonates may form inside the zeolite, blocking the honeycomb like channels of the zeolite impeller; Trace amounts of heavy metals and chlorine in water can also poison zeolite.

值得注意的是,并非所有沸石转轮材质均耐水洗,企业应在水洗再生之前,向沸石转轮设备的制造厂商做好相关的咨询工作。

It is worth noting that not all zeolite wheel materials are resistant to water washing. Enterprises should consult with the manufacturer of zeolite wheel equipment before water washing and regeneration.

04.高压空气吹扫

04. High pressure air blowing

企业在停机检维修期间,采用高压空气对沸石转轮进行吹扫。然而,高压空气吹扫通常只可清除沸石转轮表面附着的灰尘,而VOCs有机质通常吸附在分子筛孔道内部,无法得到有效的脱除,还需与上述其他处理方式配合选用。

During the shutdown inspection and maintenance period, the enterprise uses high-pressure air to blow and sweep the zeolite wheel. However, high-pressure air blowing usually only removes the dust attached to the surface of the zeolite impeller, while VOCs organic matter is usually adsorbed inside the molecular sieve pores and cannot be effectively removed. Therefore, it is necessary to choose in combination with other treatment methods mentioned above.

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