CN111001297A - Process and device for degrading chlorine-containing volatile organic compounds in two stages of hydrolysis and oxidation - Google Patents
Process and device for degrading chlorine-containing volatile organic compounds in two stages of hydrolysis and oxidation Download PDFInfo
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- CN111001297A CN111001297A CN201911387185.5A CN201911387185A CN111001297A CN 111001297 A CN111001297 A CN 111001297A CN 201911387185 A CN201911387185 A CN 201911387185A CN 111001297 A CN111001297 A CN 111001297A
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 100
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 79
- 239000000460 chlorine Substances 0.000 title claims abstract description 78
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 76
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 46
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 44
- 230000003647 oxidation Effects 0.000 title claims abstract description 42
- 230000000593 degrading effect Effects 0.000 title claims abstract description 21
- 230000008569 process Effects 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 78
- 230000003197 catalytic effect Effects 0.000 claims abstract description 74
- 238000006298 dechlorination reaction Methods 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims description 37
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
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- 238000010438 heat treatment Methods 0.000 claims description 10
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- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 12
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- 238000005516 engineering process Methods 0.000 description 10
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- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 5
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- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
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- 231100000572 poisoning Toxicity 0.000 description 3
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- 150000002910 rare earth metals Chemical class 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910004625 Ce—Zr Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 150000004826 dibenzofurans Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
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- 239000003546 flue gas Substances 0.000 description 2
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- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 description 2
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- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- BLOIXGFLXPCOGW-UHFFFAOYSA-N [Ti].[Sn] Chemical compound [Ti].[Sn] BLOIXGFLXPCOGW-UHFFFAOYSA-N 0.000 description 1
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- 231100000260 carcinogenicity Toxicity 0.000 description 1
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- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
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- 229940117389 dichlorobenzene Drugs 0.000 description 1
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- 150000002894 organic compounds Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- 238000010792 warming Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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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
- B01D53/8659—Removing halogens or halogen compounds
- B01D53/8662—Organic halogen compounds
-
- 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
- B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
- B01D2253/1124—Metal oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2065—Cerium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/808—Hydrolytic
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- 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
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Abstract
The invention discloses a hydrolysis-oxidation two-stage process and a device for degrading chlorine-containing volatile organic compounds, wherein the process comprises the following steps: (1) carrying out catalytic hydrolysis dechlorination reaction on the chlorine-containing volatile organic compounds at the temperature of 100 ℃ and 250 ℃ to generate HCl and dechlorinated volatile organic compounds; (2) passing HCl and dechlorinated volatile organic compounds through a dechlorinating agent to remove HCl therein; (3) at 200 and 500 ℃, the dechlorinated volatile organic compounds are subjected to catalytic deep oxidation reaction. The invention firstly hydrolyzes and dechlorides at low temperature, then absorbs chlorine to prevent chlorine from entering a high-temperature oxidation section, thus not only preventing the high-temperature oxidation catalyst from being poisoned by chlorine to lose activity, but also preventing the chlorine from generating chlorine-containing byproducts with stronger toxicity under the high-temperature condition.
Description
Technical Field
The invention relates to the technical field of waste gas treatment, in particular to a process and a device for degrading chlorine-containing volatile organic compounds in a hydrolysis-oxidation two-stage mode.
Background
chlorine-Containing Volatile Organic Compounds (CVOCs) are mainly derived from industrial waste gases and are increasingly receiving a great deal of attention due to their persistent environmental hazard.
CVOCs are generally derived from the production and use of vinyl chloride, herbicides, plastics, and the like. CVOCs have high biotoxicity and high durability, and some CVOCs (such as dichloromethane and tetrachloroethylene) can destroy the ozone layer and increase global warming, causing serious harm to human health. Industrial emissions of CVOCs have been banned by legislative directives in many countries and therefore need to be dealt with more properly.
The existing CVOCs treatment technology is mainly divided into recovery technology and destruction technology, wherein the former comprises an adsorption method, an absorption method, a condensation method, a membrane separation method and the like, and the latter comprises a biodegradation method, a photocatalysis method, a plasma method, a direct combustion method, a catalytic hydrodeoxygenation method, a catalytic combustion method and the like. The catalytic combustion method is considered to be the most promising treatment method at present by comprehensively considering the multiple factors such as the application range, the cost, the treatment thoroughness and the like of various methods.
The core of catalytic combustion technology is the development of catalysts, and research is mainly focused on noble metal catalysts, molecular sieve catalysts and transition metal oxide catalysts. The inactivation of the catalyst in the catalytic oxidation process of CVOCs is mainly embodied in two aspects, namely that Cl is easy to react with active components in the catalytic combustion process to generate metal chlorides and oxychlorides with lower boiling points, so that the loss of the active components is caused, and Cl is strongly adsorbed on the catalyst, so that active sites are occupied.
Chinese patent publication No. CN110404534A discloses a high-efficiency chlorine poisoning resistant volatile organic compound catalytic oxidation catalyst and a preparation method thereof, wherein the catalyst adopts RuO2As an active component, SnyTi1-yO2Or MOx-SnyTi1-yO2Mixed metal oxide as carrier, the invention uses Sn to TiO2The doping of (a) is carried out,realizes the regulation and control of the crystal form of the carrier oxide, and greatly improves the RuO while constructing the tin titanium-based catalyst carrier with high-efficiency activation performance2Dispersion on the surface of the support; the catalyst has high catalytic activity on chlorine-containing volatile organic compounds, strong chlorine poisoning resistance and CO poisoning resistance of products2The method has the characteristics of high selectivity and the like, and has good removal effect on common volatile organic compounds.
Chinese patent publication No. CN108295852A discloses a Ce-Zr catalyst for the oxidation reaction of chlorine-containing volatile organic compounds, in which Ru is loaded on Ce-Zr.
The catalytic combustion method can achieve ideal treatment effect on specific organic chloride, but polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) by-products are easily generated when the temperature is 400 ℃ in the incineration process, and the polychlorinated dibenzodioxins and the polychlorinated dibenzofurans are chloric organic pollutants with high toxicity, high carcinogenicity and high durability.
Disclosure of Invention
The invention provides a process for degrading chlorine-containing volatile organic compounds in a hydrolysis-oxidation two-stage manner, and has the advantages of low investment and operation cost, simple operation, safe operation, less high-toxicity byproducts and the like.
The specific technical scheme is as follows:
a hydrolysis-oxidation two-stage process for degrading chlorine-containing volatile organic compounds comprises the following steps:
(1) carrying out catalytic hydrolysis dechlorination reaction on the chlorine-containing volatile organic compounds at the temperature of 100 ℃ and 250 ℃ to generate HCl and dechlorinated volatile organic compounds;
(2) passing HCl and dechlorinated volatile organic compounds through a dechlorinating agent to remove HCl therein;
(3) at 200 and 500 ℃, the dechlorinated volatile organic compounds are subjected to catalytic deep oxidation reaction.
The invention combines two sections of low-temperature hydrolysis and high-temperature oxidation to treat the chlorine-containing volatile organic compounds, the front section and the rear section are provided with different catalyst materials, and dechlorinating agents are added between the two sections to absorb intermediate products. The front section mainly dechlorinates the chlorine-containing volatile organic compounds to reduce the chlorine content in the reaction system; the middle section mainly removes the intermediate product HCl, so as to prevent the intermediate product HCl from generating negative influence on the reaction effect of the rear section; the latter stage mainly degrades the volatile organic compounds after dechlorination.
The invention firstly hydrolyzes and dechlorides at low temperature, then absorbs chlorine to prevent chlorine from entering a high-temperature oxidation section, thus not only preventing the high-temperature oxidation catalyst from being poisoned by chlorine to lose activity, but also preventing the chlorine from generating chlorine-containing byproducts with stronger toxicity under the high-temperature condition.
The concentration of the chlorine-containing volatile organic compound is 10-10000 ppm; the chlorine-containing volatile organic compounds contain 0.1-25% of water vapor.
Preferably, the chlorine-containing volatile organic compound is at least one of chlorobenzene, dichloromethane, methane chloride and dichloroethylene.
It is further preferred that the space velocity of the gas in the reactor in steps (1) to (3) is 1000--1。
Preferably, in the step (1), the hydrolysis catalyst for catalyzing the hydrolytic dechlorination is a modified lanthanide-based catalyst; further preferably, the preparation method of the hydrolysis catalyst comprises the following steps: the lanthanide series metal oxide or the mixture of the oxide and the auxiliary agent is dipped in excessive phosphoric acid solution, is washed to be neutral after being adsorbed and saturated, is dried and is calcined for 3 to 10 hours at the temperature of 300 ℃ and 500 ℃ to obtain the catalyst.
The lanthanide-based catalyst is a cerium-based catalyst; the auxiliary agent is zirconium oxide.
In the step (2), the dechlorinating agent has a good HCl absorption effect. Preferably, in the step (2), the dechlorinating agent is at least one of alkali, alkali metal and alkaline earth metal oxides; most preferably, the dechlorination agent is CaO.
Preferably, in the step (3), the dechlorinated volatile organic compounds are subjected to catalytic deep oxidation reaction at the temperature of 200-300 ℃.
In the step (3), oxygen is required to be introduced during the catalytic deep oxidation reaction of the dechlorinated volatile organic compounds, so that the oxygen content is 5-20%.
Preferably, the oxidation catalyst takes a high specific surface material or a high-performance rare earth oxygen storage material as a carrier, and takes at least one of Pt, Pd, Mn and Co as a main active component.
The oxidation catalyst may be selected from commercially available oxidation catalysts, such as commercially available 1% Pt-TiO2Catalyst or Ce0.1Mn0.9O2A catalyst.
The removal rate of the chlorine-containing volatile organic compounds by the treatment process can reach more than 95%. Detection shows that the dechlorination effect of the hydrolysis section is good, and dioxin is not detected in the tail gas after deep oxidation of the oxidation section.
The invention also provides a device for degrading the chlorine-containing volatile organic compounds in a hydrolysis-oxidation two-stage mode, which comprises a catalytic hydrolysis reaction furnace, an HCl removing bin and a catalytic deep oxidation reaction furnace which are sequentially communicated;
a hydrolysis catalyst is arranged in the catalytic hydrolysis reaction furnace, and the chlorine-containing volatile organic compounds generate HCl and dechlorinated volatile organic compounds under the action of the hydrolysis catalyst at the temperature of 100-250 ℃;
a dechlorinating agent for absorbing HCl is arranged in the HCl removing bin;
the catalytic deep oxidation reaction furnace is internally provided with an oxidation catalyst, and dechlorinated volatile organic compounds are oxidized and degraded under the action of the oxidation catalyst at the temperature of 200-500 ℃.
Preferably, the hydrolysis catalyst is a modified lanthanide-based catalyst; the dechlorinating agent is at least one of alkali, alkali metal and alkaline earth metal oxide; the oxidation catalyst takes a high-performance rare earth oxygen storage material as a carrier and takes at least one of Pt, Pd, Mn and Co as a main active component.
Preferably, the furnace bodies of the catalytic hydrolysis reaction furnace and the catalytic deep oxidation reaction furnace are provided with heat insulation layers.
Preferably, the catalytic hydrolysis reaction furnace, the HCl removal bin and the catalytic deep oxidation reaction furnace are communicated through a hot air pipeline; and the inner wall and the outer surface of the hot air pipeline are both provided with heat insulation material layers.
Preferably, the catalytic hydrolysis reaction furnace and the catalytic deep oxidation reaction furnace are internally provided with electric auxiliary heaters.
Preferably, the hydrolysis-oxidation two-stage type device for degrading the chlorine-containing volatile organic compounds further comprises a control system and a temperature sensor which are electrically connected with each other; the temperature sensor is used for collecting the temperatures in the catalytic hydrolysis reaction furnace and the catalytic deep oxidation reaction furnace and transmitting the temperatures to the control system; when the temperatures in the catalytic hydrolysis reaction furnace and the catalytic deep oxidation reaction furnace are greater than a set threshold value, the control system drives the electric auxiliary heater to be closed, and heating is stopped; when the temperatures in the catalytic hydrolysis reaction furnace and the catalytic deep oxidation reaction furnace are lower than a set threshold value, the control system drives the electric auxiliary heater to be started for heating.
Preferably, the hydrolysis-oxidation two-stage type device for degrading the chlorine-containing volatile organic compounds further comprises a tail gas detection system for detecting components of the discharged tail gas.
The process and the device effectively combine two-stage catalysis of hydrolysis and oxidation, dechlorination is mainly carried out on the chlorine-containing volatile organic compounds at the front stage, and the intermediate product HCl is removed through the HCl removing bin, so that the chlorine content in a reaction system is reduced, and the inactivation of a rear-stage oxidation catalyst is prevented; the later stage mainly carries out further degradation on the dechlorinated volatile organic compounds to further decompose the dechlorinated organic compounds into CO2、H2And small molecular inorganic substances such as O and the like. The whole process has high removal efficiency and stable treatment effect on industrial chlorine-containing VOCs, ensures the discharge of low byproducts, saves cost due to low catalytic temperature, and is suitable for treating industrial chlorine-containing VOCs with large air volume and low concentration.
Compared with the prior art, the invention has the beneficial effects that:
(1) the treatment process of the industrial chlorine-containing VOCs is divided into two steps of hydrolysis and oxidation, the chlorine element of the chlorine-containing VOCs is removed in the form of HCl by the first step of hydrolysis, and the dechlorinated VOCs is further oxidized, so that the defect of poor stability of the catalyst during treatment of the industrial chlorine-containing VOCs is overcome;
(2) in the hydrolysis system of the invention, the required temperature is lower and the energy consumption is less. Because VOCs treated in the catalytic deep oxidation reaction furnace are mainly dechlorinated, the required treatment temperature is lower than that of the VOCs containing chlorine, and the energy consumption is reduced;
(3) the whole reaction system avoids the generation temperature interval of a high-toxicity byproduct dioxin, chlorine elements in the system are mainly removed from the system in the form of HCl, the chlorine elements rarely enter a rear-stage catalytic deep oxidation reaction furnace, the generation of polychlorinated high-toxicity byproducts such as dioxin and the like is reduced, and the environment-friendly effect is achieved.
Drawings
Fig. 1 is a schematic structural diagram of a hydrolysis-oxidation two-stage device for degrading chlorine-containing volatile organic compounds.
Detailed Description
The invention will be described in further detail below with reference to the drawings and examples, which are intended to facilitate the understanding of the invention without limiting it in any way.
As shown in fig. 1, the hydrolysis-oxidation two-stage device for degrading chlorine-containing volatile organic compounds of the present invention includes a catalytic hydrolysis reaction furnace 1, an HCl removal bin 2, and a catalytic deep oxidation reaction furnace 3, which are sequentially communicated. The catalytic hydrolysis reaction furnace 1, the HCl removing bin 2 and the catalytic deep oxidation reaction furnace 3 are communicated through a hot air pipeline 5, and a tail gas detection system 6 is further arranged at an air outlet of the catalytic deep oxidation reaction furnace 3. An inner heat insulation material layer is arranged on the inner wall of the hot air pipeline 5, and an outer heat insulation material layer is arranged on the outer surface of the hot air pipeline.
The catalytic hydrolysis reaction furnace 1 and the catalytic deep oxidation reaction furnace 3 are also provided with an electric auxiliary heater and control system 4, and the electric auxiliary heater and control system 4 is provided with a temperature sensor 4-1. The temperature sensor 4-1 is positioned in the catalytic hydrolysis reaction furnace 1 and the catalytic deep oxidation reaction furnace 3 and used for collecting the temperature in the furnaces, the information output end of the temperature sensor 4-1 is connected with the control system, and the output end of the control system is connected with the on-off switch of the electric auxiliary heater; when the temperature value transmitted to the control system by the temperature sensor 4-1 exceeds the maximum threshold value of the set temperature range, the control system drives the electric auxiliary heater to be closed and stops heating; when the temperature value transmitted to the control system by the temperature sensor 4-1 is lower than the minimum threshold value of the set temperature range, the control system drives the electric auxiliary heater to be started for auxiliary heating.
A heating hearth of the catalytic hydrolysis reaction furnace 1 is surrounded by a shell 1-1, and a heat insulation material 1-2 is also arranged in the shell 1-1. A hydrolysis catalyst packing layer 1-3 is arranged in the heating hearth. The hydrolysis catalyst is a lanthanide-based catalyst modified by phosphoric acid, and is prepared into a honeycomb or granular catalyst through molding.
An HCl removing filler layer 2-1 is arranged in the HCl removing bin 2. The filling material in the HCl removing bin 2 is CaO or other alkali metal/alkaline earth metal oxides, and has good absorption effect on HCl.
The structure of the catalytic deep oxidation reaction furnace 3 is similar to that of the catalytic hydrolysis reaction furnace 1, a heating hearth of the catalytic deep oxidation reaction furnace is surrounded by a shell, and a heat insulation material is further arranged in the shell. An oxidation catalyst filling layer is arranged in the heating hearth. The oxidation catalyst is prepared by taking a high-performance rare earth oxygen storage material as a carrier and taking precious metals Pt and Pd or transition metals Mn and Co as main active components by a method of uniformly distributing with high dispersion rate, wherein the mass ratio of the active components to the carrier is (0.01-0.1) to 1.
The hydrolysis-oxidation two-stage method for efficiently and stably degrading industrial chlorine-containing volatile organic compounds comprises the following steps: the industrial flue gas firstly passes through a catalytic hydrolysis reaction furnace, water vapor (the optimal range is 0.1% -25.0%) contained in the flue gas is utilized to carry out hydrolysis dechlorination reaction, HCl and dechlorinated VOCs are generated and enter an HCl removing bin, the HCl is removed by a dechlorinating agent in the HCl removing bin, the dechlorinated VOCs enter a catalytic deep oxidation reaction furnace, and the dechlorinated VOCs are further deeply oxidized in the catalytic deep oxidation reaction furnace.
The temperature in the catalytic hydrolysis reaction furnace is set to 100-250 ℃, and the temperature in the catalytic deep oxidation reaction furnace is set to 200-500 ℃.
The device and the method are suitable for degrading organic matters such as chlorobenzene, dichloromethane, methane chloride, dichloroethylene and the like, the removal rate of the organic matters can reach more than 95 percent, and toxic byproducts such as dioxin and the like are not detected in tail gas.
Example 1
(1) Catalyst:
the hydrolysis catalyst is prepared by adopting an impregnation method, 1mol/L phosphoric acid solution and cerium oxide are used as raw materials, excessive phosphoric acid is impregnated, then the raw materials are dried, and the mixture is calcined in a muffle furnace at 400 ℃ for 3 hours to obtain the hydrolysis catalyst.
The oxidation catalyst adopts 1 percent of Pt-TiO which is a commercial catalyst2(Jiangsu Bosina environmental technologies, Inc., custom).
And CaO is adopted as an adsorbent in the HCl removal bin.
(2) Application processing:
the method comprises the following steps of sequentially passing chlorine-containing volatile organic compound gas through a catalytic hydrolysis reaction furnace, an HCl removal bin and a catalytic deep oxidation reaction furnace, wherein the initial gas concentration is as follows: [ Chlorobenzene)]500ppm, nitrogen as carrier gas, 10% oxygen, 0.5% water content, and when the space velocity of the gas containing chlorine volatile organic compound is 10000h-1When the temperature of the hydrolysis section is 200 ℃ and the temperature of the oxidation section is 250 ℃, the removal rate of chlorobenzene can reach 98 percent, and byproducts such as polychlorinated benzene, dioxin and the like are not detected in tail gas.
Comparative example 1
(1) Catalyst:
the oxidation catalyst adopts 1% of Pt-TiO sold in the market2A catalyst.
And CaO is adopted as an adsorbent in the HCl removal bin.
(2) Application processing:
the chlorine-containing volatile organic compound gas passes through a catalytic deep oxidation reaction furnace, and the initial gas concentration is as follows: [ Chlorobenzene)]500ppm, nitrogen as carrier gas, 10% oxygen, 0.5% water content, and when the space velocity of the gas containing chlorine volatile organic compound is 10000h-1When the temperature of the oxidation section is 250 ℃, the removal rate of chlorobenzene is 83 percent, and 4.11 mu g/m is detected in tail gas3P-dichlorobenzene and 12 traces of dioxin.
Example 2
(1) Catalyst:
the hydrolysis catalyst is prepared by adopting an impregnation method, 1mol/L phosphoric acid solution and zirconia-ceria are used as raw materials, excessive phosphoric acid is impregnated, then the raw materials are dried, and the mixture is calcined in a muffle furnace at 400 ℃ for 3 hours to obtain the hydrolysis catalyst.
The oxidation catalyst adopts a commercially available catalyst Ce0.1Mn0.9O2(Jiangsu Bos)Nano environment technology limited, custom).
And CaO is adopted as an adsorbent in the HCl removal bin.
(2) Application processing:
the method comprises the following steps of sequentially passing chlorine-containing volatile organic compound gas through a catalytic hydrolysis reaction furnace, an HCl removal bin and a catalytic deep oxidation reaction furnace, wherein the initial gas concentration is as follows: [ methylene chloride ]]1000ppm, nitrogen as carrier gas, 10% oxygen, 1.0% water content, and 15000h when the space velocity of the gas containing chlorine volatile organic compounds is 15000h-1When the temperature of the hydrolysis section is 200 ℃ and the temperature of the oxidation section is 280 ℃, the removal rate of dichloromethane can reach 96%, and polychlorinated byproducts such as trichloromethane, tetrachloromethane, dioxin and the like are not detected in tail gas.
Example 3
(1) Catalyst:
the hydrolysis catalyst is prepared by adopting an impregnation method, 1mol/L phosphoric acid solution and cerium oxide are used as raw materials, excessive phosphoric acid is impregnated, then the raw materials are dried, and the mixture is calcined in a muffle furnace at 400 ℃ for 3 hours to obtain the hydrolysis catalyst.
The oxidation catalyst adopts 1 percent of Pt-TiO which is a commercial catalyst2(Jiangsu Bosina environmental technologies, Inc., custom).
And CaO is adopted as an adsorbent in the HCl removal bin.
(2) Application processing:
the method comprises the following steps of sequentially passing chlorine-containing volatile organic compound gas through a catalytic hydrolysis reaction furnace, an HCl removal bin and a catalytic deep oxidation reaction furnace, wherein the initial gas concentration is as follows: [ methylene chloride ]]1000ppm, nitrogen as carrier gas, 10% oxygen, 5% water content, and 15000h when the space velocity of the gas containing chlorine volatile organic compounds is 15000h-1When the temperature of the hydrolysis section is 200 ℃ and the temperature of the oxidation section is 250 ℃, the removal rate of dichloromethane can reach 98%, and polychlorinated byproducts such as trichloromethane, tetrachloromethane, dioxin and the like are not detected in tail gas.
Example 4
(1) Catalyst:
the hydrolysis catalyst is prepared by adopting an impregnation method, 1mol/L phosphoric acid solution and cerium oxide are used as raw materials, excessive phosphoric acid is impregnated, then the raw materials are dried, and the mixture is calcined in a muffle furnace at 400 ℃ for 3 hours to obtain the hydrolysis catalyst.
The oxidation catalyst adopts 1 percent of Pt-TiO which is a commercial catalyst2(Jiangsu Bosina environmental technologies, Inc., custom).
And CaO is adopted as an adsorbent in the HCl removal bin.
(2) Application processing:
the method comprises the following steps of sequentially passing chlorine-containing volatile organic compound gas through a catalytic hydrolysis reaction furnace, an HCl removal bin and a catalytic deep oxidation reaction furnace, wherein the initial gas concentration is as follows: [ methylene chloride ]]2000ppm, nitrogen as carrier gas, 10% oxygen, 2.0% water content, and when the space velocity of the gas containing chlorine volatile organic compound is 10000h-1When the temperature of the hydrolysis section is 200 ℃ and the temperature of the oxidation section is 300 ℃, the removal rate of dichloromethane can reach 95%, and polychlorinated byproducts such as trichloromethane, tetrachloromethane, dioxin and the like are not detected in tail gas.
Example 5
(1) Catalyst:
the hydrolysis catalyst is prepared by adopting an impregnation method, 1mol/L phosphoric acid solution and cerium oxide are used as raw materials, excessive phosphoric acid is impregnated, then the raw materials are dried, and the mixture is calcined in a muffle furnace at 400 ℃ for 3 hours to obtain the hydrolysis catalyst.
The oxidation catalyst adopts 1 percent of Pt-TiO which is a commercial catalyst2(Jiangsu Bosina environmental technologies, Inc., custom).
And CaO is adopted as an adsorbent in the HCl removal bin.
(2) Application processing:
the method comprises the following steps of sequentially passing chlorine-containing volatile organic compound gas through a catalytic hydrolysis reaction furnace, an HCl removal bin and a catalytic deep oxidation reaction furnace, wherein the initial gas concentration is as follows: [ monochloromethane ]]3000ppm, nitrogen as carrier gas, 10% oxygen, 1.5% water content, and when the space velocity of the gas containing chlorine volatile organic compound is 10000h-1When the temperature of the hydrolysis section is 180 ℃ and the temperature of the oxidation section is 250 ℃, the removal rate of the monochloromethane can reach 99 percent, and polychlorinated byproducts such as trichloromethane, tetrachloromethane, dioxin and the like are not detected in tail gas, but only 8.9 mu g/m is detected3Dichloromethane.
Comparative example 2
(1) Catalyst:
the oxidation catalyst adopts 1 percent of Pt-TiO which is a commercial catalyst2(Jiangsu Bosina environmental technologies, Inc., custom).
And CaO is adopted as an adsorbent in the HCl removal bin.
(2) Application processing:
the chlorine-containing volatile organic compound gas passes through a catalytic deep oxidation reaction furnace, and the initial gas concentration is as follows: [ monochloromethane ]]3000ppm, nitrogen as carrier gas, 10% oxygen, 1.5% water content, and when the space velocity of the gas containing chlorine volatile organic compound is 10000h-1When the temperature of the oxidation section is 250 ℃, the removal rate of the chloromethane can reach 92 percent, and trichloromethane, tetrachloromethane and 65.67 mu g/m are detected in the tail gas3Dichloromethane.
The above-mentioned embodiments are intended to illustrate the technical solutions and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modifications, additions, equivalents, etc. made within the scope of the principles of the present invention should be included in the scope of the present invention.
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| PCT/CN2020/084648 WO2021128658A1 (en) | 2019-12-25 | 2020-04-14 | Hydrolysis-oxidation two-stage process and device for degrading chlorinated volatile organic compounds |
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| CN113209793A (en) * | 2021-05-13 | 2021-08-06 | 湖南农业大学 | Purification system and purification process for chlorine-containing volatile organic compounds |
| CN113893581A (en) * | 2021-10-28 | 2022-01-07 | 南京沿江资源生态科学研究院有限公司 | Organic solvent innocent treatment system |
| CN116371436A (en) * | 2023-02-08 | 2023-07-04 | 美瑞科技(河南)有限公司 | Catalyst capable of efficiently decomposing phosgene and resisting chlorobenzene poisoning, and preparation and application thereof |
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| CN108126685A (en) * | 2017-11-14 | 2018-06-08 | 浙江大学 | Two-part catalyst of catalytic degradation VOCs containing chlorine and its preparation method and application |
| CN109603869A (en) * | 2019-01-23 | 2019-04-12 | 浙江大学 | Phosphoric acid modified cerium oxide catalyst and preparation method and application thereof |
| CN109939501A (en) * | 2019-04-03 | 2019-06-28 | 西安飞机工业（集团）有限责任公司 | A kind of milling glue spraying waste gas processing method containing tetrachloro-ethylene |
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| WO2006135911A1 (en) * | 2005-06-13 | 2006-12-21 | Applied Materials, Inc. | Methods and apparatus for abatement of waste gas |
| CN101559319B (en) * | 2009-05-13 | 2011-05-18 | 北京化工大学 | Vapor phase hydrolysis method for carbon tetrachloride and chloroform |
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| CN108126685A (en) * | 2017-11-14 | 2018-06-08 | 浙江大学 | Two-part catalyst of catalytic degradation VOCs containing chlorine and its preparation method and application |
| CN109603869A (en) * | 2019-01-23 | 2019-04-12 | 浙江大学 | Phosphoric acid modified cerium oxide catalyst and preparation method and application thereof |
| CN109939501A (en) * | 2019-04-03 | 2019-06-28 | 西安飞机工业（集团）有限责任公司 | A kind of milling glue spraying waste gas processing method containing tetrachloro-ethylene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113209793A (en) * | 2021-05-13 | 2021-08-06 | 湖南农业大学 | Purification system and purification process for chlorine-containing volatile organic compounds |
| CN113893581A (en) * | 2021-10-28 | 2022-01-07 | 南京沿江资源生态科学研究院有限公司 | Organic solvent innocent treatment system |
| CN113893581B (en) * | 2021-10-28 | 2022-09-16 | 南京沿江资源生态科学研究院有限公司 | Organic solvent innocent treatment system |
| CN116371436A (en) * | 2023-02-08 | 2023-07-04 | 美瑞科技(河南)有限公司 | Catalyst capable of efficiently decomposing phosgene and resisting chlorobenzene poisoning, and preparation and application thereof |
| CN116371436B (en) * | 2023-02-08 | 2024-08-09 | 美瑞科技(河南)有限公司 | Catalyst capable of efficiently decomposing phosgene and resisting chlorobenzene poisoning, and preparation and application thereof |
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