WO2022068034A1 - 一种多相催化氧化技术深度处理低浓度cs 2的系统及方法 - Google Patents

一种多相催化氧化技术深度处理低浓度cs 2的系统及方法 Download PDF

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WO2022068034A1
WO2022068034A1 PCT/CN2020/133019 CN2020133019W WO2022068034A1 WO 2022068034 A1 WO2022068034 A1 WO 2022068034A1 CN 2020133019 W CN2020133019 W CN 2020133019W WO 2022068034 A1 WO2022068034 A1 WO 2022068034A1
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catalytic oxidation
concentration
oxidation tower
tower
multiphase
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French (fr)
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孙浩
韩正昌
马军军
朱家明
张寿兵
周啸
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南京格洛特环境工程股份有限公司
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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
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • 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
    • B01D53/86—Catalytic processes
    • B01D53/8678—Removing components of undefined structure
    • B01D53/8687—Organic components
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/106—Peroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/604—Hydroxides

Definitions

  • the invention relates to the field of waste gas treatment, in particular to a system and method for advanced treatment of low-concentration CS 2 by heterogeneous catalytic oxidation technology.
  • the industrial waste gas emitted during the production of viscose staple fiber contains a large amount of CS 2 and H 2 S, which cause great harm to human body, and the emission must be strictly controlled.
  • waste gas from short fiber production will be pretreated to recover high concentrations of CS 2 and H 2 S, resulting in waste gas containing only low concentration of CS 2 , but it cannot meet the emission limit.
  • concentration of CS 2 in the process waste gas is low, the recovery method cannot effectively solve the problem, because the waste gas treated by this method still has a certain concentration of CS 2 , and it is not economical and technically difficult to recover at this time.
  • Patent CN 104923067 A discloses a CS 2 waste gas treatment integrated device.
  • the waste gas passes through the waste gas washing zone, the biological oxidation absorption zone, the biological adsorption zone, and the activated carbon adsorption zone in sequence, and finally reaches the standard discharge.
  • the waste gas washing zone the biological oxidation absorption zone
  • the biological adsorption zone the activated carbon adsorption zone
  • it is difficult to apply it on a large scale.
  • the purpose of the present invention is to provide a low-concentration CS 2 oxidation treatment process, and simultaneously remove a small amount of H 2 S and VOCs and other pollutants. Waste gas purification technology.
  • a system for advanced treatment of low-concentration CS 2 with heterogeneous catalytic oxidation technology comprising an induced draft fan, at least one complex catalytic oxidation tower, and each complex catalytic oxidation tower corresponds to a fan;
  • the induced draft fan is connected with the side bottom end of the multiphase catalytic oxidation tower through the intake pipe, the exhaust gas outlet is arranged at the top of the multiphase catalytic oxidation tower, and the exhaust gas outlet is connected to the next multiphase catalytic oxidation tower through the pipeline.
  • the multiphase catalytic oxidation tower is provided with two packing supports, and adsorption packing is laid on each layer of supports; an ozone dosing port is set at the bottom of the tower, and an oxidant liquid storage tank is set, and the compounded oxidant liquid storage tank is connected with a circulation pump, and the circulation
  • the pump is connected to the nozzle installed on the upper end of the side wall of the multiphase catalytic oxidation tower and above the packing through the pipeline; the waste gas is adsorbed and intercepted by activated carbon through the first-stage multiphase catalytic oxidation tower and simultaneously oxidized, which can remove most of CS 2 .
  • the waste gas After treatment, the waste gas enters the secondary complex-phase catalytic oxidation tower, and the spray liquid reaches a sub-saturated state, and the sulfate by-product salt is obtained through flocculation, filtration, evaporative crystallization and centrifugation.
  • the multiphase catalytic oxidation tower is an independent unit, including but not limited to two-stage combined use, which can be used alone or in combination of multiple stages.
  • the use of two cascades can meet most of the exhaust gas treatment requirements.
  • the ozone dosing port is connected with the ozone generator through a pipeline to continuously provide ozone for the complex phase catalytic oxidation tower.
  • the intake concentration of the complex catalytic oxidation tower shall not be greater than 50 mg/m 3 .
  • the compound oxidant used in the compound catalytic oxidation tower is one or more of potassium hydroxide, sodium hydroxide and hydrogen peroxide, wherein the hydrogen peroxide concentration is 0.5% to 5%, and the pH control range is 8 to 14.
  • the fillers include but are not limited to activated carbon, silica gel, carbon fiber and molecular sieves, etc.
  • activated carbon is selected.
  • the concentration of the intake air of the complex-phase catalytic oxidation tower is 20-30 mg/m 3 .
  • hydrogen peroxide and sodium hydroxide are used as compound oxidants in the complex catalytic oxidation tower, the effective concentration of hydrogen peroxide is 1%, and the optimum pH is 12.
  • the compounded oxidant in the multiphase catalytic oxidation tower is one or more of potassium hydroxide, sodium hydroxide, sodium persulfate and potassium persulfate, wherein the persulfate concentration is 0.3 to 3 mol/L, and the pH control range is 8 to 14, preferably, sodium persulfate and sodium hydroxide are used as compound oxidants, the concentration of sodium persulfate is 1mol/L, and the optimum pH is 12.
  • the process principle of heterogeneous catalytic oxidation is to use two or more oxidants in combination, pass into the heterogeneous catalytic oxidation reaction tower, and form stronger oxidizing hydroxyl radicals ( OH) under the action of the catalyst, and OH oxidation
  • OH hydroxyl radicals
  • the complex oxidant used in the complex catalytic oxidation tower is one or more of potassium hydroxide, sodium hydroxide and hydrogen peroxide, the principle is:
  • the spray liquid rich in OH and oxidant is lifted to the top of the tower for atomization and sprayed down by a pump, and reacts in countercurrent with the waste gas entering the lower part of the tower in the packing area in the tower to remove organic pollutants in the waste gas; on the other hand, During the process of flowing from bottom to top in the tower, the exhaust gas contacts the catalytic packing in the tower, and some organic pollutants in the exhaust gas will be adsorbed on the surface of the packing.
  • a liquid-phase catalyst can be selectively introduced in the process of lifting and circulating the spray liquid at the bottom of the tower with a circulating pump, so that more hydroxyl radicals ( OH) are formed in the spray liquid for use in the oxidation tower. removal of organic pollutants.
  • the compound oxidant used in the compound catalytic oxidation tower is one or more of potassium hydroxide, sodium hydroxide, sodium persulfate and potassium persulfate, the principle is:
  • persulfate produces sulfate radicals with a longer life than hydroxyl radicals, has a wide range of pH applications, and has outstanding ability to treat target pollutants.
  • Persulfate has a low reaction rate under normal conditions, but is easily activated to become sulfate radicals under conditions such as light, alkali, heat, sound or excessive metal ions. Under alkaline conditions, sulfate radicals will generate hydroxyl radicals, triggering a series of free radical chain reactions and improving the ability to degrade organic matter.
  • the invention makes full use of the existing alkaline spray liquid in the process to activate persulfate to generate sulfate radicals, and because of its long half-life and strong oxidizing ability, the organic pollutants in the exhaust gas can be degraded with high efficiency.
  • the hydroxyl radicals transformed by radical radicals act synergistically with ozone to further remove target pollutants.
  • the spray liquid rich in SO 4 and oxidant is lifted to the top of the tower by a pump to be atomized and sprayed down, and conduct countercurrent reaction with the waste gas entering the lower part of the tower in the packing area in the tower to remove organic pollutants in the waste gas; on the other hand , the exhaust gas is in contact with the catalytic packing in the tower during the process of flowing from bottom to top, and some organic pollutants in the exhaust gas will be adsorbed on the surface of the packing.
  • a method for advanced treatment of low-concentration CS 2 with heterogeneous catalytic oxidation technology specifically includes the following steps: low-concentration waste gas is sent to a first-stage complex by a first-stage fan. Phase catalytic oxidation tower to complete the pre-oxidation of CS 2 , and then sent to the secondary complex phase catalytic oxidation tower to remove residual CS 2 through complex phase oxidation, and finally discharged through the secondary fan up to the standard; after the spray liquid circulating liquid is saturated, it is prepared by evaporation and crystallization Sulfate by-product.
  • the present invention provides a process for advanced treatment of low-concentration CS 2 by heterogeneous catalytic oxidation technology, which can oxidize and remove low-concentration CS 2 , and can reduce the CS 2 concentration in the exhaust gas to below 8 mg/m 3 , which meets the requirements of “Odor Pollution”
  • the present invention provides a process for treating low-concentration CS 2 waste gas with no recovery value. Because CS 2 is insoluble in water, the solubility in water is improved by spraying with lye, which greatly improves the CS 2 oxidation efficiency.
  • the present invention removes CS 2 through catalytic oxidation, simultaneously removes pollutants such as H 2 S and VOCs, and generates CO 2 and water, which will not cause secondary pollution to the atmosphere.
  • the hydrogen peroxide and ozone used in the present invention are both green oxidizing agents and will not introduce new pollutants.
  • the present invention adopts an alkaline spray oxidation process, and the oxidized product in the spray liquid can prepare commercial-grade sulfate by-products, and there is no mother liquor discharge in the whole process, which does not pollute the environment, and reduces operating costs.
  • the waste gas treatment process provided by the present invention with alkali spraying + multi-phase oxidation technology as the core realizes the cycle process of "organic adsorption-organic oxidative decomposition, packing regeneration-organic re-adsorption" of catalytic fillers, and has operating costs. It has the advantages of low, no waste water discharge, no secondary pollution, etc., and converts pollutants into by-products, which fundamentally solves the problem of disposal of low-concentration CS 2 waste gas.
  • Fig. 1 is a process flow diagram of the present invention.
  • the flue gas produced by a company's short fiber production workshop mainly contains major pollutants such as CS 2 and H 2 S, and contains a pungent odor.
  • Waste gas treatment capacity 800 ⁇ 1000m 3 /h.
  • the initial concentration of waste gas carbon disulfide 20 ⁇ 30mg/m3, hydrogen sulfide 1 ⁇ 3mg/m3.
  • the compound oxidant is prepared by using 30% sodium hydroxide and 30% hydrogen peroxide.
  • the pilot test adopts a two-stage catalytic tower oxidation treatment process, the effective concentration of hydrogen peroxide is 0.5%, the pH is 11, and the ozone flow rate is 200g/h. Exhaust gas outlet sampling monitoring. The specific data are as follows:
  • the carbon disulfide inlet concentration is 28mg/m 3
  • the outlet concentration is 6.6mg/m 3
  • the hydrogen sulfide inlet concentration is 1.8mg/m 3
  • the outlet concentration is 0.2mg/L
  • the removal rates are 76.4 % and 88.9%
  • the exhaust gas after treatment has no obvious odor.
  • the flue gas produced by a company's short fiber production workshop mainly contains major pollutants such as CS 2 and H 2 S, and contains a pungent odor.
  • Waste gas treatment capacity 800 ⁇ 1000m 3 /h.
  • the initial concentration of waste gas carbon disulfide 20 ⁇ 30mg/m3, hydrogen sulfide 1 ⁇ 3mg/m3.
  • the compound oxidant is prepared with 30% sodium hydroxide and 30% hydrogen peroxide.
  • the pilot test adopts a two-stage catalytic tower oxidation treatment process.
  • the effective concentration of hydrogen peroxide is 1%, the pH is 12, and the ozone flow rate is 200g/h.
  • Exhaust gas outlet sampling monitoring The specific data are as follows:
  • the carbon disulfide inlet concentration is 30mg/m 3
  • the outlet concentration is 5.4mg/m 3
  • the hydrogen sulfide inlet concentration is 2.2mg/m 3
  • the outlet concentration is 0.15mg/L
  • the removal rates are 82 mg/L. % and 93.2%
  • the exhaust gas after treatment has no obvious odor.
  • the flue gas produced by a company's short fiber production workshop mainly contains major pollutants such as CS 2 and H 2 S, and contains a pungent odor.
  • Waste gas treatment capacity 800 ⁇ 1000m 3 /h.
  • Initial concentration of exhaust gas carbon disulfide 20-30 mg/m 3 , hydrogen sulfide 1-3 mg/m 3 .
  • the compound oxidant is prepared by using sodium persulfate and sodium hydroxide.
  • the pilot test adopts a two-stage catalytic tower oxidation treatment process, the molar concentration of sodium persulfate is 0.5mol/L, the pH is 11, and the ozone flow rate is 200g/h.
  • the exhaust gas outlet sampling monitoring, the specific data are as follows:
  • the carbon disulfide inlet concentration is 22mg/m 3
  • the outlet concentration is 7.2mg/m 3
  • the hydrogen sulfide inlet concentration is 2mg/m 3
  • the outlet concentration is 0.25mg/L
  • the removal rates are 67.3% respectively. and 87.5%
  • the exhaust gas after treatment has no obvious odor.
  • the flue gas produced by a company's short fiber production workshop mainly contains major pollutants such as CS 2 and H 2 S, and contains a pungent odor.
  • Waste gas treatment capacity 800 ⁇ 1000m 3 /h.
  • Initial concentration of exhaust gas carbon disulfide 20-30 mg/m 3 , hydrogen sulfide 1-3 mg/m 3 .
  • the compound oxidant is prepared by using sodium persulfate and sodium hydroxide.
  • the pilot test adopts a two-stage catalytic tower oxidation treatment process, the molar concentration of sodium persulfate is 1mol/L, the pH is 12, and the ozone flow rate is 200g/h.
  • Exhaust gas outlet sampling monitoring the specific data are as follows:
  • the carbon disulfide inlet concentration is 25mg/m 3
  • the outlet concentration is 4.4mg/m 3
  • the hydrogen sulfide inlet concentration is 2.5mg/m 3
  • the outlet concentration is 0.15mg/L
  • the removal rates are 82.4 % and 94%

Abstract

一种多相催化氧化技术深度处理低浓度CS 2的系统和方法，系统包括引风机、至少一个复相催化氧化塔，每个复相催化氧化塔对应一个引风机；引风机通过进气管道与复相催化氧化塔的侧面底端连接，复相催化氧化塔的顶端设置废气出口，废气出口通过管道与下一个复相催化氧化塔的侧面底端连接；复相催化氧化塔内设两块填料支撑，每层支撑上铺设吸附填料；塔底设置臭氧加药口，并设置复配氧化剂储液罐，复配氧化剂储液罐与循环泵连接，循环泵通过管道与安装在复相催化氧化塔侧壁上端、位于填料上方的喷头连接；复相催化氧化塔为独立单元，包括但不限于两级联用，可单独或多级组合联用；方法具体包括如下步骤：低浓度废气经引风机送至一级复相催化氧化塔，完成CS 2的预氧化，再送至二级复相催化氧化塔，经复相氧化去除残余CS 2，最后经风机达标排放；喷淋液循环液饱和后经蒸发结晶制备硫酸盐副产品。

Description

一种多相催化氧化技术深度处理低浓度CS 2的系统及方法 技术领域
本发明涉及废气治理领域，具体涉及一种多相催化氧化技术深度处理低浓度CS 2的系统及方法。
背景技术
生产粘胶短纤维的过程中排放的工业废气含有大量的CS 2和H 2S，对人体造成极大危害，必须严格控制排放。一般的，短纤维生产废气会进行预处理回收高浓度的CS 2和H 2S，得到仅含低浓度CS 2的废气，但无法满足排放限值。当工艺废气中的CS 2浓度较低时，回收法并不能有效的解决，因为该方法处理后的废气仍会有一定浓度的CS 2，此时再进行回收既不经济，又存在技术困难。目前鲜有发现废气中CS 2终端处置并达标排放的相关技术。专利CN 104923067 A公开了一种CS 2废气处理一体化装置，废气依次经废气洗涤区、生物氧化吸收区、生物吸附区、和活性炭吸附区，最终达标排放。但考虑其结构较复杂，生物吸附的稳定性不好，很难大规模应用。
基于以上情况，现有的粘胶废气处理方法并不能从根本上解决问题，开发一种低浓度CS 2废气最终处置技术迫在眉睫。
发明内容
针对上述现有技术的不足，本发明目的在于提供一种低浓度CS 2的氧化处置工艺，同时同步去除少量的H 2S及VOCs等污染物的废气净化技术。
一种多相催化氧化技术深度处理低浓度CS 2的系统，包括引风机、至少一个复相催化氧化塔，每个复相催化氧化塔对应一个风机；
所述的引风机通过进气管道与复相催化氧化塔的侧面底端连接，所述的复相催化氧化塔的顶端设置废气出口，所述的废气出口通过管道与下一个复相催化氧化塔的侧面底端连接；
所述的复相催化氧化塔内设两块填料支撑，每层支撑上铺设吸附填料；塔底设置臭氧加药口，并设置氧化剂储液罐，复配氧化剂储液罐与循环泵连接，循环泵通过管道与安装在复相催化氧化塔侧壁上端、位于填料上方的喷头连接；废气经过一级复相催化氧化塔经活性炭吸附截留并同步氧化，可去除大部分CS 2。处理后废气进入二级复相催化氧化塔，喷淋液达到亚饱和状态，经絮凝沉淀、过滤、蒸发结晶及离心工艺得到硫酸盐副产盐。
所述的复相催化氧化塔为独立单元，包括但不限于两级联用，可单独或多级组合联用。作为优选的，采用两级联用可满足大部分废气处理需求。
进一步地，所述的臭氧加药口通过管道与臭氧发生器连接，为复相催化氧化塔连续不断的提供臭氧。
进一步地，复相催化氧化塔进气浓度不得大于50mg/m 3。
进一步地，复相催化氧化塔所用的复配氧化剂为氢氧化钾、氢氧化钠和双氧水中的一种或几种，其中双氧水浓度为0.5％～5％，pH控制范围为8～14。
进一步地，所述填料包括但不限于活性炭、硅胶、碳纤维和分子 筛等，作为优选的，吸附剂选择活性炭。
进一步地，复相催化氧化塔进气浓度为20～30mg/m 3。
进一步地，复相催化氧化塔中双氧水和氢氧化钠作为复配氧化剂，双氧水有效浓度为1％，最佳pH为12。
或者，复相催化氧化塔中复配氧化剂为氢氧化钾、氢氧化钠、过硫酸钠和过硫酸钾的一种或几种，其中过硫酸盐浓度为0.3～3mol/L，pH控制范围为8～14，作为优选的，过硫酸钠和氢氧化钠作为复配氧化剂，过硫酸钠浓度为1mol/L，最佳pH为12。
多相催化氧化的工艺原理是利用两种以上的氧化剂联用，通入在多相催化氧化反应塔内，在催化剂的作用下形成更强氧化性的羟基自由基(·OH)，·OH氧化电位达到2.8V，可将几乎所有的有机物氧化成SO 2、CO 2和H 2O。
当复相催化氧化塔所用的复配氧化剂为氢氧化钾、氢氧化钠和双氧水中的一种或几种时，原理为：
富含·OH和氧化剂的喷淋液用泵提升至塔顶雾化喷淋而下，和塔下部进入的废气在塔内填料区进行逆流反应，去除废气中的有机污染物；另一方面，废气在塔内、从下往上流动的过程中与塔内的催化填料接触，废气中的部分有机污染物会吸附在填料表面，当富含·OH和氧化剂的喷淋液从顶部喷淋而下、与催化填料接触时，在催化作用下可将填料表面吸附的有机污染物进行氧化分解，同步完成了催化填料的再生，实现了催化填料的“有机物吸附—有机物氧化分解、填料再生—有机物再吸附”的循环过程。同时，为降低废气治理成本，可选 择性在塔底喷淋液用循环泵提升循环过程中引入液相催化剂，使喷淋液中形成更多的羟基自由基(·OH)用于氧化塔内的有机污染物的去除。
其反应原理的化学方程式为：C mH nO lX p+·HO→mCO 2+nH 2O+pHX
当复相催化氧化塔所用的复配氧化剂为氢氧化钾、氢氧化钠、过硫酸钠和过硫酸钾的一种或几种时，原理为：
过硫酸盐作为新型高级氧化剂，其产生的硫酸根自由基比羟基自由基寿命长，pH适用范围广，对目标污染物处理能力突出。过硫酸盐在通常状态下反应速率较低，但在光、碱、热、声或过度金属离子等条件下易活化成为硫酸根自由基。在碱性条件下，硫酸根自由基会产生羟基自由基，引发一系列自由基链式反应，提高对有机物的降解能力。本发明充分利用工艺现有的碱性喷淋液活化过硫酸盐产生硫酸根自由基，因其半衰期长，氧化能力强，可高效率地降解废气中的有机污染物，同时碱性条件下硫酸根自由基转化的羟基自由基与臭氧协同作用，可进一步去除目标污染物。
富含·SO 4和氧化剂的喷淋液用泵提升至塔顶雾化喷淋而下，和塔下部进入的废气在塔内填料区进行逆流反应，去除废气中的有机污染物；另一方面，废气在塔内、从下往上流动的过程中与塔内的催化填料接触，废气中的部分有机污染物会吸附在填料表面，当富含·SO 4和氧化剂的喷淋液从顶部喷淋而下、与催化填料接触时，在催化作用下可将填料表面吸附的有机污染物进行氧化分解，同步完成了催化填 料的再生，实现了催化填料的“有机物吸附—有机物氧化分解、填料再生—有机物再吸附”的循环过程。
一种多相催化氧化技术深度处理低浓度CS 2的方法，采用上述的多相催化氧化技术深度处理低浓度CS 2的系统，具体包括如下步骤：低浓度废气经一级风机送至一级复相催化氧化塔，完成CS 2的预氧化，再送至二级复相催化氧化塔，经复相氧化去除残余CS 2，最后经二级风机达标排放；喷淋液循环液饱和后经蒸发结晶制备硫酸盐副产品。
本发明的有益效果为：
(1)本发明提供一种多相催化氧化技术深度处理低浓度CS 2的工艺，能够氧化去除低浓度的CS 2，可使废气中的CS 2浓度降至8mg/m3以下，满足《恶臭污染物排放标准》(GB14554-1993)表1规定的排放需求。
(2)本发明提供了一种无回收价值的低浓度CS 2废气的处理工艺，因CS 2难溶于水，通过碱液喷淋提高其水中溶解度，大大提高了CS 2氧化效率
(3)本发明通过催化氧化去除CS 2的同时，同步去除H 2S和VOCs等污染物，并生成CO 2和水，不会对大气造成二次污染。
(4)本发明采用的双氧水和臭氧均为绿色氧化剂，不会引入新的污染物。
(5)本发明采用碱性喷淋氧化工艺，喷淋液中的氧化产物可制备商品级硫酸盐副产品，全程无母液排放，不污染环境的同时，降低了运行成本。
(6)本发明提供的以碱喷淋+复相氧化技术为核心的废气处置工艺，实现了催化填料的“有机物吸附—有机物氧化分解、填料再生—有机物再吸附”的循环过程，具有运行成本低、无废水排放、无二次污染等优势，而且将污染物转化成副产品，从根本上解决低浓度CS 2废气的处置难题。
附图说明
图1为本发明的工艺流程图。
具体实施方式
为了加深对本发明的理解，下面结合附图对本发明的实施例做详细的说明。
须知，本说明书所附图式所绘示的结构、比例、大小等，均仅用以配合说明书所揭示的内容，以供熟悉此技术的人士了解与阅读，并非用以限定本发明可实施的限定条件，故不具技术上的实质意义，任何结构的修饰、比例关系的改变或大小的调整，在不影响本发明所能产生的功效及所能达成的目的下，均应仍落在本发明所揭示的技术内容得能涵盖的范围内。
实施例1
某公司短纤维生产车间产生的烟气主要含CS 2和H 2S等主要污染因子，含有刺激性气味。废气处理量：800～1000m 3/h。废气初始浓度：二硫化碳20～30mg/m3、硫化氢1～3mg/m3。复配氧化剂选用30％ 氢氧化钠和30％双氧水配制。中试采用两级催化塔氧化处理工艺，双氧水的有效浓度为0.5％，pH为11，臭氧流量200g/h。废气出口取样监测。具体数据如下：
Figure PCTCN2020133019-appb-000001
从表中数据可以看出，二硫化碳进口浓度为28mg/m 3，出口浓度为6.6mg/m 3，硫化氢进口浓度为1.8mg/m 3，出口浓度为0.2mg/L，去除率分别为76.4％和88.9％，处理后废气无明显臭味。
实施例2
某公司短纤维生产车间产生的烟气主要含CS 2和H 2S等主要污染因子，含有刺激性气味。废气处理量：800～1000m 3/h。废气初始浓度：二硫化碳20～30mg/m3、硫化氢1～3mg/m3。复配氧化剂选用30％氢氧化钠和30％双氧水配制。中试采用两级催化塔氧化处理工艺，双氧水的有效浓度为1％，pH为12，臭氧流量200g/h。废气出口取样监测。具体数据如下：
Figure PCTCN2020133019-appb-000002
Figure PCTCN2020133019-appb-000003
从表中数据可以看出，二硫化碳进口浓度为30mg/m 3，出口浓度为5.4mg/m 3，硫化氢进口浓度为2.2mg/m 3，出口浓度为0.15mg/L，去除率分别为82％和93.2％，处理后废气无明显臭味。
实施例3
某公司短纤维生产车间产生的烟气主要含CS 2和H 2S等主要污染因子，含有刺激性气味。废气处理量：800～1000m 3/h。废气初始浓度：二硫化碳20～30mg/m 3、硫化氢1～3mg/m 3。复配氧化剂选用过硫酸钠和氢氧化钠配制。中试采用两级催化塔氧化处理工艺，过硫酸钠摩尔浓度为0.5mol/L，pH为11，臭氧流量200g/h。废气出口取样监测，具体数据如下：
Figure PCTCN2020133019-appb-000004
从表中数据可以看出，二硫化碳进口浓度为22mg/m 3，出口浓度为7.2mg/m 3，硫化氢进口浓度为2mg/m 3，出口浓度为0.25mg/L，去除率分别为67.3％和87.5％，处理后废气无明显臭味。
实施例4
某公司短纤维生产车间产生的烟气主要含CS 2和H 2S等主要污染因子，含有刺激性气味。废气处理量：800～1000m 3/h。废气初始浓 度：二硫化碳20～30mg/m 3、硫化氢1～3mg/m 3。复配氧化剂选用过硫酸钠和氢氧化钠配制。中试采用两级催化塔氧化处理工艺，过硫酸钠摩尔浓度为1mol/L，pH为12，臭氧流量200g/h。废气出口取样监测，具体数据如下：
Figure PCTCN2020133019-appb-000005
从表中数据可以看出，二硫化碳进口浓度为25mg/m 3，出口浓度为4.4mg/m 3，硫化氢进口浓度为2.5mg/m 3，出口浓度为0.15mg/L，去除率分别为82.4％和94％，处理后废气无明显臭味。
本发明方案所公开的技术手段不仅限于上述技术手段所公开的技术手段，还包括由以上技术特征等同替换所组成的技术方案。本发明的未尽事宜，属于本领域技术人员的公知常识。

Claims (10)

  1. 一种多相催化氧化技术深度处理低浓度CS 2的系统，其特征在于，包括引风机、至少一个复相催化氧化塔，每个复相催化氧化塔对应一个风机；
    所述的引风机通过进气管道与复相催化氧化塔的侧面底端连接，所述的复相催化氧化塔的顶端设置废气出口，所述的废气出口通过管道与下一个复相催化氧化塔的侧面底端连接；
    所述的复相催化氧化塔内设两块填料支撑，每层支撑上铺设吸附填料；塔底设置臭氧加药口，并设置氧化剂储液罐，复配氧化剂储液罐与循环泵连接，循环泵通过管道与安装在复相催化氧化塔侧壁上端、位于填料上方的喷头连接；
    所述的复相催化氧化塔为独立单元，包括但不限于两级联用，可单独或多级组合联用。
  2. 根据权利要求1所述的多相催化氧化技术深度处理低浓度CS 2的系统，其特征在于，包括两个联用的复相催化氧化塔，采用两级联用可满足大部分废气处理需求。
  3. 根据权利要求1所述的多相催化氧化技术深度处理低浓度CS 2的系统，其特征在于，所述的臭氧加药口通过管道与臭氧发生器连接，为复相催化氧化塔连续不断的提供臭氧。
  4. 根据权利要求1所述的多相催化氧化技术深度处理低浓度CS 2的系统，其特征在于，复相催化氧化塔进气浓度不得大于50mg/m 3。
  5. 根据权利要求1所述的多相催化氧化技术深度处理低浓度CS 2的系 统，其特征在于，复相催化氧化塔所用的复配氧化剂为氢氧化钾、氢氧化钠和双氧水中的一种或几种，其中双氧水浓度为0.5％～5％，pH控制范围为8～14。
  6. 根据权利要求1所述的多相催化氧化技术深度处理低浓度CS 2的系统，其特征在于，复配氧化剂为氢氧化钾、氢氧化钠、过硫酸钠和过硫酸钾的一种或几种，其中过硫酸盐浓度为0.3～3mol/L，pH控制范围为8～14。
  7. 根据权利要求1所述的多相催化氧化技术深度处理低浓度CS 2的系统，其特征在于，所述填料包括但不限于活性炭、硅胶、碳纤维和分子筛。
  8. 根据权利要求4所述的多相催化氧化技术深度处理低浓度CS 2的系统，其特征在于，复相催化氧化塔进气浓度为20～30mg/m 3。
  9. 根据权利要求5所述的多相催化氧化技术深度处理低浓度CS 2的系统，其特征在于，复相催化氧化塔中双氧水和氢氧化钠作为复配氧化剂，双氧水有效浓度为1％，最佳pH为12。
  10. 一种多相催化氧化技术深度处理低浓度CS 2的方法，其特征在于，采用权利要求1-7所述的多相催化氧化技术深度处理低浓度CS 2的系统，具体包括如下步骤：低浓度废气经引风机送至一级复相催化氧化塔，完成CS 2的预氧化，再送至二级复相催化氧化塔，经复相氧化去除残余CS 2，最后经风机达标排放；喷淋液循环液饱和后经蒸发结晶制备硫酸盐副产品。
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